RU2414474C2 - Method of producing dialkyltin dialkoxides - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a dialkyltin compound, involving: a reaction for redistribution of alkyl groups and/or a reaction for dealkylation of a composition of a deactivated form of a catalyst based on dialkyltin, which is formed during synthesis of an ester derivative using a dialkyltin-based catalyst. The dialkyltin-based catalyst is a compound of at least one type selected from a group comprising a dialkyltin compound of formula (1) and tetraalkyldistanoxane of formula (2):

(1) (where each of R¹ and R² independently denote a straight or branched alkyl group containing 1-12 carbon atoms, each of X¹ and X² independently denotes a substitute of at least one type selected from a group comprising an alkoxy group, an acyloxy group and a halogen atom, a and b independently denote an integer from 0 to 2 and a+b=2, and c and d independently denote an integer from 0 to 2 and c+d=2;

(2), (where each of R³, R⁴, R⁵ and R⁶ independently denote a straight or branched alkyl group containing 1-12 carbon atoms, each of X³ and X⁴ independently denote a substitute of at least one type selected from a group comprising an alkoxy group, an acyloxy group and a halogen atom, and e, f, g and h independently denote an integer from 0 to 2, e+f=2 and g+h=2). The ester derivative is a compound of at least one type selected from a group comprising a carboxylic ester, a carbamate and isocyanate.

EFFECT: method enables production of versions of dialkyltin alkoxide compounds in active form in form of dialkyltin alkoxide compounds.

37 cl, 34 ex, 7 dwg

Description

Technical field

The present invention relates to a method for producing dialkyltin alkoxide compounds as a catalyst for use in the production of esters, carbonic esters and to a method for producing carbonic esters and esters using dialkyltin dialkoxides.

State of the art

Dialkyltin dialkoxides are extremely useful as catalysts, ester synthesis, carbonic acid ester synthesis, ester transesterification reaction and crosslinking of silicone polymers or urethanes. In particular, while carbonic esters are used as additives to gasoline to increase octane and to diesel to reduce particulate matter in exhaust gases, these useful compounds are also used as alkylating agents, carbonylating agents or solvents, etc. P. in the synthesis of polycarbonates, urethanes, pharmaceuticals, agricultural chemicals and other organic compounds, or as electrolytes for lithium batteries, raw materials for lubricating oils and raw materials for deoxygenating agents to protect heating pipes from corrosion; all this draws attention to dialkyltin dialkoxides, in particular, as synthesis catalysts. For example, WO 2003/055840 discloses a method for producing carbonic acid esters comprising reacting an organometal compound containing a dialkyltin dialkoxide with carbon dioxide, followed by thermal decomposition of the resulting addition product.

A commonly used known method for the preparation of dialkyltin dialkoxides involves reacting dialkyltin oxides with alcohols and removing the resulting low boiling component that contains water from the reaction liquid (see, for example, US Pat. No. 5,545,600, published international patent application WO 2005/111049, published Japanese patent application. No. 2005-298433, Journal of Chemical Society, 23 (1971), 3972, and Journal of the Chemical Society of Japan - Industrial Chemistry, 72, 7 (1969), 1543-1549). It is considered proven that the processes for the production of dialkyltin dialkoxides by the dehydration reaction of dialkyltin oxides and alcohols are equilibrium reactions accompanying dehydration, as shown by the following formula (1):

(where R and R 'are alkyl groups).

The above equilibrium in the vast majority of cases shifts toward interacting substances and it is assumed that subsequent dehydration reactions take place through tetraalkyldistannoxane, as shown in the following formulas (2) and (3):

(where R and R 'are alkyl groups);

(where R and R 'are alkyl groups).

Although dialkyltin dialkoxides are obtained by removing water from each dehydration reaction from the system, this reaction has several disadvantages from an energy point of view, therefore, in order to obtain dialkyltin dialkoxides in high yield, the reaction must be carried out at a high temperature (for example, 180 ° C) for a long period of time.

On the other hand, when dialkyltin alkoxide compounds (e.g. dialkyltin dialkoxides) are heated, for example, at approximately 180 ° C, variants are known to form, such as trialkyltin alkoxides containing three alkyl groups on one tin atom (see, for example, Journal of the Chemical Society of Japan - Industrial Chemistry, 72, 7 (1969), 1543-1549). Although the type of reaction by which trialkyltin alkoxides are formed is not entirely clear, it is assumed that there is a transfer of alkyl groups, for example, and the said trialkyltin alkoxides are formed as a result of the disproportionation reaction, as shown in the following formula (4), in the case where the dialkyltin alkoxide represents is tetraalkyl dialkoxydistannoxane, or the mentioned variants are formed as a result of a disproportionation reaction, as shown in the following formula (5) in the case when the said dialkyltin alkoxide is It was lent a dialkyltin dialkoxide:

(where R and R 'are alkyl groups).

According to the above formula (4), it is assumed that the trialkyltin alkoxide and the monoalkyl compound containing one alkyl group on one tin atom are the products of the conversion of tetraalkyl dialkoxydistannoxane. In fact, since the inventors of the present invention confirm that trialkyltin alkoxides and high boiling point tin components are variants of the conversion of tetraalkyl dialkoxydistannoxanes, it is assumed that the high boiling point tin component corresponds to monoalkyl compounds.

However, the structure of the high boiling tin component, which is believed to correspond to a monoalkyl compound, has not yet been identified. Similarly, although it is assumed that the variants that are formed from dialkyltin dialkoxides are trialkyltin and monoalkyltin alkoxides, the structure of these variants has not been established.

The formation of such variants is also confirmed, for example, in the method for producing dialkyltin dialkoxides, as described above, and in methods for producing carbonic acid esters by reacting an organometallic compound containing dialkyltin dialkoxides with carbon dioxide, followed by thermal decomposition of the resulting addition product.

As is known, the ability of trialkyltin alkoxides to form carbonic acid esters upon their production by the interaction of tin compounds with carbon dioxide is extremely low (see, for example, Journal of American Chemical Society, 121 (1999), 3793). In addition, the high boiling components of tin, which are included in these variants with an unidentifiable structure, also have an extremely low ability to form carbonic acid esters when they are obtained by the interaction of tin compounds with carbon dioxide (see, for example, published Japanese patent application No. 2005-298433).

Thus, since the mentioned variants do not show activity in the reactions for producing carbonic esters by the interaction of tin compounds with carbon dioxide, if such variants are formed during the preparation of these carbonic acid esters, variants of compounds of dialkyltin alkoxides with low activity accumulate when reusing alkyltin alkoxide compounds , which leads to a decrease in the content of the active form in the form of dialkyltin dialkoxide compounds, this, in turn, causes a decrease reaction rates or reduced yield of carbonic esters. In such cases, although a method is usually used that involves adding a small amount of freshly prepared dialkyltin alkoxide compounds in order to keep the reaction rate and yield constant if inactive options remain in the system while continuing to add fresh portions of dialkyl tin alkoxide compounds, there may be a problem of accumulation in the reaction mixtures of a large number of degradation products with low activity. In addition, even if a part of the mixture of alkyltin alkoxide compounds containing variants of dialkyltin alkoxide compounds is removed from the reaction system, when fresh portions of dialkyltin alkoxide compounds are added to maintain a constant concentration of the dialkyltin alkoxide compound in the reaction system, significant problems are associated with the costs and processing of waste because, along with the deleted dialkyltin alkoxide compounds that become waste, waste disposal is also removed tsya waste active form of a dialkyl tin alkoxide compound.

Several solutions to the above problems have been proposed previously (see, for example, publication of international application WO 2004/014840 and publication of international application WO 2007/097388). More specifically, the international publication WO 2004/014840 proposes a method used in the production of carbonic acid esters using dialkyltin alkoxide compounds containing thermal denaturation products of dialkyltin alkoxide compounds to separate the components of trialkyltin compounds and dialkyltin alkoxides containing said thermal denaturation products to prevent their accumulation in the reaction system. However, since it is impossible to remove the high boiling compounds of tin of an unidentifiable structure that are contained in the dialkyltin alkoxide compound variants, it is impossible to completely prevent the accumulation of dialkyltin alkoxide compounds in this way.

In addition, the authors of the present invention described a method for the separation and recovery of products formed through dialkyltin alkoxide compounds in the form of dialkyltin dialkoxides by preliminary reaction of a dialkyltin alkoxide compound and variants of dialkyltin alkoxide compounds extracted from the reaction system with an alcohol and / or carbonic ester (see publication international application WO 2007/097388). According to this method, the problem of getting into the waste an active form in the form of a dialkyltin alkoxide compound together with the variants is solved, in this method only variants of the dialkyltin alkoxide compounds can be selectively discarded. However, since the dialkyltin alkoxide compound variants cannot be reused, the cost and waste management problems remain unresolved.

At the present level of technology there is a need to develop a technology that will allow the dialkyl tin alkoxide compound variants to be regenerated into the active form as dialkyl tin alkoxide compounds and reused to produce carbonic acid esters.

Proportionality reactions that are inverse to the aforementioned disproportionation reactions are used as a method for preparing dialkyltin compounds from mixtures of two types of compounds having different numbers of alkyl groups on the tin atom. For example, in the case of halogen-containing tin compounds, dialkyl chloro tin is formed as a result of the proportionality reaction of trialkyl chloro tin and alkyl trichloro tin, as shown in formula (6) below (see, for example, Japanese Patent Application Laid-Open No. H4-81999):

As described previously, disproportionation reactions that convert dialkyl tin alkoxide compounds to trialkyl tin alkoxides and monoalkyl tin compounds are advantageous in the case of tin alkoxide compounds, and the reverse proportioning reaction is difficult. At the same time, in the case of halogen-containing tin compounds, proportionality reactions are advantageous; they make it possible to obtain dialkyl dichlorotin from trialkyl chloro tin and alkyl trichloro tin.

Several methods for preparing alkyl trichlorotin have previously been proposed (see, for example, Japanese Patent Application Laid-Open No. H4-81999 and Japanese Published Patent Application No. S44-8489). More specifically, Japanese Patent Application Laid-Open No. H4-81999 discloses a process for preparing an alkyl trichlorotin by proportional reaction, as described above, from a mixture of tetraalkyltin and tetrachlorotin in a specific ratio. Japanese Patent Application Laid-Open No. S44-8489 discloses a method for producing an alkyl trichlorotin by reacting an alkyl stanoate with hydrogen chloride. However, the technology for the preparation of alkyl trichlorotin compounds, which uses dialkyl tin alkoxide compounds as raw materials, is still not known.

On the other hand, reactions in which trialkyltin acetoxides and alkyltin oxides of oxides are formed by the reaction of dialkyltin alkoxide compounds with acetic acid are described as reaction variants of dialkyltin alkoxide compounds (see, for example, Journal of American Chemical Society, 121 (1999), 3793) . However, a method for the preparation of dialkyltin alkoxide compounds by the reaction of proportioning trialkyltin acetoxides and alkyltin acetoxide oxides compounds is still not known.

Based on the foregoing, since technologies have not yet been developed for the regeneration of variants of dialkyltin alkoxide compounds into active forms in the form of dialkyltin alkoxide compounds, the problems of costs and waste processing in the production of carbonic acid esters remain unresolved.

Description of the invention

An object of the present invention is to provide a process for the preparation of dialkyltin compounds which will allow the variants of dialkyltin alkoxide compounds to be regenerated into dialkyltin alkoxide compounds, as well as to provide a method for using said dialkyltin compounds in the production of carbonic esters.

As a result of large-scale studies of the above problems, the authors of the present invention found that these problems can be solved by obtaining a dialkyltin compound by reacting an acid and / or acid anhydride with a composition containing a variant of a dialkyltin alkoxide compound, followed by heating the dialkyltin compound, and regenerating said dialkyltin compound into an alkoxide dialkyltin and its use in the production of carbonic acid esters, which leads to the completion of the present iso grip. In other words, the present invention is an invention described below.

The present invention relates to:

[1] a method for producing a dialkyltin compound, comprising

a redistribution reaction of alkyl groups and / or a dealkylation reaction of a composition of a deactivated form of a dialkyl tin catalyst, which is formed upon the production of an ester derivative using a dialkyl tin catalyst,

[2] the method according to [1], wherein the dialkyl tin catalyst is a compound of at least one type selected from the group consisting of a dialkyl tin compound represented by formula (1) and tetraalkyl distannoxane represented by formula (2):

(where each of R ¹ and R ² independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

each of X ¹ and X ² independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,

a and b independently represent an integer from 0 to 2 and a + b = 2, and

c and d independently represent an integer from 0 to 2 and c + d = 2;

(where each of R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

each of X ³ and X ⁴ independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom, and

e, f, g and h independently represent an integer from 0 to 2, e + f = 2 and g + h = 2),

[3] the method according to paragraph [2], where in formulas (1) and (2) the number of carbon atoms constituting X ¹ , X ² , X ³ and X ⁴ is a number selected from integers from 0 to 12,

[4] the method according to any one of [1] to [3], wherein the ester derivative is a compound of at least one type selected from the group consisting of a carboxylic acid ester, carbamic acid ester and isocyanate,

[5] the method according to paragraph [4], wherein the carboxylic acid ester is a carbonic ester,

[6] the method according to [5], wherein the composition of the deactivated form of the dialkyl tin catalyst is a composition containing the deactivated form of the dialkyl tin catalyst formed in the step of producing a carbonic ester from carbon dioxide and a dialkyl tin catalyst,

[7] the method according to any one of paragraphs [1] to [6], wherein the deactivated form of the dialkyl tin catalyst is a heat deactivated form of the dialkyl tin catalyst,

[8] the method according to any one of [1] to [7], wherein the deactivated form of the dialkyl tin catalyst is a deactivated form of the dialkyl tin catalyst formed from a dialkyl tin catalyst in which the number of alkyl groups bound to one atom tin differs from the number of alkyl groups bonded to one tin atom in a dialkyl tin catalyst,

[9] the method according to any one of paragraphs [1] to [8], wherein at least one type of deactivated form of the dialkyltin catalyst is a trialkyltin compound,

[10] the method according to any one of paragraphs [1] to [9], wherein the deactivated form of the dialkyl tin catalyst is a trialkyl tin compound and an organotin compound having a tin atom exhibiting a chemical shift of from -220 to -610 ppm. relative to tetramethyltin, when analyzing ¹¹⁹ Sn-NMR in a solution of deuterated chloroform,

[11] the method according to paragraph [10], further comprising separating the composition of the deactivated form of the catalyst based on dialkyltin into a composition containing a trialkyltin compound and a composition containing a tin atom exhibiting a chemical shift from -220 to -610 ppm relative to tetramethyltin, when analyzing ¹¹⁹ Sn-NMR in a solution of deuterated chloroform,

[12] the method according to [11], wherein the separation step is carried out in at least one method selected from the group consisting of distillation separation, extraction separation and membrane separation,

[13] the method according to any one of paragraphs [1] to [12], where in the case where pKa of an acid conjugated to at least one substituent from groups associated with tin atoms of a deactivated form of a dialkyltin catalyst and not being alkyl groups formed from a dialkyl tin catalyst is 0-6.8,

an alkyl group redistribution reaction is an alkyl group redistribution reaction in which an organotin compound containing a Sn-Y bond (where Y is Y for which pKa is conjugated with Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0- 6.8), subjected to heat treatment,

[14] the method according to any one of paragraphs [1] to [12], where in the case where pKa of an acid conjugated to at least one substituent from groups associated with tin atoms of a deactivated form of a dialkyltin catalyst and which are not alkyl groups formed from a dialkyl tin catalyst is 6.8-25,

the redistribution of alkyl groups includes the steps of:

(A) obtaining an organotin compound containing a Sn — Y bond by replacing all or part of the ligands of the deactivated form (except for the alkyl group formed from the dialkyltin catalyst and bound to the tin) with the substituent Y; and

(B) heat treating the organic compound containing the Sn — Y bond and obtained in step (A) (where Y is Y, for which pKa is conjugated with Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0- 6.8)

[15] the method according to [14], wherein step (A) comprises preparing an organotin compound containing a Sn-Y bond, in which three alkyl groups and one Y group formed from an acid and / or acid anhydride are linked to one atom tin and an organotin compound containing a Sn-Y bond, in which one alkyl group and several Y groups are formed from an acid and / or acid anhydride, the number of Y groups being selected from integers from 1 to 3, are bonded to one tin atom by reaction compositions of the deactivated form of catalysis ora based dialkyltin acid represented by the following formula (3) and / or acid anhydride represented by the following formula (4):

(where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8);

(where Y represents Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8, and O represents an oxygen atom),

[16] the method according to [15], wherein step (A) is carried out by removing the water generated during the use of the acid in step (A) by at least one method selected from the group consisting of removing water with a dehydrating agent, distillation separation and membrane separation,

[17] the method according to any one of paragraphs [1] to [12], wherein the dealkylation reaction involves the formation of a Sn-Y bond by elimination of the alkyl group from the deactivated form of the dialkyl tin catalyst (where Y is Y for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8),

[18] the method according to any one of [9] to [12], wherein a single Sn-Y bond is formed in the dealkylation reaction by eliminating one alkyl group from the trialkyltin compound contained in the composition of the deactivated form of the dialkyl tin catalyst, and a dialkyl tin compound is obtained, containing Sn-Y bond (where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8),

[19] the method according to [18], wherein the step of forming a Sn-Y bond comprises reacting a trialkyltin compound contained in the composition of the deactivated form of the dialkyltin catalyst with an acid represented by the formula (5) and / or an acid anhydride represented by the formula (6 ):

(where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8);

(where Y represents Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8, and O represents an oxygen atom),

[20] the method according to [15] or [19], wherein the acid and / or acid anhydride are liquid or gas at 60 ° C,

[21] the method according to [20], wherein the acid is hydrohalic acid,

[22] the method according to paragraph [20], wherein the acid is a hydrogen halide,

[23] the method according to paragraph [20], wherein the acid is an organic acid,

[24] the method according to paragraph [23], wherein the acid is a carboxylic acid,

[25] the method according to [20], wherein the standard boiling point of the acid anhydride is 300 ° C. or lower,

[26] the method according to paragraph [25], wherein the acid anhydride is acetic anhydride or maleic anhydride,

[27] the method according to any one of paragraphs [1] to [26], wherein the dialkyl tin compound contains two alkyl groups formed from a dialkyl tin catalyst and bonded to one tin atom, and at the same time contains at least one Sn — Y bond ( where Y represents Y, for which pKa conjugated with Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8),

[28] the method according to [27], wherein the dialkyltin compound is a compound of at least one type selected from the group consisting of a dialkyltin compound represented by formula (7) and a tetraalkyldistannoxane compound represented by formula (8):

(where R ⁷ and R ⁸ represent a group formed from a dialkyltin catalyst, and independently represent a linear or branched alkyl group containing 1-12 carbon atoms,

Y represents a group formed from a dialkyltin catalyst, or a group formed from acid (HY) and / or acid anhydride (YOY), pKa of the acid conjugated to Y, in the form of HY, where the hydrogen atom is attached to Y, is 0 -6.8, and

i and j independently represent an integer from 0 to 2 and i + j = 2);

(where R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent a group formed from a dialkyltin catalyst, and independently represent a linear or branched alkyl group containing 1-12 carbon atoms,

Y represents a group formed from a dialkyltin catalyst, or a group formed from acid (HY) and / or acid anhydride (YOY), pKa of the acid conjugated to Y, in the form of HY, where the hydrogen atom is attached to Y, is 0 -6.8, and

k, l, m and n are integers from 0 to 2, k + l = 2 and m + n = 2, respectively),

[29] the method according to any one of paragraphs [14] to [26], further comprising, after step (B), step (I) of substitution of the substituent Y of the dialkyltin compound containing the Sn-Y bond with a substituent of at least one type selected from a group consisting of an alkoxy group, an acyloxy group and a halogen atom,

[30] the method according to paragraph [29], where stage (I) comprises:

stage (I-1) of obtaining a composition containing a dialkyltin oxide by hydrolysis of a dialkyltin compound containing a Sn-Y bond by adding an aqueous alkali solution; and

a step (I-2) of reacting the composition containing the dialkyltin oxide obtained in step (I-1) with a compound of at least one type selected from the group consisting of alcohol, carboxylic acid and hydrogen halide, followed by removal of the component, containing the resulting water from the reaction liquid,

[31] the method of paragraph [30], wherein the aqueous alkali solution is at least one type of aqueous alkali solution selected from the group consisting of an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of potassium carbonate and an aqueous solution of sodium carbonate .

[32] the method according to [30] or [31], wherein step (I-2) is a step in which a compound reacting with a composition containing a dialkyl tin oxide is an alcohol to obtain a dialkyl tin alkoxide compound,

[33] the method according to paragraph [6], wherein the step of producing a carbonic ester comprises:

stage (1) obtaining a reaction liquid containing carbonic ester by reacting carbon dioxide and a dialkyltin catalyst;

a step (2) of obtaining a residual liquid by separating a carbonic ester from a reaction liquid;

a step (3) of regenerating a dialkyltin-based catalyst by reacting the residual liquid with alcohol and removing formed water from the system; and

a step (4) for recycling the dialkyltin catalyst obtained in step (3), in step (1),

[34] the method according to paragraph [33], wherein the step of regenerating the dialkyl tin catalyst from the composition of the deactivated form of the dialkyl tin catalyst formed during the step of producing the carbonic ester by the reaction of redistribution of alkyl groups and / or the dealkylation reaction is carried out after step (2) and / or steps (3), and the regenerated dialkyl tin catalyst is recycled and reused as the dialkyl tin catalyst in step (4) and / or step (1),

[35] the method according to [34], wherein the dialkyltin-based catalyst regeneration step is a step in which the steps of any one of [29] to [32] are used, and wherein the substituent Y is an acyloxy group,

[36] the method according to any one of paragraphs [1] and [33] to [35], wherein the dialkyl tin catalyst is a dialkyl tin alkoxide compound,

[37] the method according to any one of paragraphs [33] to [36], wherein the dialkyltin catalyst is a dialkyltin alkoxide compound, and X ¹ , X ² , X ³ and X ^{4 of the} compound represented by formula (1) and / or the formula (2) are alkoxygroup:

(where each of R ¹ and R ² independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

each of X ¹ and X ² independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,

a and b independently represent an integer from 0 to 2 and a + b = 2, and

c and d independently represent an integer from 0 to 2 and c + d = 2;

(where each of R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

each of X ³ and X ⁴ independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,

e, f, g and h are respectively an integer from 0 to 2, e + f = 2 and g + h = 2),

[38] the method according to [37], wherein the dialkyl tin catalyst is a dialkyl tin alkoxide, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} compounds represented by formula (1) and / or formula ( 2), simultaneously represent an n-butyl group or n-octyl group,

[39] the method according to any one of paragraphs [33] to [38], wherein the alcohol is an alcohol represented by the formula (9):

(where R ¹³ represents a linear or branched alkyl group containing 4-8 carbon atoms).

According to the present invention, a useful component in the form of a dialkyltin compound can be obtained from a composition containing variants of dialkyltin alkoxide compounds, and a dialkyltin compound can be reused to produce a carbonic ester after being converted to dialkyltin alkoxide compounds, this makes the present invention extremely useful for industrial purposes.

Brief Description of the Drawings

Figure 1 presents a diagram of a method for producing carbonic acid esters, improved as a result of combining with the production method according to a variant implementation of the present invention.

2 is a diagram showing apparatuses for the continuous production of carbonic acid esters using a dialkyltin catalyst composition in the present embodiment.

Figure 3 shows the spectrum of ¹¹⁹ Sn-NMR of tri-n-octyl (3-methylbutyloxy) tin, separated in stage (23-1) of example 23 of the present invention.

4 shows a ¹¹⁹ Sn-NMR spectrum of a high boiling point component from -240 to -605 ppm, separated in step (23-1) of Example 23 of the present invention.

Figure 5 shows the ¹¹⁹ Sn-NMR spectrum of the tri-n-octylacetoxytin obtained in step (23-2) of Example 23 of the present invention.

6 shows a ¹¹⁹ Sn-NMR spectrum of a mixture containing n-octyltriacetoxytin obtained in step (23-2) of Example 23 of the present invention.

7 shows a spectrum of ¹¹⁹ Sn-NMR of a solution containing 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane obtained in stage (23-4) of example 23 of this inventions.

Description of digital designations :

101, 107: distillation column;

102: column type reaction vessel;

103, 106: thin film evaporator;

104: autoclave;

105: decarbonization tank;

111, 112, 117: reboiler;

121, 123, 126, 127: capacitor;

1, 9: feed line;

2, 4, 5, 6, 7, 8, 10, 11, 12, 13, 14: transfer line;

3, 15: return line;

16: extraction line;

17: feed line.

Preferred Embodiment

The following is a detailed explanation of preferred embodiments of the present invention (hereinafter, embodiments). Moreover, the present invention is not limited to the following implementation options, it, of course, can be implemented without going beyond the essence and scope of the invention.

First, an explanation of the compounds used in embodiments of the present invention is provided.

Dialkyltin Catalyst

As used in embodiments of the present invention, the terms “dialkyl tin compound”, “dialkyl tin catalyst” and “dialkyl tin” refer to organotin compounds in which two alkyl groups are bonded to one tin atom.

The term “dialkyltin catalyst” in embodiments of the present invention refers to an organotin compound that exhibits catalytic activity in the preparation of ester compounds and in which two alkyl groups are bonded to one tin atom.

Examples of said dialkyl tin catalyst include compounds selected from a compound of at least one type selected from the group consisting of a dialkyl tin compound represented by the following formula (18) and a tetraalkyl distannoxane compound represented by the following formula (19):

(where each of R ¹ and R ² independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

each of X ¹ and X ² independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,

a and b are respectively an integer from 0 to 2 and a + b = 2, and

c and d are respectively an integer from 0 to 2 and c + d = 2);

(where each of R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

each of X ³ and X ⁴ independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom, and

e, f, g and h are respectively an integer from 0 to 2, e + f = 2 and g + h = 2).

Examples of R ¹ and R ² in a dialkyl tin catalyst represented by formula (18) in embodiments of the present invention and R ³ , R ⁴ , R ⁵ and R ⁶ in tetraalkyldistannoxane represented by formula (19) in embodiments of the present invention include alkyl groups in the form of aliphatic hydrocarbon groups in which the number of carbon atoms included in these groups is a number selected from integers from 1 to 12, such groups as methyl, ethyl, propyl (isomers), butyl (isomers), pentyl (isomers), hexyl (isomer s), heptyl (isomers), octyl (isomers), nonyl (isomers), decyl (isomers), dodecyl (isomers) and the like. Preferred examples include linear or branched alkyl groups in which the number of carbon atoms of these groups is an integer selected from 1 to 8, and although a dialkyl tin catalyst may be used in which the alkyl groups are groups , in which the number of carbon atoms constituting these groups may not be included in the specified interval, in this case, it is possible to reduce fluidity and decrease productivity. More preferred examples of alkyl groups include n-butyl groups or n-octyl groups, taking into account the ease of preparation in industry.

X ¹ and X ^{2 of} a dialkyl tin catalyst represented by formula (18) in embodiments of the present invention, and X ³ and X ^{4 of} a tetraalkyl distannoxane compound represented by formula (19) in embodiments of the present invention are at least one type of substituent, selected from the group consisting of alkoxy groups, acyloxy groups and halogen atoms, and when said group is an alkoxy group and / or an acyloxy group, the number of carbon atoms constituting said group is preferred is specifically a number selected from integers from 0 to 12. Examples of such groups include alkoxy groups consisting of linear or branched saturated alkyl groups and oxygen atoms, such as methoxy group, ethoxy group, propoxy group (isomers), butoxy group (isomers), pentyloxy group (isomers ), hexyloxy group (isomers), heptyloxy group (isomers), octyloxy group (isomers), nonyloxy group (isomers), decyloxy group (isomers) or the like; acyloxy groups which include linear or branched saturated alkyl groups, carbonyl groups and oxygen atoms such as an acetoxy group, a propionyloxy group, a butyryloxy group, a valeryloxy group, a lauroloxy group or the like; and halogen atoms such as chlorine, bromine or the like. Preferred examples include alkoxy groups containing 4-6 carbon atoms, taking into account the use of carbonic acid esters as a catalyst.

Examples of dialkyltin catalysts represented by the formula (18) include dialkyl dialkoxy tin compounds such as dimethyldimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethyloxy dimethio ), dimethyldinonyloxytin (isomers), dimethyldidecyloxytin (isomers), dibutyl dimethoxytin (isomers), dibutyldiethoxytin (isomers), dibutyldipropoxy Lovo (isomers), dibutildibutiloksiolovo (isomers), dibutildipentiloksiolovo (isomers), dibutildigeksiloksiolovo (isomers), dibutildigeptiloksiolovo (isomers), dibutildioktiloksiolovo (isomers), dibutildinoniloksiolovo (isomers), dibutildidetsiloksiolovo (isomers), dioktildimetoksiolovo (isomers), dioktildietoksiolovo (isomers), dioctyldipropoxytin (isomers), dioctyldibutyloxy tin (isomers), dioctyldipentyloxy tin (isomers), dioctyldihexyloxy tin (isomers), dioctyldiheptyloxy tin (isomers), dioctyldioctyloxy tin (isomers) , dioctyldinonyloxytin (isomers), dioctyldindecyloxytin (isomers) or the like; compound dialkildiatsiloksiolova such as dimetildiatsetoksiolovo, dimetildipropioniloksiolovo (isomers), dimetildibutiriloksiolovo (isomers), dimetilvaleriloksiolovo (isomers), dimetildilauroiloksiolovo (isomers), dibutildiatsetoksiolovo (isomers), dibutildipropioniloksiolovo (isomers), dibutildibutiriloksiolovo (isomers), dibutildivaleriloksiolovo (isomers), dibutildilauroiloksiolovo (isomers ), dioctyldiacetoxy tin (isomers), dioctyldipropionyloxy tin (isomers), dioctyldibutyryloxy tin (isomers), dioctylvaleryloxyols (Isomers), dioktildilauroiloksiolovo (isomers) or the like; and dialkyl dihalo tin such as dimethyldichloro tin, dimethyldibromo tin, dibutyl dichloro tin (isomers), dibutyl dibromo tin (isomers), dioctyldichloro tin (isomers), dioctyldibromo tin (isomers) or the like.

More preferred are dialkyltin dialkoxide, such as dimetildimetoksiolovo, dimetildietoksiolovo, dimetildipropoksiolovo (isomers), dimetildibutoksiolovo (isomers), dimetildipentiloksiolovo (isomers), dimetildigeksiloksiolovo (isomers), dimetildigeptiloksiolovo (isomers), dimetildioktiloksiolovo (isomers), dimetildinoniloksiolovo (isomers), dimetildidetsiloksiolovo (isomers), dibutyldimethoxytin (isomers), dibutyl diethoxytin (isomers), dibutyl dipropoxytin (isomers), dibutyl dibutyloxy tin (isomers), di butildipentiloksiolovo (isomers), dibutildigeksiloksiolovo (isomers), dibutildigeptiloksiolovo (isomers), dibutildioktiloksiolovo (isomers), dibutildinoniloksiolovo (isomers), dibutildidetsiloksiolovo (isomers), dioktildimetoksiolovo (isomers), dioktildietoksiolovo (isomers), dioktildipropoksiolovo (isomers), dioktildibutiloksiolovo (isomers), dioctyldipentyloxy tin (isomers), dioctyldihexyloxy tin (isomers), dioctyldihetyloxy tin (isomers), dioctyldioctyloxy tin (isomers), dioctyldinonyloxy tin (isomers) or dioctyldide iloksiolovo (isomers); more preferred compounds dialkildialkoksiolova such as dibutildipropoksiolovo (isomers), dibutildibutiloksiolovo (isomers), dibutildipentiloksiolovo (isomers), dibutildigeksiloksiolovo (isomers), dibutildigeptiloksiolovo (isomers), dioktildipropoksiolovo (isomers), dioktildibutoksiolovo (isomers), dioktildipentiloksiolovo (isomers), dioktildigeksiloksiolovo (isomers ) or dioctyldiheptyloxytin (isomers); and dibutildibutiloksiolovo (isomers), dibutildipentiloksiolovo (isomers), dibutildigeksiloksiolovo (isomers), dibutildigeptiloksiolovo (isomers), dibutildioktiloksiolovo (isomers), dioktildibutiloksiolovo (isomers), dioktildipentiloksiolovo (isomers), dioktildigeksiloksiolovo (isomers), dioktildigeptiloksiolovo (isomers) or dioktildioktiloksiolovo (isomers) are more preferred.

Although the monomer structure of the dialkyl tin catalyst is shown by formula (18), it may have a polymer structure or an aggregate structure.

Examples of the tetraalkyl dialkoxydistannoxane represented by the formula (19) include 1,1,3,3-tetraalkyl-1,3-dialkoxydistannoxanes, such as 1,1,3,3-tetramethyl-1,3-dimethoxydistannoxane, 1,1,3, 3-tetramethyl-1,3-diethoxydistannoxane, 1,1,3,3-tetramethyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-dibutoxydistannoxane (isomers), 1, 1,3,3-tetramethyl-1,3-dipentyloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3- diheptyloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-t tramethyl-1,3-dinonyl oxidystannoxane (isomers), 1,1,3,3-tetramethyl-1,3-didecyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dimethoxydistannoxane (isomers), 1 , 1,3,3-tetrabutyl-1,3-diethoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3 -dibutoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dipentyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3, 3-tetrabutyl-1,3-diheptyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dino nyloxide distannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-didecyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dimethoxydistannoxane (isomers), 1,1,3,3 -tetraoctyl-1,3-diethoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dibutoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dipentyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1, 3-diheptyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dinonyl oxide xan (isomers), 1,1,3,3-tetraoctyl-1,3-didecyloxydistannoxane (isomers) or the like; 1,1,3,3-tetraalkyl-1,3-diacyloxydistannoxanes such as 1,1,3,3-tetramethyl-1,3-diacetoxydistannoxane, 1,1,3,3-tetramethyl-1,3-dipropionyloxydistannoxane ( isomers), 1,1,3,3-tetramethyl-1,3-dibutyryloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-divaleryloxydistannoxane (isomers), 1,1,3,3-tetramethyl -1,3-dilauroyl oxide-stannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-diacetoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dipropionyloxydistannoxane (isomers), 1, 1,3,3-tetrabutyl-1,3-dibutyryloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-divaleryloxydistannoxane (isomers), 1,1, 3,3-tetrabutyl-1,3-dilauroyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-diacetoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dipropionyloxydistannoxane ( isomers), 1,1,3,3-tetraoctyl-1,3-dibutyryloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-divaleryloxydistannoxane (isomers), 1,1,3,3-tetraoctyl -1,3-dilauroyl oxide distannoxane (including isomers) or the like; and 1,1,3,3-tetraalkyl-1,3-dihalohendistannoxanes such as 1,1,3,3-tetramethyl-1,3-dichlorodistannoxane, 1,1,3,3-tetramethyl-1,3-dibromodistannoxane 1,1,3,3-tetrabutyl-1,3-dichlorodistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dibromodistannoxane (isomers) 1,1,3,3-tetraoctyl-1 , 3-dichlorodistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dibromodistannoxane (isomers) or the like.

Of these, 1,1,3,3-tetraalkyl-1,3-dialkoxydistannoxanes are preferred, such as 1,1,3,3-tetramethyl-1,3-dimethoxydistannoxane, 1,1,3,3-tetramethyl-1, 3-diethoxydistannoxane, 1,1,3,3-tetramethyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-dibutoxydistannoxane (isomers), 1,1,3,3- tetramethyl-1,3-dipentyloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-diheptyloxydistannoxane (isomers), 1 1,3,3-tetramethyl-1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-tetramethyl-1,3-dinonyloxydistannoxane (isomers), 1 1,3,3-tetramethyl-1,3-didecyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dimethoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3 -diethoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dibutoxydistannoxane (isomers), 1,1,3, 3-tetrabutyl-1,3-dipentyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-diheptyloxydistannoxane (isomers) 1,1,3,3-tetrabutyl-1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dinonyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1 , 3-didecyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dimethoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-diethoxydistannoxane (isomers), 1,1,3 , 3-tetraoctyl-1,3-dipropoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dibutoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dipentyloxydistannoxane (isomers ), 1,1,3,3-tetraoctyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-diheptyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl- 1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dinonyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-didecyloxydis tannoxane (isomers) or the like, and 1,1,3,3-tetrabutyl-1,3-dibutoxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dipentyloxydistannoxane (isomers), 1,1 , 3,3-tetrabutyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-diheptyloxydistannoxane (isomers), 1,1,3,3-tetrabutyl-1,3-dioctyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dibutoxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-dipentyloxydistannoxane (isomers), 1,1,3,3- tetraoctyl-1,3-dihexyloxydistannoxane (isomers), 1,1,3,3-tetraoctyl-1,3-diheptyloxydistannoxane (isomers) or the like, more dpochtitelen 1,1,3,3-tetraoctyl-1,3-dioktiloksidistannoksan (including isomers).

Although the monomer structure of tetraalkyl dialkoxydistannoxane is shown by formula (19), it may have a polymer structure or an aggregate structure.

In general, organotin compounds easily accept an aggregate structure, and although it is known that, for example, a dialkoxytin dialkyltin forms a dimeric structure, tetraalkyl dialkoxydistannoxanes are known to have a ladder structure in which two or three molecules are aggregated even in cases in which there are changes in this aggregate state, the image of the compound in the form of a monomeric structure is common and easily understood by a person skilled in the art.

In addition, the previously mentioned dialkyltin alkoxide may be used alone, or two or more of its types may be used as a mixture.

A commercially available product can be used as a dialkyl tin catalyst, or can be prepared by a known method (for example, the method described in US Pat. No. 5,545,600) by reacting organic tin oxide with at least one compound selected from the group consisting of alcohol, carboxylic acid, acid anhydride, carbonic ester and hydrogen halide, followed by removal from the reaction liquid of components containing the formed water, in the case when water is formed.

In the structural formula of this dialkyltin-based catalyst, the dialkyltin oxide represented by the formula (20) is preferably used for an organotin oxide:

(where each of R ¹⁴ and R ¹⁵ independently represents a linear or branched alkyl group containing 1-12 carbon atoms).

Examples of R ¹⁴ and R ¹⁵ include alkyl groups in the form of aliphatic hydrocarbon groups containing 1-12 carbon atoms, such as methyl, ethyl, propyl (isomers), butyl (isomers), pentyl (isomers), hexyl (isomers), heptyl ( isomers), octyl (isomers), nonyl (isomers), decyl (isomers), undecyl (isomers), dodecyl (isomers) or the like, preferably linear or branched saturated alkyl groups containing 1-8 carbon atoms, and more preferably a butyl group or an n-octyl group.

Examples of compounds interacting with organotin oxide include alcohols in which the number of carbon atoms constituting the alcohol is a number selected from 1 to 12 integers, such as methanol, ethanol, propanol (isomers), butanol (isomers), pentanol (isomers), hexanol (isomers), heptanol (isomers), octanol (isomers), nonanol (isomers) or decanol (isomers); carboxylic acids in which the number of carbon atoms constituting the carboxylic acid is a number selected from integers from 1 to 12, such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, isovalerianic acid , 2-methylbutanoic acid, trimethylacetic acid, hexanoic acid, isocaproic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, heptanoic acid (isomers), octanoic acid (isomers), nonanoic acid (isomers), deca oic acid (isomers), undecanoic acid (isomers) or dodecanoic acid (isomers); acid anhydrides in which the number of carbon atoms in the acid anhydride is a number selected from integers from 3 to 25, such as acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valerian anhydride, isovaleric anhydride, succinic anhydride maleic anhydride or propionic anhydride; carboxylic acid esters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate (isomers), dibutyl carbonate (isomers), dipentyl carbonate (isomers), dihexyl carbonate (isomers), diheptyl carbonate (isomers) or dioctyl carbonate (isomers); and hydrogen halides such as hydrogen chloride, hydrogen bromide or the like.

Even if the interacting compounds vary, in the case where the interacting compound is alcohol and / or carboxylic acid, the amount of alcohol is preferably excessive, counting on the organotin oxide (since it is assumed that the reaction is equilibrium), which is 2-1000 times the stoichiometric ratio alcohol and / or carboxylic acid to the organotin oxide, taking into account the size of the reaction vessel, preferably 2-100 times and more preferably 5-50 times. As previously described, the reaction is equilibrium and it is preferably carried out by removing the water that forms. A known method can be used to remove water. Examples of such methods for removing water include membrane separation, dehydrating agents, and distillation. An example of membrane separation involves evaporation through a semipermeable hollow fiber membrane, and an organic dehydrating agent or an inorganic dehydrating agent can be used as the dehydrating agent. Examples of organic dehydrating agents include acetals, ketals and orthoesters, while examples of inorganic dehydrating agents include molecular sieves. In the case of distillation, alcohol and / or carboxylic acid, which have a boiling point higher than the boiling point of water at normal pressure, is used as a reacting alcohol, and the reaction is preferably carried out by extracting from the system water formed in the reaction as a gas phase component. The reaction temperature is usually from room temperature (20 ° C) to 350 ° C (for example, 80-180 ° C in the case where the reacting compound is alcohol), and although a high reaction temperature is preferred to increase the reaction rate, as there are cases in which undesirable reactions, such as decomposition, occur at high temperatures, thereby reducing the yield, the reaction is preferably carried out in the temperature range from 100 to 160 ° C. Known cooling devices or heating devices can be installed in the reaction vessel in order to maintain a constant reaction temperature. In addition, although the types of compounds used, the reaction temperature, and the like, vary, the reaction pressure may be reduced pressure, normal pressure, or increased pressure, and usually the reaction is carried out in the pressure range from 20 to 1 × 10 ⁶ Pa. There are no particular restrictions on the reaction time (residence time in the device in the case of a continuous process) and it usually ranges from 0.001 to 50 hours, preferably from 0.01 to 10 hours, and more preferably from 0.1 to 2 hours. In embodiments of the present invention, although the use of a solvent is not necessary, a suitable inert solvent may be used as a reaction solvent, examples of such solvents include ethers, aliphatic hydrocarbons and aromatic hydrocarbons. As the reaction vessel, a known tank type reaction vessel, a tower type reaction vessel or a distillation column as a reaction vessel can be used, and although known materials can be used for the reaction vessel and lines, provided that they do not adversely affect the starting materials or participating in the reaction. compounds, preferably inexpensive materials such as SUS304, SUS316 and SUS316L can be used.

In the case where the compound involved in the reaction is an acid anhydride or carbonic ester, although a dehydrating agent is not required, as indicated above, since this reaction does not lead to the formation of water, other conditions are the same as in the case of using alcohol and / or carboxylic acid as described above.

Since the reaction in the case where the compound participating in the reaction is hydrogen halide leads to the formation of water, the reaction is preferably carried out while removing the water formed. Hydrogen halide can also be used in a gaseous state and in the form of an aqueous solution. The reaction conditions and reaction temperature are the same as in the case of using alcohol and / or carboxylic acid, as described above.

Ester derivatives

Although the dialkyl tin catalyst used in embodiments of the present invention relates to an organotin compound that exhibits a catalytic effect in the preparation of ester derivatives, the term “ester derivative” used in embodiments of the present invention refers to a carboxylic acid ester, carbamic acid ester, isocyanate or carbonic ester.

Examples of carboxylic acid esters include aliphatic carboxylic acid esters such as ethyl acetate, propyl acetate (isomers), butyl acetate (isomers), pentyl acetate (isomers), hexyl acetate (isomers), cetyl acetate, vinyl acetate, 2-ethyl butyl acetate, 2-ethylhexyl acetate, 2 2-methoxyethyl acetate, methylene diacetate, ethylene diacetate, diacetin, triacetin, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, vinyl butyrate, ethyl hexanoate, ethyl heptanoate, ethyl heptanoate, ethyl heptanoate Daubney; and aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate, diethyl benzoate, benzyl benzoate, ethylene dibenzoate, diethyl phthalate and the like.

Examples of carbamic acid esters include ethyl N-methyl carbamate, diethyl N, N'-ethylidene dicarbamate, ethyl N-acetyl carbamate, dimethyl ether N, N'-hexanediyl bis-carbamic acid, diethyl ether N, N'-hexanediyl bis -carbamic acid, N, N'-hexanediyl-bis-carbamic acid dibutyl ether (isomers), N, N'-hexanediyl-bis-carbamic acid dibutyl ether (isomers), N, N'-hexanediyl-bis-carbamic acid dihexyl ester acids (isomers), N, N'-hexanediyl-bis-carbamic acid dioctyl ether (isomers), N, N'-hexanediyl-bis-carb didecyl ether amine acid (isomers), diphenyl ether N, N'-hexanediyl-bis-carbamic acid (isomers), di (methylphenyl) ester N, N'-hexanediyl-bis-carbamic acid (isomers), di (ethylphenyl) ester N, N'-hexanediyl-bis-carbamic acid, bis- (dimethylphenyl) ester N, N'-hexanediyl-bis-carbamic acid (isomers), bis- (dibutylphenyl) ester N, N'-hexanediyl bis- carbamic acid (isomers), N, N'-hexanediyl-bis-carbamic acid bis- (dipentylphenyl) ester (isomers), N, N'-hexanediyl-bis-carbamic acid bis- (dioctylphenyl) ester or the like Wow.

Examples of isocyanic acid esters include ethyl isocyanate, propyl isocyanate (including isomers), butyl isocyanate (isomers), pentyl isocyanate (isomers), hexyl isocyanate (isomers), heptyl isocyanate (isomers), octyl isocyanate (isomers), nonyl isomers cyanate (isomers) (isomers) (isomers) isomers), methyl phenyl isocyanate (isomers), ethyl phenyl isocyanate (isomers), butyl phenyl isocyanate (isomers), pentyl phenyl isocyanate (isomers), hexyl phenyl isocyanate (isomers), dimethyl phenyl isocyanate (isomers), diethylene diphenyl isocyanate (isomers) nat (isomers), naphthyl isocyanate (isomers), hexamethylene diisocyanate or the like.

Examples of carbonic acid esters include aliphatic carbonic acid esters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate (isomers), dibutyl carbonate (isomers), dipentyl carbonate (isomers), dihexyl carbonate (isomers), dipentyl carbonate (isomers) or the like; and aromatic carbonic esters such as diphenyl carbonate, di (methylphenyl) carbonate (isomers), di (ethylphenyl) carbonate, di (butylphenyl) carbonate (isomers) or the like.

Among the ester derivatives mentioned, carbonic esters are preferred.

In addition, the composition of the deactivated forms of the dialkyl tin catalyst formed during the process for producing carbonic acid esters from carbon dioxide and the dialkyl tin catalyst is preferably used as the composition of the deactivated forms of the dialkyl tin catalyst in embodiments of the present invention.

Deactivated form

As used herein, the term “deactivated form of a dialkyl tin catalyst” is used with respect to the aforementioned dialkyl tin catalyst, an explanation of the term is given below.

The deactivated forms of the dialkyl tin catalyst in embodiments of the present invention relate to organotin compounds formed from the aforementioned dialkyl tin catalyst, having a structure that is different from the structure of said dialkyl tin catalyst, and whose catalytic effect upon receipt of said ester derivatives is less than that dialkyltin catalyst.

The deactivated forms of said dialkyl tin catalyst are preferably thermally deactivated forms of a dialkyl tin catalyst. In many cases, the number of alkyl groups bonded to the tin atom in such deactivated forms of the dialkyl tin catalyst is changed to 0, 1, 3, or 4. That is, as previously determined, although the dialkyl tin catalyst contains two alkyl groups bonded to one tin atom, the deactivated form is an organotin compound formed from a dialkyltin catalyst in which the number of alkyl groups bonded to one tin atom is different from the number of alkyl groups bonded one tin atom in the dialkyltin catalyst based. The deactivated forms of the dialkyl tin catalysts are believed to result from the disproportionation reaction shown in the following formula (21) when the catalyst is tetraalkyl dialkoxydistannoxane or the following formula (22) when the catalyst is a dialkyltin dialkoxide:

(where each of R and R 'independently represents a linear or branched alkyl group containing 1-12 carbon atoms).

Although it is difficult to identify the structures of all deactivated forms of the dialkyltin catalyst, at least one type of said deactivated forms is the trialkyltin compound shown below. For example, there are many cases in which the trialkyltin compound represented by the following formula (23) is contained in a deactivated dialkyl tin catalyst and is approximately half of said deactivated form, counting in a stoichiometric ratio. The trialkyltin compound referred to in embodiments of the present invention relates to an organotin compound in which three alkyl groups are bonded to a tin atom and said alkyl groups are formed in a dialkyltin catalyst:

(where each of R ¹⁶ , R ¹⁷ , R ¹⁸ and X represents a group formed in a dialkyltin catalyst, R ¹⁶ , R ¹⁷ and R ¹⁸ are selected from R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ and X are selected from X ¹ , X ² , X ³ and X ⁴ ).

Examples of such a trialkyltin compounds include trialkilalkoksiolova such as trimetilmetoksiolovo, trimetiletoksiolovo, trimetilpropoksiolovo (isomers), trimetilbutoksiolovo (isomers), trimetilpentiloksiolovo (isomers), trimetilgeksiloksiolovo (isomers), trimetilgeptiloksiolovo (isomers), trimetiloktiloksiolovo (isomers), butildimetilmetoksiolovo (isomers), butildimetiletoksiolovo (isomers), butyldimethylpropoxytin (isomers), butyldimethylbutoxytin (isomers), butyldimethylpentyloxytin (isomers), butyldimethyl ksiloksiolovo (isomers), butildimetilgeptiloksiolovo (isomers), butildimetiloktiloksiolovo (isomers), butildimetilnoniloksiolovo (isomers), butildimetildetsiloksiolovo (isomers), dibutilmetilmetoksiolovo (isomers), dibutilmetiletoksiolovo (isomers), dibutilmetilpropoksiolovo (isomers), dibutilmetilbutoksiolovo (isomers), dibutilmetilpentiloksiolovo (isomers), dibutylmethylhexyloxytin (isomers), dibutylmethylheptyloxytin (isomers), dibutylmethyloctyloxytin (isomers), butyldiethylmethoxytin (isomers), butyl diethylethoxytin (Isomers), butildietilpropoksiolovo (isomers), butildietilbutoksiolovo (isomers), butildietilpentiloksiolovo (isomers), butildietilgeksiloksiolovo (isomers), butildietilgeptiloksiolovo (isomers), butildietiloktiloksiolovo (isomers), dibutiletilmetoksiolovo (isomers), dibutiletiletoksiolovo (isomers), dibutiletilpropoksiolovo (isomers), dibutiletilbutoksiolovo (isomers), dibutyl ethyl pentyloxy tin (isomers), dibutylethyl ethylhexyloxy tin (isomers), dibutylethyl ethyl heptyloxy tin (isomers), dibutylethyl ethyl hydroxy tin (isomers), butyl dipropyl metoksiolovo (isomers), butildipropiletoksiolovo (isomers), butildipropilpropoksiolovo (isomers), butildipropilbutoksiolovo (isomers), butildipropilpentiloksiolovo (isomers), butildipropilgeksiloksiolovo (isomers), butildipropilgeptiloksiolovo (isomers), butildipropiloktiloksiolovo (isomers), dibutilpropilmetoksiolovo (isomers), dibutilpropiletoksiolovo (isomers), dibutylpropylpropoxytin (isomers), dibutylpropylbutoxytin (isomers), dibutylpropylpentyloxytin (isomers), dibutylpropylhexyloxytin (isomers), dibutylpropyl geptiloksiolovo (isomers), dibutilpropiloktiloksiolovo (isomers), tributylmethoxytin (isomers), tributylethoxytin (isomers), tributilpropoksiolovo (isomers), tributilbutoksiolovo (isomers), tributilpentiloksiolovo (isomers), tributilgeksiloksiolovo (isomers), tributilgeptiloksiolovo (isomers), tributiloktiloksiolovo (isomers), octyldimethylmethoxytin (isomers), octyldimethylethoxytin (isomers), octyldimethylpropoxytin (isomers), octyldimethylbutoxytin (isomers), octyldimethylpentyloxytin (isomers), octyldimethylhexyloxy tin (isomers), oktildimetilgeptiloksiolovo (isomers) oktildimetiloktiloksiolovo (isomers), oktildimetilnoniloksiolovo (isomers), oktildimetildetsiloksiolovo (isomers), dioktilmetilmetoksiolovo (isomers), dioktilmetiletoksiolovo (isomers), dioktilmetilpropoksiolovo (isomers), dioktilmetilbutoksiolovo (isomers), dioktilmetilpentiloksiolovo (isomers), dioktilmetilgeksiloksiolovo (isomers), dioctylmethylheptyloxytin (isomers), dioctylmethyloctyloxytin (isomers), octyldiethylmethoxytin (isomers), octyldiethyl ethoxytin (isomers), oktildietilpropoksiolovo (isomers), oktildietilbutoksiolovo (isomers), oktildietilpentiloksiolovo (isomers), oktildietilgeksiloksiolovo (isomers), oktildietilgeptiloksiolovo (isomers), oktildietiloktiloksiolovo (isomers), dioktiletilmetoksiolovo (isomers), dioktiletiletoksiolovo (isomers), dioktiletilpropoksiolovo (isomers), dioktiletilbutoksiolovo (isomers), dioctyl ethyl pentyloxy tin (isomers), dioctylethyl ethylhexyloxy tin (isomers), dioctylethyl ethyl heptyloxy tin (isomers), dioctylethyl ethyloxy tin (isomers), octyldipropylmethoxy ovo (isomers), oktildipropiletoksiolovo (isomers), oktildipropilpropoksiolovo (isomers), oktildipropilbutoksiolovo (isomers), oktildipropilpentiloksiolovo (isomers), oktildipropilgeksiloksiolovo (isomers), oktildipropilgeptiloksiolovo (isomers), oktildipropiloktiloksiolovo (isomers), dioktilpropilmetoksiolovo (isomers), dioktilpropiletoksiolovo (isomers), dioctylpropylpropoxytin (isomers), dioctylpropylbutoxytin (isomers), dioctylpropylpentyloxytin (isomers), dioctylpropylhexyloxytin (isomers), dioctylpropylheptyl the lenses are (isomers), dioktilpropiloktiloksiolovo (isomers), oktildibutilmetoksiolovo (isomers), oktildibutiletoksiolovo (isomers), oktildibutilpropoksiolovo (isomers), oktildibutilbutoksiolovo (isomers), oktildibutilpentiloksiolovo (isomers), oktildibutilgeksiloksiolovo (isomers), oktildibutilgeptiloksiolovo (isomers), oktildibutiloktiloksiolovo (isomers), dioctylbutylmethoxytin (isomers), dioctylbutyl ethoxytin (isomers), dioctylbutylpropoxytin (isomers), dioctylbutylbutoxytin (isomers), dioctylbutylpentyloxytin (isomer ) Dioktilbutilgeksiloksiolovo (isomers), dioktilbutilgeptiloksiolovo (isomers), dioktilbutiloktiloksiolovo (isomers), trioktilmetoksiolovo (isomers), trioktiletoksiolovo (isomers), trioktilpropoksiolovo (isomers), trioktilbutoksiolovo (isomers), trioktilpentiloksiolovo (isomers), trioktilgeksiloksiolovo (isomers), trioktilgeptiloksiolovo (isomers ), trioctyloctyloxytin (isomers) or the like; compound trialkilatsiloksiolova such as trimetilatsetoksiolovo, trimetilpropioniloksiolovo (isomers), trimetilbutiriloksiolovo (isomers), trimetilvaleriloksiolovo (isomers), trimetillauroiloksiolovo (isomers), butildimetilatsetoksiolovo (isomers), butildimetilpropioniloksiolovo (isomers), butildimetilbutiriloksiolovo (isomers), butildimetilvaleriloksiolovo (isomers), butildimetillauroiloksiolovo (isomers ), dibutylmethylacetoxytin (isomers), dibutylmethylpropionyloxytin (isomers), dibutylmethylbutyryloxytin (isomers), di utilmetilvaleriloksiolovo (isomers), dibutilmetillauroiloksiolovo (isomers), butildietilatsetoksiolovo (isomers), butildietilpropioniloksiolovo (isomers), butildietilbutiriloksiolovo (isomers), butildietilvaleriloksiolovo (isomers), butildietillauroiloksiolovo (isomers), dibutiletilatsetoksiolovo (isomers), dibutiletilpropioniloksiolovo (isomers), dibutiletilbutiriloksiolovo (isomers), dibutylethyl ethyl valeryloxy tin (isomers), dibutylethyl ethyl lauroyl oxy tin (isomers), butyl dipropyl acetoxy tin (isomers), butyl dipropyl propionyloxy in (isomers), butildipropilbutiriloksiolovo (isomers), butildipropilvaleriloksiolovo (isomers), butildipropillauroiloksiolovo (isomers), dibutilpropilatsetoksiolovo (isomers), dibutilpropilpropioniloksiolovo (isomers), dibutilpropilbutiriloksiolovo (isomers), dibutilpropilvaleriloksiolovo (isomers), dibutilpropillauroiloksiolovo (isomers), tributilatsetoksiolovo (isomers), tributylpropionyloxytin (isomers), tributylbutyryloxytin (isomers), tributylvaleryloxytin (isomers), tributyl lauroyloxytin (isomers), octyldimethylacetate toksiolovo (isomers), oktildimetilpropioniloksiolovo (isomers), oktildimetilbutiriloksiolovo (isomers), oktildimetilvaleriloksiolovo (isomers), oktildimetillauroiloksiolovo (isomers), dioktilmetilatsetoksiolovo (isomers), dioktilmetilpropioniloksiolovo (isomers), dioktilmetilbutiriloksiolovo (isomers), dioktilmetilvaleriloksiolovo (isomers), dioktilmetillauroiloksiolovo (isomers), octyldiethylacetoxytin (isomers), octyldiethylpropionyloxytin (isomers), octyldiethylbutyryloxytin (isomers), octyldiethylvaleryloxytin (isome s), oktildietillauroiloksiolovo (isomers), dioktiletilatsetoksiolovo (isomers), dioktiletilpropioniloksiolovo (isomers), dioktiletilbutiriloksiolovo (isomers), dioktiletilvaleriloksiolovo (isomers), dioktiletillauroiloksiolovo (isomers), oktildipropilatsetoksiolovo (isomers), oktildipropilpropioniloksiolovo (isomers), oktildipropilbutiriloksiolovo (isomers), oktildipropilvaleriloksiolovo ( isomers), octyldipropyl lauroyloxytin (isomers), dioctylpropylacetoxytin (isomers), dioctylpropylpropionyloxytin (isomers), dioctylprop lbutiriloksiolovo (isomers), dioktilpropilvaleriloksiolovo (isomers), dioktilpropillauroiloksiolovo (isomers), trioktilatsetoksiolovo (isomers), trioktilpropioniloksiolovo (isomers), trioktilbutiriloksiolovo (isomers), trioktilvaleriloksiolovo (isomers), trioktillauroiloksiolovo (including isomers) or the like; and compounds trialkilgalogenolova such as trimetilhlorolovo, trimetilbromolovo, butildimetilhlorolovo, butildimetilhlorolovo (isomers), dibutilmetilhlorolovo (isomers), dibutilmetilbromolovo (isomers), butildietilhlorolovo (isomers), butildietilbromolovo (isomers), dibutiletilhlorolovo (isomers), dibutiletilbromolovo (isomers), butildipropilhlorolovo (isomers ), butyldipropyl bromo tin (isomers), dibutyl propyl chloro tin (isomers), dibutyl propyl bromo tin (isomers), tributyl chloro tin (isomers), tributyl bromo tin (isomers), octyldimethy hlorolovo (isomers), oktildimetilbromolovo (isomers), dioktilmetilhlorolovo (isomers), dioktilmetilbromolovo (isomers), oktildietilhlorolovo (isomers), oktildietilbromolovo (isomers), dioktiletilhlorolovo (isomers), dioktiletilbromolovo (isomers), oktildipropilhlorolovo (isomers), oktildipropilbromolovo (isomers), dioctyl propyl chloro tin (isomers), dioctyl propyl bromo tin (isomers), trioctyl chloro tin (isomers), trioctyl bromo tin (isomers) or the like.

In addition to the trialkyl tin compound represented by the above formula (23), deactivated forms of the dialkyl tin catalyst include tin containing components having a high boiling point (e.g., 250 ° C. or higher at 50 Pa) and an unidentifiable structure. Such tin-containing components having a high boiling point and an unidentifiable structure can be characterized by their chemical shifts in the ¹¹⁹ Sn-NMR spectrum. That is, at least one deactivated form of the dialkyl tin catalyst is an organotin compound containing a tin atom exhibiting a chemical shift of from -220 to -610 ppm. relative to tetramethyltin, by analysis of ¹¹⁹ Sn-NMR in a solution of deuterated chloroform. In other words, the deactivated forms of the dialkyl tin catalyst are trialkyl tin compounds (the trialkyl tin compounds used herein refer to organotin compounds in which three alkyl groups are linked to a tin atom and said alkyl groups are alkyl groups from a dialkyl tin catalyst) and Organotin compounds containing a tin atom exhibiting a chemical shift from -220 to -610 ppm relative to tetramethyltin, by analysis of ¹¹⁹ Sn-NMR in a solution of deuterated chloroform.

The dialkyl tin catalyst represented by the formula (7) and / or the formula (8) containing a tin atom exhibiting a chemical shift of 200 to -200 ppm relative to tetramethyltin, by analyzing ¹¹⁹ Sn-NMR in a solution of deuterated chloroform, and by deactivating the dialkyltin-based catalyst by denaturing, a tin component that contains a tin atom with a chemical shift in the above range is determined. Since the composition of deactivated forms gives a lot of signals in the specified range from -220 to -610 ppm in almost all cases, it is assumed that not only monoalkylalkoxytin oxide and monoalkyltrialkoxytinone represented by formula (21) and / or formula (22), but also other structures are contained in the composition of deactivated forms in most cases. However, although the composition of the deactivated forms is formed from compounds having thus undetectable structure, it was unexpectedly found that using the method in accordance with embodiments of the present invention makes it possible to obtain a dialkyltin compound, which leads to the completion of the present invention.

As described above, the structure of deactivated dialkyltin-based catalysts containing tin atoms exhibiting a chemical shift in the ¹¹⁹ Sn-NMR spectrum is not defined in detail. At the same time, since the trialkyltin compounds are contained in deactivated forms as described above, it can be assumed that, for example, the monoalkyltin compounds are contained as shown in formula (21) and / or formula (22), taking into account the balance of the alkyl groups . Here, the monoalkyltin compounds are organotin compounds in which one alkyl group formed from a dialkyltin catalyst is bonded to one tin atom. Examples of monoalkyltin compounds include monoalkylalkoxytin oxides, such as methyl methoxytin oxide, methylethoxytin oxide, methylpropoxytin oxide (isomers), methylbutoxytin oxide (isomers), methylpentyloxytin oxide (isomers, methyl ishexyloxytin oxide, isomers) , butyl methoxy tin oxide (isomers), butyl ethoxy tin oxide (isomers), butyl propoxy tin oxide (isomers), butyl butoxy tin oxide (isomers), butyl pentyloxy tin oxide (isomers), but oxide ylhexyloxytin (isomers), butylheptyloxytin oxide (isomers), butylctyloxytin oxide (isomers), octylmethoxytin oxide (isomers), octylethoxytin oxide (isomers), octylphenoxymethoxymethoxybutoxide, isomers), octylheptyloxytin oxide (isomers), octyloctyloxytin oxide (isomers) or the like; monoalkyltrialkoxytin compounds, such as methyltrimethoxytin, methyltriethoxytin, methyltripropoxytin (isomers), methyltribytoxytin (isomers), methyltripentyloxytin (isomers), methyltrihexyloxytin (isomers), methyltrhetyloxytinethioethiomers (isomers) butyltripropoxytin (isomers), butyltributoxytin (isomers), butyltripentyloxytin (isomers), butyltrihexyloxytin (isomers), butyltriheptyloxytin (isomers), butyltrio tiloksiolovo (isomers), oktiltrimetoksiolovo (isomers), oktiltrietoksiolovo (isomers), oktiltripropoksiolovo (isomers), oktiltributoksiolovo (isomers), oktiltripentiloksiolovo (isomers), oktiltrigeksiloksiolovo (isomers), oktiltrigeptiloksiolovo (isomers), oktiltrioktiloksiolovo (isomers) or the like; monoalkyl acyloxy tin oxides, such as methyl acetoxy tin oxide, methyl propionyloxy tin oxide (isomers), methyl butyryloxy tin oxide (isomers), methyl valeryl tin oxide (isomers), methyl lauroyl oxy tin oxide, butyryl butyryl butyryl butyryl butyryl oxide butyryl butyryl butyryl oxide (isomers), butyl lauroyl oxytin oxide (isomers), octyl acetoxy tin oxide (isomers), octyl propionyloxy tin oxide (isomers), octyl butyryloxy tin oxide (isomers), octyl valery oxide oksiolova (isomers), oktillauroiloksiolova oxide (isomers) or the like; compound monoalkiltriatsiloksiolova such as metiltriatsetoksiolovo, metiltripropioniloksiolovo (isomers), metiltributiriloksiolovo (isomers), metiltrivaleriloksiolovo (isomers), metiltrilauroiloksiolovo (isomers), butiltriatsetoksiolovo (isomers), butiltripropioniloksiolovo (isomers), butiltributiriloksiolovo (isomers), butiltrivaleriloksiolovo (isomers), butiltrilauroiloksiolovo (isomers ), octyltriacetoxytin (isomers), octyltripropionyloxytin (isomers), octyltribyryloxytin (isomers), octyltrivaleryloxytin (isome s), oktiltrilauroiloksiolovo (isomers) or the like; and monoalkyl halo tin oxides such as methyl chlorotin oxide, methyl bromine oxide, butyl chloride tin oxide, butyl bromine oxide, octyl chloride tin oxide, octyl bromine oxide or the like.

It is easy to assume that the structures of the deactivated forms of the dialkyl tin catalyst may be different than the examples listed above. In addition, compounds containing a unit in which two alkyl groups are bonded to tin and a link where an integer number of alkyl groups other than two are bonded to tin (units of the deactivated form component) as a result of the formation of a stannoxane backbone can also form. The structures of the alleged deactivated forms and / or deactivated forms containing the component links of the deactivated forms are shown below together with the above examples:

(where R and X are groups formed from a dialkyltin catalyst, R is selected from R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and X is selected from X ¹ , X ² , X ³ and X ⁴ ).

The composition of the deactivated forms of the dialkyltin catalyst according to the present invention relates to a composition containing the aforementioned deactivated forms. That is, it can be a mixture of a dialkyl tin catalyst and deactivated forms of said dialkyl tin catalyst, or a composition containing only deactivated forms. In addition, it can also be a component in which the deactivated form (i.e., an organotin compound formed from a dialkyltin catalyst, in which the number of alkyl groups bonded to one tin atom differs from their number in the dialkyltin catalyst) and a component in which the number of alkyl groups bonded to one tin atom is equal to two is covalently linked as previously described. The composition of deactivated forms, which can preferably be used in embodiments of the present invention, relates to a composition of deactivated forms containing, in mol.%, Deactivated forms, in which the number of alkyl groups bound to the tin atom differs from two by 10 mol% or more, preferably 30 mol% or more and more preferably 50 mol% or more, based on the total number of moles of tin atoms of the alkyl tin compounds contained in the composition of the deactivated forms of the base catalyst dialkyl and said deactivated forms are accumulated and / or concentrated.

Although a dialkyl tin, tetraalkyl tin, tin oxide (SnO ₂ ) catalyst and the like may be contained in a composition of deactivated dialkyl tin catalyst forms, as the case may be, these compounds may be contained to the extent that does not violate the meaning of the present invention .

In addition, the redistribution reaction of alkyl groups and / or the dealkylation reaction, which will be described later, can also be carried out using a composition containing trialkyltin compounds and a composition containing compounds whose tin atom exhibits a chemical shift of from -220 to -610 ppm . relative to tetramethyltin, when analyzing ¹¹⁹ Sn-NMR in a solution of deuterated chloroform, they are separated from the composition of deactivated forms of the dialkyltin catalyst.

At least one separation method selected from distillation separation, extraction separation and membrane separation can be used as a method of separating a composition containing trialkyltin compounds and a composition containing compounds whose tin atom exhibits a chemical shift of from -220 to -610 m. d. relative to tetramethyltin, when analyzing ¹¹⁹ Sn-NMR in a solution of deuterated chloroform, from a composition of deactivated forms of a dialkyltin catalyst, it is preferable to use distillation separation.

The composition of the deactivated forms of the catalyst based on dialkyltin

The composition of the deactivated forms of the dialkyltin catalyst based on the carbonic ester process using the dialkyl tin catalyst, and specifically the composition containing the deactivated forms of the dialkyl tin alkoxide catalyst obtained during the process for producing the carbonic ester by reacting a catalyst based on dialkyltin alkoxide and carbon dioxide, can be used for the composition of deactivated forms of the dialkylol catalyst Used in embodiments of the present invention. Here, the dialkyltin alkoxide catalyst relates to the previously described dialkyl dialkoxy tin and / or tetraalkyl dialkoxydistannoxane, and it is preferable to use a compound selected from a compound of at least one type selected from the group consisting of a dialkyl tin compound represented by the above formula (7) and a tetraalkyl distane compound represented by the above formula (8), wherein X ¹ and X ^{2 of} formula (7) and X ³ and X ^{4 of} formula (8) are alkoxy groups. The following data indicate an example of a process for the production of carbonic acid esters.

First, the dialkyl tin dialkoxide catalyst is contacted with carbon dioxide at a stoichiometric ratio of 1 to 50, based on the dialkyl tin dialkoxide catalyst in the pressure range from normal to 200 MPa, to form an additive form of the dialkyl tin dialkoxide catalyst with carbon dioxide. Further, the aforementioned dialkyltin dialkoxide-based additive catalyst form is thermally decomposed in a temperature range of 20 to 300 ° C. and for a period of time from 10 minutes to 500 hours to obtain a mixture comprising carbonic ester, dialkyltin alkoxide catalyst and deactivated catalyst forms based on dialkyltin alkoxide. In embodiments of the present invention, said mixture of a carbonic ester, a dialkyl tin alkoxide catalyst and deactivated forms of a dialkyl tin alkoxide catalyst can be used as a composition of deactivated forms of a dialkyl tin catalyst. In addition, a mixture comprising a carbonic ester, a dialkyl tin alkoxide catalyst and deactivated forms of a dialkyl tin alkoxide catalyst, obtained by removing all or part of the carbonic ester from said mixture in a manner such as filtration, solvent extraction, distillation or membrane separation can also be used as a composition of deactivated forms of a dialkyl tin catalyst.

In addition, the portion remaining after extraction of the dialkyltin dialkoxide catalyst from the mixture containing the dialkyltin dialkoxide catalyst obtained by reacting a carbonic ester with a composition of a deactivated form of a dialkyltin catalyst obtained during the production of a carbonic ester by reacting the catalyst on dialkyltin alkoxide-based, as previously described by the authors of the present invention (see publication of international application WO 2007/097388), you can also use as a composition deactivated forms of the dialkyl tin catalyst in embodiments of the present invention.

Redistribution of alkyl groups

An explanation of the redistribution of alkyl groups in embodiments of the present invention is provided below.

The redistribution reaction of alkyl groups in embodiments of the present invention is a reaction where two or more types of different organotin compounds in which the number of alkyl groups bonded to one tin atom is two or more are reacted to average the number of alkyl groups bonded to one a tin atom, and said redistribution of alkyl groups is an equilibrium reaction. Although the details of the reaction mechanism are unclear, it is believed that as a result of the interaction of an organotin compound containing three alkyl groups bonded to one tin atom with an organotin compound in which one alkyl group is bound to one tin atom, organotin compounds are formed in which the number of alkyl groups bonded to one tin atom is equal to two, as in the following formula (24):

(where R represents a linear or branched alkyl group containing 1-12 carbon atoms, and Y represents a non-alkyl group).

The specified reaction of the redistribution of alkyl groups occurs as a result of heat treatment of a mixture of two or more types of organotin compounds, in which the difference in the number of alkyl groups associated with one tin atom is 2 or more.

The specified heat treatment is preferably carried out in the temperature range from 20 to 300 ° C and, if necessary, to accelerate the reaction or to obtain a higher concentration of the dialkyl form, it is advantageous to increase the reaction temperature, more preferably from 50 to 280 ° C, to shift the equilibrium to the right. Although a high heat treatment temperature is preferable to increase the reaction rate, it is even more preferable to carry out the reaction in a temperature range of from 80 to 260 ° C., since undesired reactions, such as decomposition and the like, also occur at high temperatures, causing a decrease in yield. The reaction time may become excessively long if the temperature is below 20 ° C, while the yield of the dialkyltin compound may decrease due to the denaturation of organotin compounds caused by decomposition and similar processes at temperatures above 300 ° C. Despite the variation in the compounds used and the heat treatment time, the reaction time is from 0.001 to 50 hours and preferably from 0.01 to 10 hours, and taking into account industrial performance, the reaction time is set from 0.1 to 2 hours. The reaction can be stopped when the desired dialkyltin compound is obtained, which is determined by ¹¹⁹ Sn-NMR and the like. As will be described below, since it is assumed that the redistribution of the alkyl groups in the embodiments of the present invention is equilibrium in order to obtain a higher concentration of the tin compound in which the number of alkyl groups bonded to one tin atom is two, the reaction is carried out in this range concentrations, that the concentration of products is higher than the concentration of interacting substances, by measuring the equilibrium concentrations of the compounds used, depending on temperature or so that the concentration dialkyltin compound I increases in the products from the conversion process substituents which will be described below. In addition, in the case of heat treatment at high temperatures (for example, 150 ° C. or higher), there are cases in which the yield of the dialkyltin compound is reduced if a too long period of time is required for cooling. This is because the reaction system attempts to approximate the equilibrium concentration at low temperature during cooling, and therefore, quick cooling after heat treatment at high temperature is preferred. The known method can preferably be used to cool the reaction liquid, and, for example, it is preferable to use a method using saturated brine or a method comprising washing in a reaction vessel of low pressure from a heat treatment tank.

The indicated redistribution of alkyl groups can also be carried out in the presence of a metal halide catalyst. Examples of metal halide catalysts include tin (II) chloride, mercury (II) chloride, lead (II) chloride, mercury (II) fluoride, lead (II) fluoride, tin (II) fluoride, tin (II) iodide, lead iodide (II), mercury (II) iodide, tin (II) bromide, mercury (II) bromide, lead (II) bromide or the like, and said metal halides can be used individually or as a mixture of two or more types. Mentioned metal halides can preferably be used in the range from 0.1 to 10 wt.%, Based on the solution used for heat treatment.

Although a solvent is not required for the redistribution of alkyl groups, the solvent can be used to increase fluidity or to facilitate the reaction. Examples of such solvents include linear, branched or cyclic hydrocarbons containing 5-16 carbon atoms, ethers formed from linear, branched or cyclic hydrocarbons containing 4-16 carbon atoms, and linear, branched or cyclic halogenated hydrocarbons containing 1-16 atoms carbon. Specific examples include linear and cyclic hydrocarbons selected from pentane (isomers), hexane (isomers), heptane (isomers), octane (isomers), nonane (isomers), decane (isomers), hexadecane (isomers), cyclohexane, cycloheptane, cyclooctane benzene, toluene, xylene (isomers), ethylbenzene or the like; ethers selected from diethyl ether, dipropyl ether (isomers), dibutyl ether (isomers), dihexyl ether (isomers), dioctyl ether (isomers), diphenyl ether or the like; and halogenated hydrocarbons selected from methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, tetrachloroethane, dichlorobenzene (isomers) or the like. These solvents can be used individually or as a mixture of one or more types. Solvents can be used to increase fluidity in order to facilitate the reaction or to effectively remove water from the system in case water forms in the reaction. Examples of such solvents include linear, branched or cyclic hydrocarbons containing 5-16 carbon atoms, ethers formed from linear, branched or cyclic hydrocarbons containing 4-16 carbon atoms, and linear, branched or cyclic halogenated hydrocarbons containing 1-16 atoms carbon. Specific examples include linear and cyclic hydrocarbons selected from pentane (isomers), hexane (isomers), heptane (isomers), octane (isomers), nonane (isomers), decane (isomers), hexadecane (isomers), cyclohexane, cycloheptane, cyclooctane benzene, toluene, xylene (isomers), ethylbenzene or the like; ethers selected from diethyl ether, dipropyl ether (isomers), dibutyl ether (isomers), dihexyl ether (isomers), dioctyl ether (isomers), diphenyl ether or the like; and halogenated hydrocarbons selected from methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, tetrachloroethane, dichlorobenzene (isomers) or the like. These solvents can be used individually or as a mixture of one or more types.

In addition, the dialkyltin compound can also be obtained by carrying out the dealkylation reaction described below, simultaneously with said redistribution of alkyl groups.

As indicated previously, it is assumed that the above reaction of the redistribution of alkyl groups is an equilibrium reaction. As a result of large-scale studies conducted by the authors of the present invention, it was unexpectedly discovered that the question of whether this equilibrium is shifted towards the interacting substances or towards the products depends on the substituents associated with the tin atom and / or the temperature at which redistribution of alkyl groups. As for the substituents bound to the tin atom, for example, an alkyl group other than the alkyl groups formed from the dialkyltin catalyst bonded to the tin atom, in the case where the pKa of the conjugated acid of this group is 0-6.8, the equilibrium is shifted to the side products in most cases, as was determined, although on the other hand, when the pKa of the conjugated acid of the specified group is 6.8–25, the equilibrium is shifted towards the interacting substances in most cases. In addition, in the case where the pKa of the conjugate acid is 0-6.8, the equilibrium has been shown to shift toward products as the temperature rises.

That is, based on the above data, the present inventors have developed a method for regenerating a dialkyl tin compound from deactivated forms of a dialkyl tin catalyst (or redistribution of alkyl groups), which leads to the completion of the present invention. In the event that the deactivated forms of the dialkyl tin catalyst contain Sn — Y bonds, the dialkyl tin compound can be obtained by heat treating the deactivated forms of the dialkyl tin catalyst. Here, Y is Y, for which the pKa of the Y-conjugated acid HY, where the hydrogen atom is attached to Y, is 0-6.8.

On the other hand, in the case where the deactivated forms of the dialkyl tin catalyst do not contain Sn-Y bonds, that is, when the pKa of the acid conjugated to a group other than the alkyl group formed from the dialkyl tin catalyst is 6.9-25, the dialkyltin compound can be obtained by carrying out step (A) described below before the heat treatment.

Stage (A): (substitution step)

All substituents from the substituent part of said deactivated forms, with the exception of alkyl groups formed from a dialkyltin catalyst, are converted to Deputy Y to obtain an organotin compound containing a Sn — Y bond.

Here, Y is Y, for which the pKa of the Y-conjugated acid HY, where the hydrogen atom is attached to Y, is 0-6.8.

An explanation of step (A) is provided below.

Step (A) is a step in which a composition of deactivated forms of a dialkyl tin catalyst is reacted with an acid represented by formula (25) below and / or an acid anhydride represented by formula (26) below to produce an organotin compound containing Sn bond -Y, in which three alkyl groups and one Y group, formed from an acid and / or acid anhydride, are bonded to one tin atom, and an organotin compound containing a Sn-Y bond, which contains one alkyl group, and the number of Y groups formed from acid and / or acid anhydride selected from integers from 1 to 3, are associated with one tin atom.

As indicated above, it is preferable to use an acid represented by the following formula (25):

(where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8).

As such an acid, an organic or inorganic acid may be used. Examples of inorganic acids that may be used include hydrogen halides, hydrohalic acids, sulfuric acid, nitric acid, phosphoric acid, carbonic acid or the like, although it is preferable to use hydrogen halides and more preferably use hydrogen chloride. Examples of organic acids that can be used include carboxylic acids, sulfonic acids, sulfinic acids, phenols, enols, thiophenols, imides, oximes, aromatic sulfonamides or the like, although carboxylic acids, sulfonic acids, sulfinic acids and phenols are preferred and more preferably use carboxylic acids. Examples of carboxylic acids include saturated and unsaturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, isovaleric acid, 2-methylbutanoic acid, pivalic acid, hexanoic acid, isocaproic acid 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, heptanoic acid (isomers), octanoic acid (isomers), nonanoic acid (isomers), decanoic acid (isomers), undecanoic acid (isome ery), dodecanoic acid (isomers), tetradecanoic acid (isomers), hexadecanoic acid (isomers), acrylic acid, crotonic acid, isocrotonic acid, vinylacetic acid, methacrylic acid, angelic acid, tiglinic acid, allyl acetic acid, undecene or the like; saturated or unsaturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid (isomers), octanedioic acid (isomers), nonandionic acid (isomers), decandionic acid (isomers), fumaric acid, methyl maleic acid, methyl fumaric acid, pentenedionic acid (isomers), itaconic acid, allyl malonic acid or the like; saturated or unsaturated aliphatic tricarboxylic acids, such as 1,2,3-propanetricarboxylic acid, 1,2,3-propentricarboxylic acid, 2,3-dimethylbutane-1,2,3-tricarboxylic acid or the like; aromatic carboxylic acid compounds such as benzoic acid, methylbenzoic acid (isomers), ethylbenzoic acid (isomers), propylbenzoic acid (isomers), dimethylbenzoic acid (isomers), trimethylbenzoic acid (isomers) or the like; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, methyl isophthalic acid (isomers) or the like; and aromatic tricarboxylic acids, such as hemimellitic acid, trimellitic acid, trimesic acid, and the like. Of these carboxylic acids, it is preferable to use saturated monocarboxylic acids, it is more preferable to use monocarboxylic acids having a standard boiling point of 300 ° C or lower, and even more preferably using saturated monocarboxylic acids having a standard boiling point of 250 ° C or lower. The standard boiling point refers to the boiling point at a pressure of 1 atmosphere, as described in Encyclopedia Chimica (published on October 1, 2003 by Kyoritsu Publishing Co., Ltd.). More specifically, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, isovaleric acid, 2-methylbutanoic acid, pivalic acid and hexanoic acid are preferably used.

The acid anhydride represented by the following formula (26) is preferably used as the acid anhydride in step (A):

(where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8, and O is an oxygen atom).

Examples of such acid anhydrides include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valerian anhydride, isovaleric anhydride, succinic anhydride, maleic anhydride, propionic anhydride, glutaric anhydride; and aromatic acid anhydrides such as benzoic anhydride, phthalic anhydride, pyromellitic anhydride or the like. Of these, acid anhydrides having a standard boiling point of 300 ° C. or lower are preferred, and in order to facilitate removal of excess acid anhydride from the subsequent reaction, it is more preferable to use acid anhydrides having a standard boiling point of 200 ° C. or lower. In addition, maleic anhydride and acetic anhydride are preferred in terms of ease of removal of by-products from the system, such as carboxylic acid esters and acyl halides, and their easy preparation in industry.

Although these acids and acid anhydrides can be used individually or as a mixture of many types, when using an acid in many cases water is formed when it reacts with deactivated forms of a dialkyltin catalyst. Distillation separation or membrane separation may be carried out, or a dehydrating agent may be used to remove said water. In addition, the combined use of acid anhydride and as a dehydrating agent is preferred. Moreover, in the case of using only acid anhydride, since in many cases water does not form when the acid anhydride reacts with the deactivated forms of the dialkyl tin catalyst, methods using only acid anhydride are preferred.

The amount of acid and / or acid anhydride used is preferably a stoichiometric ratio ranging from 0.1 to 50, based on the tin atom contained in the composition of the deactivated forms of the dialkyl tin catalyst, taking into account the reaction rate and yield of the final dialkyl tin compound in step (A ), and more preferably, this amount is a stoichiometric ratio of 0.5-20, taking into account the size of the reaction vessel and the reaction rate. With a stoichiometric ratio of less than 0.1, there are cases where the reaction is difficult, although, on the other hand, even with a stoichiometric ratio of 50 or more, in many cases there is no effect on the reaction rate or on the yield of the final dialkyltin compound at this stage.

The reaction of step (A) is preferably carried out at a temperature of from -20 to 300 ° C, more preferably at a reaction temperature of from -10 to 250 ° C, and although a high reaction temperature is preferred to increase the reaction rate, since there are cases when at high temperatures occur undesirable reactions, such as decomposition, which lead to a decrease in yield, the reaction is more preferably carried out in the temperature range from 0 to 230 ° C. In this case, the reaction of step (A) is preferably carried out in an atmosphere of an inert gas, such as a gas containing argon, neon or nitrogen.

Although the use of a solvent is not required in step (A), the solvent can be used to increase fluidity or to facilitate the reaction or to effectively remove water from the system if water forms in the reaction. Examples of such solvents include linear, branched or cyclic hydrocarbons containing 5-16 carbon atoms, ethers formed from linear, branched or cyclic hydrocarbons containing 4-16 carbon atoms, and linear, branched or cyclic halogenated hydrocarbons containing 1-16 carbon atoms. Specific examples of solvents that can be used include linear and cyclic hydrocarbons selected from pentane (isomers), hexane (isomers), heptane (isomers), octane (isomers), nonane (isomers), decane (isomers), hexadecane (isomers) ), cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene (isomers), ethylbenzene or the like; ethers selected from diethyl ether, dipropyl ether (isomers), dibutyl ether (isomers), dihexyl ether (isomers), dioctyl ether (isomers), diphenyl ether or the like; and halocarbons selected from methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, tetrachloroethane, dichlorobenzene (isomers) or the like. These solvents can be used individually or as a mixture of two or more types.

An optimal method for preparing a dialkyltin compound by a redistribution of alkyl groups of the present invention as described above preferably involves converting a substituent of the composition of deactivated dialkyltin catalysts, where the pKa of the acid conjugated to said substituent of the dialkyltin catalyst is 6.8-25 in the above Y followed by further heat treatment at high temperature. Since the redistribution reaction of the alkyl groups in the embodiments of the present invention is an equilibrium reaction and is based on typical properties of the equilibrium reaction, the redistribution reaction of the alkyl groups in the embodiments of the present invention is preferably carried out according to the method described above using the deactivated form composition in which said deactivated forms have accumulated and / or concentrated to a high concentration (for example, a composition of deactivated forms, where The number of deactivated forms in which the number of alkyl groups attached to the tin atom of the alkyltin compound is equal to a number different from 2 relative to the total number of moles of tin of the alkyltin compound contained in the composition of the deactivated forms of the dialkyltin catalyst, expressed in mol%, is 10% mol% or more, preferably 30 mol% or more and more preferably 50 mol% or more).

Option for separating trialkyltin compounds from the composition of deactivated dialkyltin catalyst forms

The following is an explanation of the case of separation of a composition comprising trialkyltin compounds and a composition comprising compounds containing a tin atom exhibiting chemical shifts from -220 to 610 ppm. relative to tetramethyltin, in the analysis of ¹¹⁹ Sn-NMR in a solution of deuterated chloroform, from the composition of deactivated forms of the catalyst based on dialkyltin to stage (A).

In the case of separated compositions of the deactivated forms of the dialkyltin catalyst, each composition can be reacted with an acid and / or acid anhydride at different temperatures.

The reaction temperature of the composition containing the trialkyltin compounds separated from the composition of the deactivated forms of the dialkyltin catalyst with the acid and / or acid anhydride is preferably from −20 to 100 ° C., more preferably from −10 to 85 ° C., and although a high temperature is preferred to increase the reaction rate, it is even more preferable when the reaction temperature is from 0 to 70 ° C, since undesirable reactions such as decomposition occur at high temperatures, which leads to a decrease exit. On the other hand, the reaction temperature of a composition comprising organotin compounds containing a tin atom exhibiting a chemical shift of from -220 to 610 ppm relative to tetramethyltin in the spectrum of ¹¹⁹ Sn-NMR in deuterated chloroform, separated from the composition of the deactivated forms of the catalyst based on dialkyltin, with acid and / or acid anhydride is preferably from -20 to 300 ° C, more preferably from -10 to 250 ° C, and although a high temperature is preferable to increase the reaction rate, it is even more preferable when the reaction temperature is from 0 to 230 ° C, since undesirable reactions such as decomposition occur at high temperatures, which leads to a decrease th output. Each reaction product is mixed into a single mixture followed by heat treatment to obtain a dialkyltin compound.

Removal of unreacted substances and by-products

The reaction products obtained by reacting a composition of deactivated forms of a dialkyltin-based catalyst with an acid and / or acid anhydride in step (A) can be directly subjected to heat treatment or you can first remove unreacted acid and / or acid anhydride and / or atom-free organic compounds tin formed in the reaction, and then carry out heat treatment. Known methods such as filtration separation, distillation separation, membrane separation or solvent extraction can be used to remove unreacted acid and / or acid anhydride and / or organic compounds not containing tin atoms formed in the reaction.

Dealkylation Reaction

The following is an explanation of the dealkylation reaction in embodiments of the present invention.

As a result of large-scale studies performed by the authors of the present invention, it was unexpectedly found that by reacting a composition of deactivated forms of a dialkyl tin catalyst with a specific acid, it is possible to easily obtain dialkyl tin compounds from trialkyl tin components (organotin compounds in which three alkyl groups are bonded to a tin atom) contained in said deactivated forms. The following is a detailed explanation of said dealkylation reaction.

The dealkylation reaction in embodiments of the present invention relates to a reaction in which a composition of deactivated forms of a dialkyltin catalyst is reacted with an acid and / or acid anhydride to form an organotin compound containing a Sn — Y bond, wherein the Y group is formed from acid and / or an acid anhydride bound to the tin atom by eliminating the alkyl group bound to the tin atom. Although the detailed mechanism of this dealkylation reaction has not been established, it is assumed, for example, that the dialkyltin compound containing the Sn-Y bond is formed by the interaction of the trialkyltin compound with acid HY, as shown in the following formula (27):

(where R represents a linear or branched alkyl group containing 1-12 carbon atoms, and Y represents a group different from the alkyl group).

In said dealkylation reaction, an acid represented by the following formula (25) is preferably used as an acid:

(where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8).

As the specified acid, an organic acid or an inorganic acid may be used. Examples of inorganic acids include hydrogen halides, hydrohalic acids, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, although hydrogen halides and more preferably hydrogen chloride are preferably used. Examples of organic acids that can be used include carboxylic acids, sulfonic acids, sulfinic acids, phenols, enols, thiophenols, imides, oximes and aromatic sulfonamides, although carboxylic acids, sulfonic acids, sulfinic acids and phenols are preferably used, and more preferably carboxylic acids are used. acids. Examples of carboxylic acids include saturated and unsaturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, isovaleric acid, 2-methylbutanoic acid, pivalic acid, hexanoic acid, isocaproic acid 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, heptanoic acid (isomers), octanoic acid (isomers), nonanoic acid (isomers), decanoic acid (isomers), undecanoic acid (isome ery), dodecanoic acid (isomers), tetradecanoic acid (isomers), hexadecanoic acid (isomers), acrylic acid, crotonic acid, isocrotonic acid, vinylacetic acid, methacrylic acid, angelic acid, tiglinic acid, allyl acetic acid, undecene or the like; saturated or unsaturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid (isomers), octanedioic acid (isomers), nonandionic acid (isomers), decandionic acid (isomers), fumaric acid, methyl maleic acid, methyl fumaric acid, pentenedionic acid (including isomers), itaconic acid, allyl malonic acid or the like; saturated or unsaturated aliphatic tricarboxylic acids, such as 1,2,3-propanetricarboxylic acid, 1,2,3-propentricarboxylic acid, 2,3-dimethylbutane-1,2,3-tricarboxylic acid or the like; aromatic carboxylic acid compounds such as benzoic acid, methylbenzoic acid (isomers), ethylbenzoic acid (isomers), propylbenzoic acid (isomers), dimethylbenzoic acid (isomers), trimethylbenzoic acid (isomers) or the like; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, methyl isophthalic acid (isomers) or the like; and aromatic tricarboxylic acids, such as hemimellitic acid, trimellitic acid, trimesic acid, and the like. Of these carboxylic acids, saturated monocarboxylic acids are preferably used, although saturated monocarboxylic acids having a standard boiling point of 300 ° C or lower are more preferably used, and even more preferably saturated monocarboxylic acids having a standard boiling point of 250 ° C or lower are used. More specifically, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, isovaleric acid, 2-methylbutanoic acid, pivalic acid and hexanoic acid are preferably used.

In addition, acid anhydride represented by the following formula (26) is also preferably used in said dealkylation reaction:

(where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8, and O is an oxygen atom).

Examples of such acid anhydrides include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valerian anhydride, isovaleric anhydride, succinic anhydride, maleic anhydride, propionic anhydride, glutaric anhydride; and aromatic acid anhydrides such as benzoic anhydride, phthalic anhydride, pyromellitic anhydride or the like. Of these, acid anhydrides having a standard boiling point of 300 ° C or lower are preferably used, and in order to facilitate removal of excess acid anhydride from the subsequent reaction, it is more preferable to use acid anhydrides having a standard boiling point of 200 ° C or lower. In addition, maleic anhydride and acetic anhydride are preferable in terms of ease of removal of by-products from the system, such as carboxylic acid esters and acyl halides, as well as their easy production in industry.

These acids and acid anhydrides can be used individually or as a mixture of many types.

The amount of acid and / or acid anhydride used is preferably in the range of 0.1 to 50 stoichiometric relative to the tin atom contained in the composition of the deactivated forms of the dialkyl tin catalyst, taking into account the reaction rate and yield of the final dialkyl tin compound, and more preferably ranging from 0.5 to 20, taking into account the size of the reaction vessel and the reaction rate. With a stoichiometric ratio of less than 0.1, there are cases where the reaction is difficult, although, on the other hand, even with a stoichiometric ratio of 50 or more, in many cases there is no effect on the reaction rate or on the yield of the final dialkyltin compound in said dealkylation reaction.

The specified dealkylation reaction is preferably carried out at a reaction temperature of from -20 to 300 ° C, more preferably carried out at a reaction temperature of from -10 to 250 ° C, and although a high reaction temperature is preferred to increase the reaction rate, since there are cases when at high temperatures unwanted reactions occur, such as decomposition, which lead to a decrease in yield, the reaction is preferably carried out in the temperature range from 0 to 230 ° C. In this case, the dealkylation reaction is preferably carried out in an atmosphere of an inert gas, such as a gas containing argon, neon or nitrogen.

Although the use of a solvent is not required in said dealkylation reaction, the solvent can be used to increase fluidity or to facilitate the reaction, or to efficiently remove water from the system if water forms in the reaction. Examples of such solvents include linear, branched or cyclic hydrocarbons containing 5-16 carbon atoms, ethers formed from linear, branched or cyclic hydrocarbons containing 4-16 carbon atoms, and linear, branched or cyclic halogenated hydrocarbons containing 1-16 atoms carbon. Specific examples of solvents that can be used include linear and cyclic hydrocarbons selected from pentane (isomers), hexane (isomers), heptane (isomers), octane (isomers), nonane (isomers), decane (isomers), hexadecane (isomers) ), cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene (isomers), ethylbenzene or the like; ethers selected from diethyl ether, dipropyl ether (isomers), dibutyl ether (isomers), dihexyl ether (isomers), dioctyl ether (isomers), diphenyl ether or the like; and halogenated hydrocarbons selected from methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, tetrachloroethane, dichlorobenzene (isomers) or the like. These solvents can be used individually or as a mixture of two or more types.

The aforementioned alkyl group redistribution reaction can be carried out simultaneously with said dealkylation reaction. Since this dealkylation reaction is not equilibrium, while the redistribution of alkyl groups is an equilibrium reaction, both reactions are combined, if necessary.

Dialkyltin Compounds

Dialkyltin compounds obtained by the redistribution of alkyl groups and / or the dealkylation reaction described above are compounds that include a compound of at least one type selected from the group consisting of a dialkyltin compound represented by the following formula (13) and tetraalkyldistannoxane represented by the following formula (14):

(where R ⁷ and R ⁸ are groups formed from a dialkyl tin catalyst, and each independently represents a linear or branched alkyl group containing 1-12 carbon atoms,

Y represents a group formed from a dialkyltin catalyst, or a group formed from acid (HY) and / or acid anhydride (YOY), pKa of an acid conjugated to Y (in the form of HY), where the hydrogen atom is attached to Y, is 0-6.8, and

i and j independently represent an integer from 0 to 2 and i + j = 2);

(where R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are groups formed from a dialkyl tin catalyst and independently represent a linear or branched alkyl group containing 1-12 carbon atoms,

Y represents a group formed from a dialkyltin catalyst, or a group formed from acid (HY) and / or acid anhydride (YOY), pKa of an acid conjugated to Y (in the form of HY), where the hydrogen atom is attached to Y, is 0-6.8, and

k, l, m and n respectively represent an integer from 0 to 2, k + l = 2 and m + n = 2).

Obtaining a dialkyl tin catalyst from a dialkyl tin compound as a starting material

The dialkyl tin catalyst can be prepared by the method of step (I) using the dialkyl tin compound obtained by the method described above as the starting material.

Stage (I). The step in which the substituent Y of the dialkyltin compound containing the Sn — Y bond is converted to a substituent of at least one type selected from the group consisting of alkoxy, acyloxy and halogen.

The specified stage (I) is preferably a stage comprising the following stages (I-1) - (I-2):

Stage (I-1): (hydrolysis stage). A composition comprising a dialkyltin oxide compound is prepared by hydrolysis of a dialkyltin compound containing a Sn — Y bond by adding an aqueous alkali solution; and

Stage (I-2). The component containing the water formed is removed from the reaction liquid by subjecting the composition containing the dialkyltin oxide obtained in step (I-1) to a compound of at least one type selected from the group consisting of alcohol, carboxylic acid and hydrogen halide .

The following is an explanation of the indicated steps (I-1) to (I-2).

Step (I-1) is the step of preparing a composition containing dialkyltin oxide compounds by adding an alkaline aqueous solution to the dialkyltin compound obtained by a redistribution of alkyl groups and / or a dealkylation reaction. As used herein, the term “aqueous alkali solution” refers to an aqueous solution in which the alkali is dissolved in water. The term “alkali” is a generic term for a substance that takes the form of MOH hydroxide and dissolves in water, as described in Encyclopedia Chimica Volume 1 (Kyoritsu Publishing Co., Ltd., 38th Compact Edition). Although M refers to an alkali metal or ammonium group, in addition, the term “alkali” refers to calcium and barium hydroxides, the term “hydroxides” is also used in a broad sense and includes sodium carbonate, ammonium carbonate, sodium phosphate and the like.

There are no specific restrictions on the aqueous alkali solution used in the indicated step (I-1), provided that the pH of said solution is greater than 7, and examples include an aqueous lithium hydroxide solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous solution of cesium hydroxide, an aqueous solution of potassium carbonate, an aqueous solution of sodium carbonate, an aqueous solution of sodium bicarbonate, an aqueous solution of ammonium carbonate, an aqueous solution of sodium phosphate and the like. Of these, it is preferable to use an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of potassium carbonate. These aqueous solutions of alkali can be used individually or as a mixture of two or more types. There are no particular restrictions on the amount of aqueous alkali solution used, provided that the amount corresponds to the amount necessary for the formation of a precipitate, a mass ratio of from 1 to 10 to the amount of the mixture containing dialkyltin compounds obtained by the redistribution of alkyl groups and / or dealkylation reaction is preferably used. .

There is no particular limitation on the temperature of said step (I-1), and the temperature is preferably from -10 to 100 ° C, more preferably from -5 to 50 ° C, and although a higher reaction temperature is preferred to increase the reaction rate, more preferred is a temperature of from 0 to 30 ° C, as there are cases when undesirable reactions, such as decomposition, occur at high temperatures, which leads to a decrease in yield.

A composition containing dialkyltin oxide compounds is prepared in step (I-1). A composition containing dialkyltin oxide compounds can be separated as a precipitate. For separation, a known method can be used and the composition can be separated, for example, by filtration.

Step (I-2) is a step of reacting a composition containing dialkyltin oxide compounds separated in step (I-1) with a compound of at least one type selected from the group consisting of alcohol, carboxylic acid and hydrogen halide to remove from the reaction liquid of the component containing the formed water. Examples of alcohols used in the indicated step (I-2) include alcohols in which the number of carbon atoms included in the indicated alcohol is a number selected from integers from 1 to 12, such as methanol, ethanol, propanol (isomers) , butanol (isomers), pentanol (isomers), hexanol (isomers), heptanol (isomers), octanol (isomers), nonanol (isomers), decanol (isomers) or the like. Moreover, examples of carboxylic acids used in this step (I-2) include carboxylic acids, in which the number of carbon atoms included in said carboxylic acid is a number selected from integers from 1 to 12, such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, isovalerianic acid, 2-methylbutanoic acid, pivalic acid, hexanoic acid, isocaproic acid, 2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, heptanoic acid lots (isomers), octanoic acid (isomers), nonanoic acid (isomers), decanoic acid (isomers), undecanoic acid (isomers), dodecanoic acid (isomers) or the like. In addition, examples of hydrogen halides used in this step (I-2) include hydrogen chloride, hydrogen bromide and the like.

The stoichiometric ratio of the amount of reagent used in the indicated step (I-2) (the term “reagent”, used hereinafter, refers to alcohol, carboxylic acid and hydrogen halide), based on tin atoms, in a composition containing dialkyltin oxide, ranges from 1 to 1000, preferably from 2 to 100, and although an excess amount is preferable to increase the reaction rate, an amount from 3 to 50 is even more preferred, taking into account the ease of removal after reaction. The aforementioned range is preferable since a significant amount of energy is required to remove the reagent after the reaction if an excessively excessive amount of reagent is used.

Although the use of a solvent is not necessary at the indicated stage (I-2), a solvent that gives an azeotropic mixture with water can be added to increase fluidity, facilitate the reaction and quickly remove the resulting water from the system. The solvents that can be used can be any, provided that the solvent does not react with the dialkyltin oxide or dialkyltin catalyst formed in this step. Examples of such solvents include branched, linear or cyclic aliphatic hydrocarbons such as hexane (isomers), heptane (isomers), octane (isomers) or the like; aromatic hydrocarbons such as benzene, toluene, xylene (including isomers) or the like; ethers.

Although there is a variation in the reagents, solvents and component ratios used, the temperature of said step (I-2) is preferably from 80 to 200 ° C, and although high temperature is preferred to increase the reaction rate, a reaction temperature in the range of from 100 to 180 is more preferred. ° C, since at high temperatures in some cases there are undesirable reactions, such as decomposition.

There is no particular pressure limitation at which the indicated step (I-2) is carried out, and although it can be carried out under reduced pressure to effectively remove water from the system, the indicated step is preferably carried out at a pressure of from 10 Pa to 1 MPa, and more preferably in the range from 10 kPa to 0.5 MPa.

As indicated above, although it is necessary to remove from the reaction system the water generated in the reaction in the indicated step (I-2), a known method can be used for dehydration, examples of which include distillation separation, distillation under reduced pressure, distillation under pressure, thin-film distillation, azeotropic distillation or the like. For membrane separation, a method such as pervaporation can be used, while a known dehydrating agent such as molecular sieves can be used as a dehydrating agent.

There are no particular restrictions on the reaction vessels used for each of the reactions in the embodiments of the present invention, and known types of reaction vessels can be used. Typically used reaction vessels can be combined appropriately for use, examples of reaction vessels include a stirred tank, a sealed stirred tank, a pressurized stirred tank, a column type reactor, a distillation column, a packed column, a thin film distillation device, or the like. There are also specific limitations on the material of the reaction vessel, and known materials can be used. For example, you can use a reaction vessel made of glass, stainless steel, carbon steel or Hastelloy, or a reaction vessel made of a base material provided that the reaction vessel is coated with glass or a reactor coated with Teflon. Since in some cases acid corrosion can be significant and depends on the stage and conditions, in such cases you can choose a suitable glass reaction vessel with a glass lining equipped with a Teflon coating (registered trademark), or a reaction vessel made of Hastelloy alloy.

The dialkyltin catalyst obtained in the previously described steps can be used to prepare ester compounds. As previously described, the optimal method for producing a dialkyltin compound by a redistribution of alkyl groups according to embodiments of the present invention makes it possible to obtain extremely dialkyltin compounds in the case of conversion of a substituent of a composition of deactivated forms of a dialkyltin catalyst, the pKa of the conjugated acid of which is 6.8-25, to the aforementioned Y followed by heat treatment at high temperature. In this example, after treating the composition of the deactivated forms of the dialkyltin alkoxide formed in the production of the carbonic ester, where the dialkyltin alkoxide is used as a dialkyltin catalyst as described below with an acid and / or acid anhydride, preferably acid anhydride and more preferably acetic anhydride according to the previously described step (A), the redistribution of the alkyl groups is carried out by heat treatment, and the resulting dialkyltin compound (and preferred about dialkildiatsetoksiolovo) was converted to the dialkyl tin alkoxide, followed by recycling of the catalyst for producing carbonic acid ester. In this case, since the redistribution reaction of the alkyl groups in the embodiments of the present invention is an equilibrium reaction, as previously described, and is based on the typical properties of the equilibrium reaction, the redistribution reaction of the alkyl groups in the embodiments of the present invention is carried out according to the method described above, using the composition of deactivated forms wherein said deactivated forms are accumulated and / or concentrated to a high concentration (e.g., the composition is deactivated forms, where the content of deactivated forms, in which the number of alkyl groups attached to the tin atom of the alkyltin compound, is a number other than 2, relative to the total number of moles of tin of the alkyltin compound contained in the composition of the deactivated forms of the dialkyltin catalyst, when expressed in mol .% is 10 mol.% or more, preferably 30 mol.% or more and more preferably 50 mol.% or more).

That is, one objective of the present invention is to obtain a dialkyl tin compound from a composition of deactivated dialkyl tin catalysts formed during the ester production process, regenerate said dialkyl tin compound as a dialkyl tin catalyst and reuse it as a catalyst to produce ester compounds, and specifically carbonic acid esters.

The method for producing carbonic acid esters preferably includes the following steps (1) to (4):

stage (1) (stage of formation of carbonic esters): carbon dioxide and a dialkyl tin catalyst are reacted to produce a reaction liquid containing carbonic ester;

stage (2) (stage for the separation of carbonic acid esters): the carbonic ester is isolated from the reaction liquid to obtain a residual liquid;

step (3) (dialkyltin catalyst-based regeneration step): the residual liquid is reacted with alcohol and the formed water is removed from the system to regenerate the dialkyltin catalyst; and

step (4) (recycling step): the dialkyltin-based catalyst obtained in step (3) is reused in step (1).

A detailed explanation of each step is provided below with an example of a method for producing a carbonic ester using a dialkyl tin alkoxide for a dialkyl tin catalyst.

(i) A step for synthesizing an alkyltin alkoxide (a step for starting a continuous operation)

At this stage, it is preferable to use the previously described method for producing alkyltin alkoxide (such as in WO 2005/111049). This step is a step for producing alkyltin alkoxide from dialkyltin oxide and alcohol.

Alcohols in which the number of carbon atoms in the alcohol is a number selected from integers from 1 to 12, such as methanol, ethanol, propanol (isomers), butanol (isomers), pentanol (isomers), hexanol (isomers ), heptanol (isomers), octanol (isomers), nonanol (isomers), decanol (isomers) or the like, are preferably used as alcohols.

The dialkyltin oxide represented by the following formula (28) is used as the dialkyltin oxide in the synthesis of the alkyltin alkoxide:

(where R ¹⁴ and R ¹⁵ independently represent a linear or branched alkyl group containing 1-12 carbon atoms).

Examples of R ¹⁴ and R ¹⁵ include alkyl groups, which are aliphatic hydrocarbon groups containing 1-12 carbon atoms, such as methyl, ethyl, propyl (isomers), butyl (isomers), pentyl (isomers), hexyl (isomers), heptyl (isomers), octyl (isomers), nonyl (isomers), decyl (isomers), undecyl (isomers), dodecyl (isomers) groups or the like, preferably linear or branched saturated alkyl groups containing 1-8 carbon atoms, and more preferably n-butyl Rupp or n-octyl group.

The specified alcohol and the specified dialkyltin oxide are subjected to a dehydration reaction and the resulting water is removed from the system to obtain tetraalkyl dialkoxydistannoxane and / or dialkyltin dialkoxide. The temperature at which the reaction is carried out is, for example, from 80 to 180 ° C, and to remove the formed water from the system, the reaction temperature is preferably from 100 to 180 ° C, although the temperature varies according to pressure, and although high temperature is preferred to increase the reaction rate, it is more preferable when the reaction temperature is from 100 to 160 ° C, since undesirable reactions such as decomposition occur at high temperatures. The reaction pressure is the pressure that allows the water to be removed from the system, and although the pressure varies according to the reaction temperature, it is from 20 to 1 × 10 ⁶ Pa. There is no particular limitation on the dehydration reaction time, and it usually ranges from 0.001 to 50 hours, preferably from 0.01 to 10 hours, and more preferably from 0.1 to 2 hours. The reaction is completed as soon as the desired alkyltin alkoxide composition is obtained. The progress of the reaction is determined by measuring the amount of water recovered from the system, or by analyzing ¹¹⁹ Sn-NMR samples of the reaction liquid.

In order to obtain a mixture according to embodiments of the present invention, in step (1), the reaction is completed after confirming receipt of a composition in which the molar ratio of tetraalkyl dialkoxydistannoxane to dialkyltin dialkoxide contained in the alkyltin alkoxide composition obtained in the above reaction is from 0: 100 to 80:20 (when presenting both as mol.%), and more preferably from 10:90 to 70:30. The alcohol used may be left in the system or it may be removed by distillation, as the case may be. It is preferable to remove as much alcohol as possible, as this gives the advantage that it is possible to reduce the size of the reaction vessels at other stages. Removal by a known distillation method is preferred, and known distillation devices can be used as distillation devices used to distill alcohol. As distillation devices, it is preferable to use thin film distillation devices, since they allow the removal of alcohol in a short period of time. There are no particular restrictions on the type of reaction vessel for the dehydration reaction, and a known tank type or column type reaction vessel can be used. A low boiling point reaction mixture containing water is recovered from the reaction vessel by gas distillation, while a high boiling point reaction mixture containing the obtained alkyltin alkoxide or a mixture of alkyltin alkoxides is recovered from the bottom of the reaction vessel as a liquid. Various well-known methods are used for such a reaction vessel, such as methods using reaction vessels including any of, for example, a stirred tank, a multi-stage stirred tank, a distillation column, a multi-stage distillation column, a multi-tube reactor, a continuous multi-stage column distillation, packed column, thin-film evaporator, internally supported reactor, forced-circulation reactor, falling film evaporator, evaporator a falling droplet, the narrow flow phase reactor or a column-bubbler, and combinations thereof. Processes using a column type reactor are preferable from the point of view of an effective equilibrium shift towards products, and a structure having a large gas-liquid contact area is preferred, which makes it possible to quickly transfer the resulting water to the gas phase. Although continuous methods using a multi-tube reactor, a distillation column, or a packing column filled with packing material can also be used, since the dialkyltin oxide used in this step is usually a solid, the process in which the step is first carried out in a reaction vessel is most preferred reservoir type with a subsequent increase in the content of dialkyltin dialkoxide in the reaction vessel of the column type. Although well-known materials can be used to make the reaction vessel and lines, provided that they do not have a harmful effect, inexpensive materials such as SUS304, SUS316 or SUS316L can preferably be used. Well-known process equipment, including instruments, such as flow meters and thermometers, reboilers, pumps and compressors, can be added if necessary; for heating, a known method, such as heating with steam or a heater, can be used, and for cooling, a known method, such as cooling with air, cold water or brine, can be used.

(ii) a Dialkyltin-based catalyst regeneration step (step 3)

Although this step is carried out after obtaining the residual liquid in step (2), it will be explained earlier, since it resembles the step for the synthesis of dialkyltin alkoxide described above. This step is a step in which the residual liquid obtained in step (2) and the alcohol are dehydrated to regenerate the dialkyltin alkoxide.

Although alcohols in which the number of carbon atoms in the alcohol is a number selected from integers from 1 to 12, such as methanol, ethanol, propanol, (isomers), butanol (isomers), pentanol (isomers), hexanol (isomers), heptanol (isomers), octanol (isomers), nonanol (isomers), decanol (isomers) or the like, are preferably used as the alcohol, more preferably the same alcohol used in the aforementioned alkyltin alkoxide synthesis step.

The dehydration reaction is preferably carried out under the same conditions as the synthesis stage of the alkyltin alkoxide. The reaction is completed immediately after the desired alkyltin alkoxide composition is obtained. The progress of the reaction is monitored by measuring the amount of water recovered from the system or by ¹¹⁹ Sn-NMR analysis of the collected samples of the reaction liquid. In order to obtain a mixture according to embodiments of the present invention, in step 1, the reaction is completed after confirming receipt of a composition in which the molar ratio of tetraalkyl dialkoxydistannoxane to dialkyltin dialkoxide in the alkyltin alkoxide composition obtained in the above reaction is from 0: 100 to 80:20, both of which are mol.%, and more preferably ranges from 10:90 to 70:30. The alcohol used may be left in the reaction vessel or it may be removed by distillation, as the case may be. It is preferable to remove as much alcohol as possible, as this gives the advantage that it is possible to reduce the size of the reaction vessels at other stages. Removing alcohol by a known distillation method is preferred, and known distillation devices can be used as distillation devices used to distill off the alcohol. As distillation devices, it is preferable to use thin-film distillation devices, since they allow alcohol to be removed in a short period of time. In contrast to the alkyltin alkoxide synthesis step, the dialkyltin oxide is not usually used in the solid state at this stage, therefore, there are few restrictions on the reaction vessel. That is, there are no particular restrictions on the type of reaction vessel for the dehydration reaction, and a tank type reaction vessel and a column type reaction vessel can be used. A low boiling point reaction mixture containing water is recovered from the reaction vessel by gas distillation, while a high boiling point reaction mixture containing the obtained alkyltin alkoxide or a mixture of alkyltin alkoxides is recovered from the bottom of the reaction vessel as a liquid. Various well-known methods are used for such a reaction vessel, such as methods using reaction vessels including any of, for example, a stirred tank, a multi-stage stirred tank, a distillation column, a multi-stage distillation column, a multi-tube reactor, a continuous multi-stage column distillation, packed column, thin-film evaporator, internally supported reactor, forced-circulation reactor, falling film evaporator, evaporator a falling droplet, the narrow flow phase reactor or a column-bubbler, and combinations thereof. Methods using a column type reaction vessel are preferable from the point of view of an effective shift of equilibrium towards products, and a structure having a large gas-liquid contact area is preferable, which makes it possible to quickly transfer the resulting water to the gas phase. It is particularly preferable to use continuous processes using a multi-tube reactor, a multi-stage distillation column, or a packed column filled with packed material. Although well-known materials can be used to make the reaction vessel and lines, provided that they do not have a harmful effect, inexpensive materials such as SUS304, SUS316 or SUS316L can preferably be used. Well-known process equipment including instruments such as flow meters and thermometers, reboilers, pumps and compressors can be added, if necessary, a known method, such as steam or a heater, can be used for heating, and a known method, such as air cooling with cold water or brine.

(iii) Stage of formation of a carbonic ester (stage 1)

Although the present step is a step of reacting a dialkyltin alkoxide with carbon dioxide gas, it is preferable to use the previously described method for producing a carbonic ester (such as WO 03/055840 or WO 04/014840) for this step.

The alkyltin alkoxide composition to be supplied to said step can be submitted either from the synthesis of the alkyltin alkoxide at its initial moment, or from the alkyltin alkoxide production step of step (3) during the continuous process. In addition, there are cases in which said composition is also supplied from the dialkyltin catalyst-based regeneration step, which will be described later.

At this stage, gaseous carbon dioxide is first absorbed on the above-mentioned dialkyltin alkoxide, causing a chemical reaction, and gives a mixture containing a form of dialkyltin alkoxide bound to carbon dioxide.

During said chemical reaction, said dialkyltin alkoxide is reacted as a liquid or as a liquid with a solvent and the like. Preferably, a method for producing a liquid by heating is used and the dialkyltin oxide is converted to a liquid state. In addition, the dialkyltin oxide may be converted to a liquid by a solvent or the like. Despite varying the temperature at which the reaction is carried out, the pressure preferred for the reaction is in the range from normal to 1 MPa, and more preferably in the range from normal to 0.6 MPa. Despite varying the reaction pressure, the reaction temperature is preferably from -40 to 80 ° C and, taking into account the viscosity during transfer, is more preferably from 0 to 80 ° C and most preferably from room temperature, for example 20 ° C, to 80 ° C. The reaction time is from a few seconds to 100 hours and, taking into account the productivity, is preferably from a few minutes to 10 hours. As the reaction vessel, a known tank type reaction vessel or column type reaction vessel can be used. In addition, many reaction vessels can be used by combining them. Since the reaction consists of a reaction between carbon dioxide (gas) and an alkyltin alkoxide (liquid) composition, it is preferable to increase the gas-liquid contact area by increasing the gas-liquid interface for the reaction to proceed efficiently. Known data can be used for interaction by increasing the gas-liquid interface, and in the case of a tank type reactor, for example, it is preferable to increase the stirring speed or generate air bubbles in the liquid, whereas in the case of a column type reactor, it is preferable to use a packed column or plate column. Examples of such column-type reaction vessels that can be used include types of poppet columns using bubble trays, porous trays, cock plates or counterflow trays, and types of packed columns filled with various types of nozzles such as Raschig rings, Lessing rings, pole rings , Burl saddle nozzle, Interlock saddle nozzle, Dixon nozzle, McMahon nozzle, Helipack, Sulzer nozzle, Mellapack nozzle or the like. Although well-known materials can be used to make the reaction vessel and lines, provided that they do not have a harmful effect, inexpensive materials such as SUS304, SUS316 or SUS316L can preferably be used. Well-known process equipment including instruments such as flow meters and thermometers, reboilers, pumps and compressors can be added, if necessary, a known method, such as steam or a heater, can be used for heating, and a known method, such as air cooling with cold water or brine. Since the reaction is usually exothermic, it is possible to carry out cooling or it is possible to carry out cooling by dissipating heat from the reaction vessel. Alternatively, heating can be carried out in order to cause the simultaneous esterification of carbonic acid. The known method using a jacket or an internal coil can be used to cool and heat the reactor. Gaseous carbon dioxide and an alkyltin alkoxide composition fed to the reaction vessel may be fed individually or may be mixed before being fed into the reaction vessel. You can also submit them to many places in the reactor. The completion of the reaction can be determined, for example, by analysis of ¹¹⁹ Sn-NMR.

Next, the reaction liquid containing the carboxylic acid ester is prepared from the carbon dioxide bound form of the dialkyltin alkoxide obtained above by the method described below.

Although the reaction conditions are such that the reaction temperature is from 110 to 200 ° C, and a high reaction temperature is preferable to increase the reaction rate, the reaction is preferably carried out at a temperature of from 120 to 180 ° C, since there are cases when undesirable reactions occur at high temperatures such as decomposition, which lead to a decrease in yield; the reaction time is from 0.1 to 10 hours, and the pressure is from 1.5 to 20 MPa, and preferably in the range from 2.0 to 10 MPa. The reaction is completed after the desired carbonic ester is formed in the reaction vessel. The progress of the reaction can be confirmed by sampling the reaction liquid from the reaction vessel and analyzing ¹ H-NMR of the formed carbonic ester or gas chromatography. For example, the reaction can be completed immediately after 10% or more ether is formed with respect to the number of moles of dialkyl tin alkoxide and / or dialkyl tin alkoxide form contained in the dialkyl tin alkoxide and / or dialkyl tin alkoxide form associated with carbon dioxide, or if necessary, increase the yield of carbonic ester, the reaction can be completed after continuing the reaction until the indicated value reaches 90% or more. A known reaction vessel can be used as a reaction vessel, and a column type or reservoir type reaction vessel is preferred. Although well-known materials can be used to make the reaction vessel and lines, provided that they do not have a detrimental effect, it is preferable to use inexpensive materials such as SUS304, SUS316 or SUS316L. Well-known process equipment, including devices such as flow meters and thermometers, reboilers, pumps and compressors, can be attached, if necessary, for heating, you can use the known method, such as heating with steam or a heater, and for cooling, you can use the known method, such as air cooling with cold water or brine.

(iv) a step for separating a carbonic ester (step 2)

The specified stage is a stage of separation of the carbonic ester from the reaction liquid containing the carbonic ester obtained in stage (1), and obtain a residual liquid. For separation, it is preferable to use known methods and devices. A preferred separation method is distillation separation.

The carbonic ester and residual liquid are obtained by periodic, semi-periodic or continuous distillation of the reaction liquid of stage (1). A preferred distillation method comprises supplying said reaction liquid to a distillation cube; separating the carbonic ester from the top of the distillation cube outside the system as a gaseous component; and recovering the residual liquid from the bottom of the distillation cube as a liquid component. Despite varying the boiling point of the specified carbonic ester, at this stage a temperature is used in the range from room temperature, for example 20 ° C, to 200 ° C, and since there are cases where tin compounds are denatured in the residual liquid at high temperatures, and also cases where the formation of a carbonic ester decreases due to a reverse reaction, it is preferable that the temperature is from room temperature, for example 20 ° C., to 150 ° C. Despite varying the type of carbonic ester and the temperature at which this stage is carried out, the pressure is usually in the range from normal to low and, taking into account the productivity, it is preferable to use a pressure of 100 Pa to 80 kPa and most preferably a pressure of 100 Pa to 50 kPa The time for the stage under consideration can be from 0.01 to 10 hours, and since there are cases where the stage is carried out at high temperature for a long period of time, where the tin compounds contained in the reaction liquid can undergo denaturation or the content of carbonic ester may decrease due to a reversible reaction, a reaction time of from 0.01 to 0.5 hours is preferred and most preferably from 0.01 to 0.3 hours. A known distillation cube can be used as a distillation cube, and it is preferable to use a distillation cube of column type or reservoir type, or many other types can be used by combining them. More preferably, the distillation cube is a thin-film evaporator or thin-film distillation cube, although a thin-film evaporator equipped with a distillation column or a thin-film distillation cube is most preferred. Although well-known materials can be used to make the reaction vessel and lines, provided that they do not have a harmful effect, inexpensive materials such as SUS304, SUS316 or SUS316L can preferably be used. Well-known process equipment including instruments such as flow meters and thermometers, reboilers, pumps and compressors can be added, if necessary, a known method, such as steam or a heater, can be used for heating, and a known method, such as cooling by air, cold water or saline.

Although the preceding description shows an example of producing a carbonic ester using a dialkyl tin alkoxide catalyst, deactivated forms of the dialkyl tin alkoxide catalyst are formed during the process for producing said carbonic ester. These deactivated forms of the dialkyltin alkoxide catalyst accumulate in the reaction system as the carbonic ester production process is repeated and may cause a decrease in the reaction rate or a decrease in the yield of carbonic ester. Therefore, it is preferable to partially remove the composition of the deactivated forms of the dialkyl tin alkoxide catalyst from the reaction system and regenerate the dialkyl tin catalyst from the specified composition of the deactivated forms. The regeneration of said composition of deactivated forms is preferably carried out in accordance with the aforementioned step (2) and / or step (3). There are no particular restrictions on the amount of said composition of deactivated forms recovered from the reaction system. In addition, there are also no specific restrictions on the number of deactivated forms of the dialkyl tin catalyst contained in said deactivated form composition.

The deactivated forms of the dialkyl tin catalyst recovered from the reaction system are regenerated as the dialkyl tin catalyst in the manner according to the embodiments of the present invention as described above, and then used as a catalyst to produce said carbonic ester. The regenerated dialkyltin catalyst is preferably used as the dialkyl tin catalyst in the aforementioned step (4) and / or step (1).

Figure 1 shows a flow chart of an improved method for producing a carbonic ester, which combines a method for producing a carbonic ester and a method for producing a dialkyltin compound according to embodiments of the present invention. As described previously, all or part of the reaction liquid is recovered from step (2) and / or step (3) of the carbonic acid ester preparation process and is used as the starting material of the present reaction (i.e., a composition of deactivated dialkyltin catalyst forms). Although it has been previously found that residual liquid is obtained in step (2), said residual liquid is used as a composition of deactivated forms in the present embodiment. At this time, the aforementioned step (A) is carried out since the dialkyltin alkoxide used in the carbonic ester production step is an alkoxide in which a group other than the tin-linked alkyl group referred to in the embodiments of the present invention is is an alkoxy group, and the pKa of the acid conjugated to said alkoxy group (i.e., an alcohol) is approximately 17. Although water and a carboxylic acid ester are obtained as by-products in step (A), these are by-products products are preferably removed at a suitable stage during the above step. It is more preferable to unload by-products from the system during stage (A). Alternatively, these by-products are removed from the system as gaseous components during the flushing of the system to cool the reaction liquid, followed by a redistribution of the alkyl groups. As described above, in the case of using acid in carrying out step (A) in the step of producing a carbonic ester using a dialkyltin alkoxide as a catalyst, there are cases where water is formed as a by-product, and since there are also cases where the starting materials and / or the products hydrolyze during the reaction, leading to the formation of a solid component, carboxylic anhydride is preferred as the compound used for the reaction (acid and / or acid anhydride). In addition, in the case of the reaction of an acid anhydride, a carboxylic acid ester formed from said acid anhydride and an alkoxy group is obtained as a by-product. The optimum carboxylic acid anhydride for easy removal of said carboxylic acid ester from the system is acetic anhydride. After completion of step (A), the redistribution reaction of the alkyl groups of the present invention is carried out by heat treatment. Then, in order to reuse the obtained dialkyltin compound as a catalyst for the step for producing the carbonyl ester as a dialkyltin alkoxide, the substituent of the dialkyltin compound is converted to an alkoxy group. At the indicated step of converting the substituent to an alkoxy group, a known synthesis method or method is used. For example, after obtaining dialkyltin oxide by carrying out the aforementioned step (I-1), the alkoxylation step explained below is carried out on said dialkyltin oxide to obtain an alkyltin alkoxide. The resulting alkyltin alkoxide is then reused, for example, in step (1) or step (4). In addition to the steps described above, a purification step and the like can be added.

Alkoxylation step (one aspect of step (I-2))

This step is a step of reacting an alcohol with a composition containing a dialkyltin oxide obtained in the previously described steps, followed by removing from the system water formed as a by-product that leads to the formation of dialkyltin alkoxide. This step is carried out in the same manner as the previously described step for the synthesis of alkyltin alkoxide in its preparation from dialkyltin oxide and alcohol. That is, this step is carried out using, as a starting material, the above composition containing dialkyltin oxide instead of dialkyltin oxide.

As described previously, since the redistribution reaction of the alkyl groups of the variants of the present invention is an equilibrium reaction, and based on the typical properties of the equilibrium reaction, the redistribution of the alkyl groups of the variants of the present invention is preferably carried out according to the method described above, where a composition of deactivated forms in which deactivated forms accumulate and / or concentrate to a high concentration (for example, a composition of deactivated forms, where the content of deactivated forms in which the number of alkyl groups bound to the tin atom of the alkyltin compound is an integer other than 2 with respect to the total number of moles of tin atoms of the alkyltin compound contained in the composition of the deactivated forms of the dialkyltin catalyst, expressed in mol% is 10 mol% or more, preferably 30 mol% or more and more preferably 50 mol% or more). That is, after obtaining a carbonic ester at the stage of producing a carbonic ester under such conditions that the content of the deactivated forms is in the above range, or after the active catalyst is returned from the composition of the deactivated forms, for example, by the method previously described by the authors of the present invention (see WO 2007 / 097388), a component containing a composition of highly concentrated deactivated forms is used as a composition of deactivated forms of variants of the present invention, thereby making extremely efficient use of the dialkyl tin catalyst is possible by adding the steps of the embodiments of the present invention.

The carbonic esters obtained in the above steps can preferably be used as starting materials for polycarbonates, starting materials for isocyanates, other chemical feedstocks, as an electrolyte for lithium batteries and the like. Using the proposed method can be solved the problems of costs and waste during the production of carbonic acid esters, since from deactivated forms of the catalyst based on dialkyltin, which were previously discarded, the catalyst can be regenerated. Therefore, the present invention is extremely important from the point of view of industrial production.

Examples

Although a more detailed explanation of examples of the present invention is provided below, embodiments of the present invention are not limited to the examples given.

In addition, analytical methods used in embodiments of the present invention are as follows.

Analytical methods

NMR analysis

Devices: JNM-A400 FT-NMR system manufactured by JEOL Ltd.

(1) Preparation of samples for analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR

Approximately 0.3 g of the sample solution is weighed, then approximately 0.7 g of deuterated chloroform (Aldrich Corp., 99.8%) and 0.05 g of tetramethyltin internal standard (Wako Pure Chemical Industries, Ltd., Wako Grade 1) are added. ) and use a homogeneous solution after stirring as a sample for NMR analysis.

(2) Quantitative analysis

Quantitative analysis is carried out on a sample for analysis using a calibration curve obtained by analysis of each standard substance.

Example 1

Stage (1-1). Obtaining a catalyst based on dialkyltin

627 g (2.7 mol) of dibutyltin oxide (Sankyo Organic Chemicals Co., Ltd., Japan) and 2000 g (22.7 mol) of 3-methyl-1-butanol (Kuraray Co., Ltd., Japan) are placed in 5000 ml pear-shaped volumetric flask. The flask is connected to an evaporator (R-144, Shibata Co., Ltd., Japan), to which an oil bath (OBH-24, Masuda Corp., Japan) equipped with a temperature controller, and a vacuum pump (G-50A, Ulvac Inc.) are connected. , Japan) and a vacuum regulator (VC-10S, Okano Seisakusho Co., Ltd., Japan). The outlet of the purge valve of said evaporator is connected to a line containing nitrogen gas at normal pressure. After closing the purge valve of the evaporator to reduce the pressure inside the system, the purge valve is gradually opened to allow nitrogen to enter the system and return to normal pressure. The temperature of the oil bath is set to approximately 145 ° C, the flask is immersed in the oil bath and the evaporator starts to rotate. After heating for about 40 minutes at atmospheric pressure of nitrogen, the evaporator is left open and the distillation of 3-methyl-1-butanol containing water begins. After maintaining in this state for 7 hours, the purge valve is closed, the pressure in the system is gradually reduced, and the excess of 3-methyl-1-butanol is distilled at a pressure in the system from 74 to 35 kPa. After distillation of the specified fraction, the flask is removed from the oil bath. The flask was allowed to cool to approximately room temperature (25 ° C), the purge valve was gradually opened and the pressure in the system restored to atmospheric. 1173 g of reaction liquid was obtained in the flask. An analysis of ¹¹⁹ Sn-, ¹ H- and ¹³ C-NMR determined that 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained in 99% yield, calculated on dibutyltin oxide. The same procedure is repeated 12 times to obtain a total of 10,345 g of 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane.

Stage (1-2). Preparation of carbonic ester and return of a composition of deactivated forms of a dialkyl tin catalyst

The carbonic ester is produced in continuous devices, such as those shown in FIG. 2. 1,1,3,3-Tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane obtained by the method described above is fed at a rate of 4388 g / h from line 4 to a column type reaction vessel 102 filled Metal Gauze CY Packing (Sulzer Chemtech Ltd., Switzerland) and having an internal diameter of 151 mm and an effective length of 5040 mm, and 3-methyl-1-butanol, purified on distillation column 101, is fed at a speed of 14953 g / h from pipeline 2. The temperature of the liquid inside the reaction vessel 102 is controlled to 160 ° C. by a heater and reboiler 112, and the pressure is adjusted to approximately 120 kPa-G by a tap, adjusting yuschim pressure. The residence time in the reaction vessel was approximately 17 minutes. 3-Methyl-1-butanol containing water, at a speed of 15037 g / h from the top of the reaction vessel through transfer line 6, and 3-methyl-1-butanol at a speed of 825 g / h through feed line 1, are pumped into a distillation column 101, filled with Metal Gauze CY Packing and equipped with a reboiler 111 and condenser 121 to perform distillation cleaning. In the upper part of the distillation column 101, a fraction containing a high concentration of water is condensed with a condenser 121 and returned from the return line 3. Purified 3-methyl-1-butanol is pumped into the column type reaction vessel 102 through a conduit 2 located at the bottom of the distillation column 101. An alkyltin alkoxide-based catalyst composition containing di-n-butyl bis (3-methylbutyloxy) tin and 1 , 1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane, obtained from the bottom of the reaction vessel 102 of the column type and fed to a thin film evaporator 103 (Kobelco Eco-Solutions Co., Ltd. , Japan) via transfer line 5. 3-Methyl-1-butanol is distilled off on a film evaporator 103 and returned to the column type reaction vessel 102 through a condenser 123, transfer line 8 and transfer line 4. The alkyl tin alkoxide catalyst composition is pumped from the bottom of the film evaporator 103 through line 7 and fed to the autoclave 104, adjusting the flow rate of di-n-butyl bis (3-methylbutyloxy) tin and 1,1,3,3-tetra-n -butyl-1,3-bis (3-methylbutyloxy) -distannoxane to about 5130 g / hour. Carbon dioxide is fed into the autoclave via line 9 at a speed of 973 g / h and the pressure in the autoclave is maintained at 4 MPa-G. The temperature in the autoclave was set to 120 ° C, the residence time was adjusted to 4 hours, and the carbon dioxide was reacted with the alkyltin alkoxide catalyst composition to obtain a reaction liquid containing bis (3-methylbutyl) carbonate. The resulting reaction liquid is transferred to a decarbonization tank 105 through line 10 and a control valve to remove the remaining carbon dioxide, and carbon dioxide is returned to line 11. Then, the reaction liquid is transferred to a film evaporator (Kobelco Eco-Solutions Co., Ltd., Japan) 106 for which a temperature of approximately 142 ° C. and a pressure of approximately 0.5 kPa are set via line 12 and 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane is fed at a flow rate up to approximately 4388 g / h to obtain a fraction containing bi c (3-methylbutyl) carbonate. On the other hand, the evaporation residue is circulated through a column type reaction vessel 102 through a transfer line 13 and a transfer line 4 while adjusting the flow rate of 1,1,3,3-tetrabutyl-1,3-bis (3-methylbutyloxy) distannoxane to approximately 4388 g / hour. The fraction containing bis (3-methylbutyl) carbonate is fed to a distillation column 107 filled with a Metal Gauze CY filler and equipped with a reboiler 117 and a condenser 127, through a condenser 126 and a transfer line 14 at a speed of 959 g / h, 99 masses are obtained by subsequent purification by distillation .% bis (3-methylbutyl) carbonate from line 16 return at a speed of 944 g / hour. When analyzing ¹¹⁹ Sn, ¹ H and ¹³ C-NMR of the alkyltin alkoxide catalyst composition from line 13, it was determined that it contains 1,1,3,3-tetra-n-butyl-1,3-bis (3 -methylbutyloxy) distannoxane but does not contain di-n-butyl bis (3-methylbutyloxy) tin. After performing the continuous operation described above for 240 hours, the alkyltin alkoxide-based catalyst composition is removed from the extraction line 16 at a rate of 18 g / h, 1,1,3,3-tetra-n-butyl-1,3-bis (3- methylbutyloxy) -distannoxane obtained by the above method is supplied from the feed line 17 at a rate of 18 g / h, and approximately 120 g of the catalyst composition 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) distanoxane is recovered from line 16. As a result of the analysis, ¹¹⁹ Sn-NMR, except for about 60 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutylox i) distannoxane, tri-n-butyl (3-methylbutyloxy) tin, the deactivated components of 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) distannoxane, which exhibit many chemical shifts, were detected, observed from -240 to -605 ppm The specified catalyst composition is used as a composition of deactivated forms.

Stage (1-3). Tri-n-butyl (3-methylbutyloxy) tin separation

120 g of the composition of the deactivated forms obtained in stage (1-2), transferred into a 500 ml pear-shaped flask. A three-way valve is attached to the flask, a distillation column filled with a 45 cm Helipack No. 3 with a fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer; the vessel is purged with nitrogen under reduced pressure. The nitrogen pressure in the vessel was brought to atmospheric pressure and the flask was immersed in an oil bath heated to approximately 190 ° C. After approximately 20 minutes, the pressure in the vessel is gradually reduced and the distilled components are returned when the temperature of the composition of the deactivated forms reaches approximately 180 ° C. Finally, distillation is stopped when the pressure in the vessel reaches approximately 0.01 kPa. The distillate and residue inside the flask were analyzed by ¹ H- and ¹¹⁹ Sn-NMR. The distillate is tri-n-butyl (3-methylbutyloxy) tin. The residue in the flask contains 76.5 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane and, according to ¹¹⁹ Sn-NMR, is a mixture of organotin compounds containing atoms tin, showing many chemical shifts from -240 to -605 ppm Received 25.5 g of distillate and 94.0 g of the residue in the flask.

Stage (1-4). Substitution reaction of substituents in deactivated forms of a dialkyl tin catalyst

24.7 g of the Tri-n-butyl (3-methylbutyloxy) tin obtained in step (1-3) are placed in a 300 ml pear-shaped flask under a nitrogen atmosphere, then 34.5 g of acetic anhydride is added (Aldrich Corp., USA ) and stirred for 1 hour at 25 ° C. Sampling the solution and analyzing it by gas chromatography confirm the formation of isoamyl acetate. A fractionation nozzle equipped with a reflux condenser connected to a receiver and a thermometer is attached to the flask, and after flushing the flask with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 50 ° C. The pressure inside the vessel is gradually reduced, isoamyl acetate and excess acetic anhydride are distilled off, and 22.8 g of a residue are obtained in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-butylacetoxytin.

At the same time, 93.2 g of a residue containing 76.5 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane obtained in stage (1-1 ), placed in a 500 ml metal autoclave (Model TSV-N2, Taiatsu Techno Corp., Japan), 150.0 g of acetic anhydride are added and mixed. The autoclave is then immersed in an oil bath heated to 200 ° C and heated for 3 hours. The autoclave is allowed to cool to a temperature close to room temperature (approximately 25 ° C), the contents are transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to a receiver and a thermometer is attached to the flask, and after flushing the flask with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 50 ° C. The pressure inside the vessel is gradually reduced, and the excess of acetic anhydride and the like. distilled off to obtain 103.3 g of a residue in a flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture containing di-n-butyldiacetoxytin and n-butyltriacetoxytin and the content of di-n-butylacetoxytin in the residue was 75.4 wt.%, While the content of n-butyltriacetoxytin is 24.5 wt.%. The resulting mixture is mixed with previously obtained tri-n-butylacetoxytin and used as a starting material in the next step (1-5).

Stage (1-5). Redistribution of alkyl groups

125.3 g of the Mixture obtained in stage (1-4), is placed in a 200 ml metal autoclave (Model TSV-N2, Taiatsu Techno Corp., Japan) in a nitrogen atmosphere. The autoclave is then immersed in an oil bath heated to 250 ° C and heated for 30 minutes. After the autoclave was allowed to cool to a temperature close to room temperature, 124.5 g of reaction liquid was recovered. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that the reaction liquid is a mixture containing di-n-butyldiacetoxytin and n-butyltriacetoxytin, and the content of di-n-butyldiacetoxytin in the mixture is 96.3 wt.%.

Stage (1-6). Alkoxylation of dialkyltin compounds

122.1 g of the Reaction liquid obtained in stage (1-5) is placed in a 500 ml pear-shaped volumetric flask, the flask is immersed in an oil bath heated to 50 ° C. By adding 300 ml of a 0.1 mol / L aqueous potassium hydroxide solution (Wako Pure Chemical Industries, Ltd.) and stirring the contents of the flask, a white precipitate formed. The mixture was filtered through filter paper and 82.1 g of a white precipitate was recovered.

81.1 g of a white precipitate and 238.0 g (2.70 mol) of 3-methyl-1-butanol are placed in a 500 ml pear-shaped volumetric flask. The flask is attached to a rotary evaporator, which is connected to an oil bath equipped with a temperature controller, with a vacuum pump and a vacuum controller. The outlet of the purge valve is connected to a line containing nitrogen gas at atmospheric pressure. After filling the system with nitrogen, the temperature of the oil bath is set to 146 ° C, the flask is immersed in the oil bath and it starts to rotate on a rotary evaporator. After distillation of the low-boiling component for approximately 7 hours in the presence of nitrogen at atmospheric pressure with an open purge valve, the pressure in the system is gradually reduced and the remaining low-boiling component is distilled off at an internal pressure of 76 to 30 kPa. As soon as the distillation of the low boiling component is no longer observed, the flask is removed from the oil bath and allowed to cool. 107.0 g of a liquid residue is obtained in a flask. When analyzing ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR, it was determined that the content of 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) distannoxane in the liquid residue in the flask was 96.4 wt.%.

Stage (1-7). The use of a regenerated dialkyltin-based catalyst in the production of carbonic ester

Production stage

A solution containing 96.5 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane obtained in stage (1-6), is fed from the supply line 17 with at a rate of 18 g / h, at the same time as the dialkyltin-based catalyst composition is removed from the extraction line 16 at a speed of 18 g / h at the stage of production of carbonic ester, which is explained in stages (1-2), 99 mass% bis (3 -methylbutyl) carbonate is recovered from the recovery line 15 at a rate of 944 g / h, and the effects of using the dialkyltin catalyst obtained in step (1-6) in the step and the production of carbonic ester is not confirmed.

Example 2

Stage (2-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

125 g of the composition of the deactivated forms obtained in the same manner as described in step (1-2) of example 1 are placed in a 500 ml pear-shaped flask under nitrogen, then 145.0 g of acetic anhydride is added and stirred for 1 hour at 25 ° C. After attaching the fractionation nozzle to the flask equipped with a reflux condenser connected to the distillate receiver and a thermometer, and after flushing the flask with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 50 ° C. The pressure inside the vessel is gradually reduced, the excess of acetic anhydride is distilled off and 125.9 g of the residue are obtained in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue is a mixture of tri-n-butylacetoxytin and di-n-butyldiacetoxytin, and according to ¹¹⁹ Sn-NMR, organotin compounds containing tin atoms exhibiting many chemical shifts from - 240 to -605 ppm The content of tri-n-butyl acetoxy tin in the mixture is 21.1 wt.%, While the content of di-n-butyl diacetoxy tin is 63.7 wt.%.

Stage (2-2). Redistribution of alkyl groups

123.7 g of the Mixture obtained in step (2-1) was placed in a 200 ml metal autoclave (Model TSV-N2, Taiatsu Techno Corp., Japan) in a nitrogen atmosphere. A metal autoclave is immersed in an oil bath heated to 250 ° C and heated for 30 minutes. After the autoclave was allowed to cool to a temperature close to room temperature, 122.9 g of reaction liquid was recovered. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that the reaction liquid is a mixture of organotin compounds containing di-n-butyldiacetoxytin, tri-n-butylacetoxytin and 1,1,3,3-tetra-n-butyl -1,3-diacetoxydistannoxane; and the content of di-n-butyl diacetoxy tin is 63.7 wt.%, the content of tri-n-butyl acetoxy tin is approximately 1 wt.%, and the content of 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistannoxane is 31.4 wt.%.

Stage (2-3). Alkoxylation of dialkyltin compounds

118.6 g of a Solution containing 91.0 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane, obtained in the same manner as in stage (1- 6) of example 1, except that 121.3 g of the mixture obtained in stage (2-2), 290 ml of a 0.1 mol / l aqueous solution of potassium hydroxide and 220.3 g of 3-methyl-1-butanol are used .

Example 3

Stage (3-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

130 g of the composition of the deactivated forms obtained in the same manner as used in step (1-2) of Example 1, and 100 g of toluene (guaranteed reagent, Wako Pure Chemical Industries, Ltd., Japan) are placed in a 500 ml pear-shaped flask. A Dean-Stark nozzle, a Dimrot refrigerator and a three-way valve are connected to a pear-shaped flask. A three-way valve is connected to a line through which nitrogen gas is supplied at normal pressure.

The flask is immersed in an oil bath preheated to 140 ° C, then the mixture with toluene is refluxed, making it possible to transfer gaseous hydrogen chloride into the flask at a rate of approximately 150 ml / min. Water is returned to the Dean-Stark trap along with boiling toluene, and the reaction is completed after it is carried out for 16 hours. After the flask was allowed to cool to approximately room temperature, the flask was purged with nitrogen for 3 hours. Toluene is distilled off from the resulting solution to obtain 120.4 g of a solution. In the analysis of ¹ H- and ¹¹⁹ Sn-NMR of this solution, it was determined that the solution was a mixture of tri-n-butylchloro tin and di-n-butyl dichloro tin, and the content of tri-n-butyl chloro tin was 17.1 wt.%, While the content di-n-butyldichlorotin is 64.2 wt.%.

Stage (3-2). Redistribution of alkyl groups

118.2 g of the Mixture obtained in step (3-1) was placed in a 300 ml double-walled Teflon vessel (registered trademark) (Model TAF-SR, Taiatsu Techno Corp., Japan) in a nitrogen atmosphere. The vessel is immersed in an oil bath heated to 250 ° C and heated for 15 hours. The vessel was allowed to cool to a temperature close to room temperature, and 116.9 g of the reaction liquid were recovered. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that the reaction liquid is a solution containing 93.1 wt.% Of di-n-butyldichlorotin.

Stage (3-3). Alkoxylation of dialkyltin compounds

119.1 g of a Solution containing 98.0 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained in the same manner as in step (1). -6) of Example 1, except that 115.9 g of the solution obtained in stage (3-2) are used instead of the solution obtained in stage (1-5) and 330 ml of a 0.1 mol / L aqueous solution potassium hydroxide and 292.2 g of 3-methyl-1-butanol.

Example 4

Stage (4-1). Dealkylation Reaction

150.0 g of the composition of the deactivated forms obtained in the same manner as in stage (1-2) of example 1, and 120.3 g of 1-decanol (guaranteed reagent, Wako Pure Chemical Industries, Ltd., Japan) are placed in 500- ml pear-shaped flask. A Dean-Stark nozzle, a Dimrot refrigerator and a three-way valve are connected to the flask. A three-way valve is connected to a line through which nitrogen gas is supplied at normal pressure.

The flask is immersed in an oil bath preheated to 250 ° C, then boiled with 1-decanol, allowing gaseous hydrogen chloride to enter the flask at a speed of approximately 150 ml / min. When the 1-decanol is boiled, water enters the Dean-Stark nozzle with it and the reaction ends after the reaction is completed for 15 hours. Then the flask was cooled to approximately room temperature, the flask was purged with nitrogen for 3 hours. 1-decanol is distilled off from the resulting solution to obtain 135.8 g of a solution. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained solution, it was determined that it contains 81.1 wt.% Of di-n-butyldichlorotin.

Stage (4-2). Separation of Dialkyltin Compounds

133.2 g of the Mixture obtained in stage (4-1) is placed in a 200 ml pear-shaped flask to which a fractionation nozzle is attached, equipped with a reflux condenser and connected to a distillate receiver and a thermometer. After replacing the gas inside the vessel with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 100 ° C. The pressure inside the vessel is gradually reduced to a final pressure of 1.3 kPa and 26.3 g of distillate and 106.3 g of residue are returned. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that it was di-n-butyldichlorotin.

Stage (4-3). Alkoxylation of dialkyltin compounds

106.1 g of 1,1,3,3-Tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane were obtained using the same method as in step (1-6) of Example 1, except the use of 105.5 g of di-n-butyldichlorotin obtained in stage (4-2), instead of the solution obtained in stage (1-3), and the use of 320 ml of 0.1 mol / l aqueous solution of potassium hydroxide and 287.8 g of a solution of 3-methyl-1-butanol.

Example 5

Stage (5-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

201.5 g of a Mixture of tri-n-butylacetoxytin, di-n-butyldiacetoxytin and organotin compounds containing tin atoms, exhibiting many chemical shifts from -240 to -605 ppm. according to ¹¹⁹ Sn-NMR, obtained by performing the same method as in stage (2-1) of example 2, except for using 200 g of the composition of deactivated forms obtained in the same way in stage (1-2) of example 1, and using 305.2 g of a mixture of 182.9 g of acetic acid and 124.4 g of acetic anhydride instead of 145.0 g of acetic anhydride. The content of tri-n-butyl acetoxy tin in the mixture is 20.1 wt.%, While the content of di-n-butyl diacetoxy tin is 64.1 wt.%.

Stage (5-2). Redistribution of alkyl groups

199.3 g of a Mixture containing di-n-butyl diacetoxy tin, tri-n-butyl acetoxy tin and 1,1,3,3-tetra-n-butyl-1,3-diacetoxydistannoxane are obtained using the same procedure as in the step ( 2-2) of example 2, with the exception of using 200.1 g of the mixture obtained in stage (5-1), instead of the mixture obtained in stage (2-1). The content of di-n-butyl diacetoxy tin in the mixture is 63.7 wt.%, The content of tri-n-butyl acetoxy tin is approximately 1 wt.%, And the content of 1,1,3,3-tetra-n-butyl-1,3- diacetoxydistannoxane is 32.3 wt.%.

Stage (5-3). Alkoxylation of dialkyltin compounds

184.7 g of a solution containing 95.6% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as in the step (1-4) of Example 1, except for using 198.3 g of the mixture obtained in step (5-2), 360 ml of a 0.1 mol / L aqueous solution of potassium hydroxide and 544.3 g of 3-methyl-1-butanol .

Example 6

Stage (6-1). Dealkylation Reaction

180 g of the composition of the deactivated forms obtained in the same manner as in stage (1-2) of example 1, is placed in a 500 ml pear-shaped flask in a nitrogen atmosphere, followed by the addition of 164.6 g of acetic acid and 280.0 g of acetic anhydride. The flask was immersed in an oil bath heated to 155 ° C, then stirred for 5 hours while boiling the solution under reflux. Then the flask was allowed to cool to room temperature, a fractionation nozzle equipped with a reflux condenser and connected to a distillate receiver and a thermometer was attached to the flask, and the flask was purged with nitrogen in a vacuum. After immersing the flask in an oil bath heated to 50 ° C, the pressure inside the vessel is gradually reduced and the excess of acetic acid and acetic anhydride are distilled off and 181.5 g of residue are obtained in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that it contains 84.8 wt.% Of di-n-butyldiacetoxytin.

Stage (6-2). Separation of Dialkyltin Compounds

180.0 g of a Solution containing 84.8 wt.% Of di-n-butyldiacetoxytin obtained in Step 6-1 is placed in a 300-ml pear-shaped flask and a fractionation nozzle equipped with a reflux condenser and connected to the distillate receiver is connected to the flask and a thermometer. After flushing the flask with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 180 ° C. The pressure inside the vessel is gradually reduced to a final pressure of 0.01 kPa and 150.3 g of distillate is isolated. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained distillate, it was determined that it was di-n-butyldiacetoxytin.

Stage (6-3). Dialkyltin-based catalyst regeneration from dialkyltin compounds

130.8 g of 1,1,3,3-Tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane are obtained using the same method as in step (1-6) of Example 1, except the use of 149.1 g of di-n-butyldiacetoxytin obtained in stage (6-2), instead of the reaction liquid obtained in stage (1-5), and the use of 350 ml of 0.1 mol / l aqueous solution of potassium hydroxide and 350, 9 g of 3-methyl-1-butanol.

Example 7

Stage (7-1). Obtaining a catalyst based on dialkyltin

972 g (2.7 mol) of di-n-octyltin oxide (Sankyo Organic Chemicals Co., Ltd., Japan) and 2100 g (23.9 mol) of 3-methyl-1-butanol are placed in a 5000 ml pear-shaped flask. The flask is connected to an evaporator, to which an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller is connected. The outlet of the evaporator purge valve is connected to a line containing nitrogen gas at normal pressure. After closing the purge valve of the evaporator to reduce the pressure inside the system, the purge valve is gradually opened to allow nitrogen to enter the system and return to normal pressure. The temperature of the oil bath is set to approximately 145 ° C, the flask is immersed in an oil bath and the evaporator starts to rotate. After heating for approximately 40 minutes at atmospheric nitrogen pressure and with the evaporator valve open, distillation of 3-methyl-1-butanol containing water begins. After being kept open for 7 hours, the valve is closed, the pressure in the system is gradually reduced, and excess 3-methyl-1-butanol is distilled off at a pressure in the system from 74 to 35 kPa. After the cessation of the appearance of the fraction, the flask is removed from the oil bath. After the flask is allowed to cool to approximately room temperature (25 ° C), the purge valve is gradually opened and the pressure in the system rises to atmospheric. 1176 g of reaction liquid are obtained in the flask. An analysis of ¹¹⁹ Sn-, ¹ H- and ¹³ C-NMR determined that 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained in 99% yield, calculated on di-n-octyltin oxide. Then the same procedure is repeated 12 times to obtain a total of 14120 g of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane.

Stage (7-2). Production of carbonic ester and return of the composition of deactivated forms of the catalyst based on dialkyltin

The carbonic ester is obtained in a continuous apparatus similar to that shown in FIG. 2. 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane obtained by the method described above is fed at a rate of 5887 g / hour from transfer line 4 to a column type reaction vessel 102, filled with Metal Gauze CY Packing (Sulzer Chemtech Ltd., Switzerland) having an internal diameter of 151 mm and an effective length of 5040 mm, and 3-methyl-1-butanol, purified in a distillation column 101, is fed at a speed of 14953 g / h from line 2 transfer. The temperature of the liquid in the reaction vessel 102 was adjusted to 160 ° C. with a heater and reboiler 112, and the pressure was adjusted to approximately 120 kPa-G using a pressure regulating valve. The residence time in the reaction vessel is approximately 17 minutes. 3-Methyl-1-butanol containing water, at a speed of 15037 g / h from the top of the reaction vessel through transfer line 6 and 3-methyl-1-butanol at a speed of 824 g / h through feed line 1, are pumped into distillation column 101 filled with Metal Gauze CY Packing and equipped with a reboiler 111 and a condenser 121, and distillation cleaning is performed. In the upper part of the distillation column 101, a fraction with a high concentration of water is condensed by a condenser 121 and returned from the return line 3. The purified 3-methyl-1-butanol is pumped into the column type reaction vessel 102 through a transfer line 2 located at the bottom of the distillation column 101. An alkyltin alkoxide catalyst composition comprising di-n-octyl bis (3-methylbutyloxy) tin and 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane, obtained from the bottom of the reaction vessel 102 of the column type and fed to a thin-film evaporator 103 via transfer line 5. 3-Methyl-1-butanol is distilled off on a thin-film evaporator 103 and returned to the column type reaction vessel 102 through a condenser 123, transfer line 8 and transfer line 4. The alkyl tin alkoxide catalyst composition is pumped from the bottom of the thin film evaporator 103 through a transfer line 7 and fed to the autoclave 104, while the flow rate of di-n-octyl bis (3-methylbutyloxy) tin and 1,1,3,3- tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane to about 6627 g / hour. Carbon dioxide is fed into the autoclave via transfer line 9 at a speed of 973 g / h and the pressure in the autoclave is maintained at 4 MPa-G. The temperature was set in an autoclave to 120 ° C., the residence time was adjusted to about 4 hours, the carbon dioxide was reacted with the alkyltin alkoxide catalyst composition, and a reaction liquid containing bis (3-methylbutyl) carbonate was obtained. The reaction liquid is transferred to a decarbonization tank 105 through a transfer line 10, and a control valve to remove carbon dioxide residue and carbon dioxide are returned from the transfer line 11. The reaction liquid is then transferred to a thin film evaporator 106 (approximately 142 ° C. and approximately 0.5 kPa), via transfer line 12, and fed by adjusting the flow rate of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane to about 5887 g / hr, and a fraction containing bis (3-methylbutyl) carbonate is obtained. On the other hand, the evaporation residue is circulated in a column type reaction vessel 102 through a transfer line 13 and a transfer line 4 while controlling the flow rate of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane to about 5887 g / hour. The fraction containing bis (3-methylbutyl) carbonate is fed to a distillation column 107 filled with Metal Gauze CY packing and equipped with a reboiler 117 and condenser 127 through condenser 126 via transfer line 14 at a speed of 959 g / hr, followed by purification by distillation to obtain 99 mass .% bis (3-methylbutyl) carbonate from the return line 15 at a speed of 944 g / h. When analyzing ¹¹⁹ Sn-, ¹ H- and ¹³ C-NMR of the alkyltin alkoxide-based catalyst composition in transfer line 13, it was determined that it contains 1,1,3,3-tetra-n-octyl-1,3-bis ( 3-methylbutyloxy) distannoxane but does not contain di-n-octyl bis (3-methylbutyloxy) tin. After performing the aforementioned continuous operation for approximately 240 hours, the alkyltin alkoxide-based catalyst composition is removed from the extraction line 16 at a rate of 18 g / h, 1,1,3,3-tetra-n-octyl-1,3-bis (3- methylbutyloxy) distanoxane obtained by the above method is supplied from the feed line 17 at a rate of 18 g / h, and 200 g of a composition of deactivated forms 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distanoxane is removed from extraction line 16. When analyzing ¹¹⁹ Sn-NMR, it was determined that along with 60 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane and tri-n-octyl (3- methyl butyloxy) tin, the deactivated components of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane were detected, exhibiting many chemical shifts from -240 to -605 ppm. The resulting catalyst composition is used as a composition of deactivated forms.

Stage (7-3). Exchange of substituents of deactivated forms of a dialkyltin catalyst

201.2 g of a Mixture of tri-n-octylacetoxytin, di-n-octyldiacetoxytin and organotin compounds containing tin atoms showing chemical shifts from -240 to -605 ppm. according to ¹¹⁹ Sn-NMR, obtained by performing the same method as in stage (2-1) of example 2, except for using 200 g of the composition of deactivated forms obtained in stage (7-2), instead of the composition of deactivated forms obtained in stage (1-2), and the use of 231.0 g of acetic anhydride. The content of tri-n-octyl acetoxy tin in the mixture is 23.4 wt.%, While the content of di-n-octyl diacetoxy tin is 62.8 wt.%.

Stage (7-4). Redistribution of alkyl groups

197.3 g of the reaction liquid was returned using the same method as described for step (2-1) of Example 2, except for using 199.3 g of the mixture obtained in step (7-3) instead of the mixture obtained in step ( 2-1). When analyzing ¹¹⁹ Sn- and ¹ H-NMR of the obtained reaction liquid, it was determined that it is a mixture that contains di-n-octyldiacetoxytin, tri-n-octylacetoxytin and 1,1,3,3-tetra-n-octyl- 1,3-diacetoxydistannoxane, and the content of di-n-octyl diacetoxy tin is 62.5 wt.%, The content of tri-n-octyl acetoxy tin is approximately 3 wt.%, And the content of 1,1,3,3-tetra-n-octyl- 1,3-diacetoxydistannoxane is 32.0% by weight.

Stage (7-5). Alkoxylation of dialkyltin compounds

181.0 g of a Solution containing 95.2% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as in the step (1-6) of Example 1, with the exception of using 194.4 g of the mixture obtained in stage (7-4), instead of the mixture obtained in stage (1-5), and using 290 ml of a 0.1 mol / L aqueous solution potassium hydroxide and 297.6 g of 3-methyl-1-butanol.

Example 8

Stage (8-1). Dealkylation Reaction

225.7 g of the Mixture containing 85.8 wt.% Of di-n-octyldiacetoxytin are obtained by carrying out the same method as described for step (6-1) of Example 6, except for using 230 g of the composition of deactivated forms obtained by the same by the method as in step (7-2) of Example 7, instead of the composition of the deactivated forms obtained in step (1-2) of Example 1 and using 158.0 g of acetic acid and 283.5 g of acetic anhydride.

Stage (8-2). The separation of dialkyl forms

191.9 g of distillate is obtained by carrying out the same method as described for step (6-2) of Example 6, except for using 224.1 g of a mixture containing 85.8 wt.% Of di-n-octyldiacetoxytin obtained in step ( 8-1). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained distillate, it was determined that the distillate was di-n-octyldiacetoxytin.

Stage (8-3). Alkoxylation of dialkyltin compounds

175.4 g of 1,1,3,3-Tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane were prepared using the same procedure as described for step (1-6) of Example 1, except the use of 190.0 g of di-n-octyldiacetoxytin obtained in stage (8-2), instead of the mixture obtained in stage (1-5) of example 1, and the use of 334 ml of 0.1 mol / l aqueous solution of potassium hydroxide and 280 6 g of 3-methyl-1-butanol.

Example 9

Stage (9-1). Dealkylation Reaction

191.4 g of a mixture containing 86.2 wt.% Of di-n-octyldiacetoxytin are obtained by performing the same method as described for step (6-1) of Example 6, except for using 195 g of a composition of deactivated forms prepared in the same manner. by the method as in step (7-2) of Example 7, instead of the composition of the deactivated forms obtained in step (1-2) of Example 1 and using 271.1 g of acetic anhydride (but no acetic acid is used).

Stage (9-2). The separation of dialkyl forms

184.6 g of distillate is obtained by carrying out the same method as described for step (6-2) of Example 6, except for using 190.2 g of a mixture containing 86.2 wt.% Of di-n-octyldiacetoxytin obtained in step ( 9-1), and temperatures of 200 ° C. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained distillate, it was determined that the distillate was di-n-octyldiacetoxytin.

Stage (9-3). Alkoxylation of dialkyltin compounds

166.7 g of 1,1,3,3-Tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane was prepared using the same procedure as described for step (1-6) of Example 1, except using 181.2 g of di-n-octyldiacetoxytin obtained in step (9-2); using 292 ml of 0.1 mol / L aqueous potassium hydroxide solution and 266.7 g of 3-methyl-1-butanol.

Example 10

Stage (10-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

221.3 g Mixtures of tri-n-octylacetoxytin, di-n-octyldiacetoxytin and organotin compounds containing tin atoms, which give many chemical shifts in the range from -240 to -605 ppm. according to ¹¹⁹ Sn-NMR, obtained by performing the same method as described for stage (7-3) of example 7, except for using 220 g of the composition of deactivated forms obtained in the same manner as in stage (7-2) of example 7 and using a mixture of 403.2 g of 150.1 g of acetic acid and 255.4 g of acetic anhydride instead of acetic anhydride. The content of tri-n-octyl acetoxy tin in the resulting mixture was 22.8 wt.%, While the content of di-n-octyl diacetoxy tin was 62.2 wt.%.

Stage (10-2). Redistribution of alkyl groups

218.8 g of the reaction liquid was obtained using the same method as described for step (7-4) of Example 7, except for using 220.1 g of the mixture obtained in step (10-1) instead of the mixture obtained in step ( 7-3) of Example 7. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained reaction liquid, it was determined that the reaction liquid is a mixture containing di-n-octyldiacetoxytin, tri-n-octylacetoxytin and 1,1,3,3 -tetra-n-octyl-1,3-diacetoxydistannoxane; and the content of di-n-octyl diacetoxy tin is 62.7 wt.%, the content of tri-n-octyl acetoxy tin is approximately 3 wt.%, and the content of 1,1,3,3-tetra-n-octyl-1,3-diacetoxydistannoxane is 31.8 wt.%.

Stage (10-3). Alkoxylation of dialkyltin compounds

200.4 g of a solution containing 95.2% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of Example 1, except for using 215.8 g of the mixture obtained in (10-2), instead of the mixture obtained in (1-5) of Example 1, and using 277 ml of 0.1 mol / L an aqueous solution of potassium hydroxide and 328.5 g of 3-methyl-1-butanol.

Example 11

Stage (11-1). Tri-n-octyl (3-methylbutyloxy) tin separation

130 g of the composition of the deactivated forms obtained in the same manner as in stage (7-2) of example 7 are placed in a 500 ml pear-shaped flask to which a three-way valve is attached, a distillation column filled with Helipack No. 3, 45 cm long, nozzle for fractionation, equipped with a reflux condenser connected to a distillate receiver and a thermometer, the vessel is filled with nitrogen in a vacuum. The nitrogen pressure in the vessel was brought to atmospheric pressure and the flask was immersed in an oil bath heated to approximately 230 ° C. After approximately 20 minutes, the pressure inside the vessel is gradually reduced and the distilled components are returned when the temperature of the composition of the deactivated forms reaches approximately 210 ° C. Finally, distillation is stopped when the pressure in the vessel reaches approximately 0.01 kPa. The distillate and residue in the flask were analyzed by ¹ H- and ¹¹⁹ Sn-NMR. The distillate is tri-n-octyl (3-methylbutyloxy) tin. The residue in the flask contains 77.2 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane and, as determined by ¹¹⁹ Sn-NMR, is a mixture of organotin compounds containing tin atoms, showing many chemical shifts from -240 to -605 ppm The result is 28.9 g of distillate and 100.1 g of the residue in the flask.

Stage (11-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

27.4 g of the Tri-n-octyl (3-methylbutyloxy) tin obtained in step (11-1) are placed in a 300 ml pear-shaped flask, then 27.2 g of acetic anhydride are added and stirred for 1 hour at 25 ° C. A fractionation nozzle is attached to the flask, equipped with a reflux condenser connected to the distillate receiver and a thermometer, and after filling the system with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced and the excess of acetic anhydride, etc. distilled off to obtain 25.9 g of a residue in a flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-octylacetoxytin.

On the other hand, 99.4 g of a residue containing 77.2 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane obtained in stage (11-1 ), placed in a 500 ml metal autoclave and 121.6 g of acetic anhydride are added with stirring. Then, a metal autoclave is immersed in an oil bath heated to 200 ° C and heated for 3 hours. After the metal autoclave was allowed to cool to approximately room temperature (approximately 25 ° C), the contents of the autoclave were transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the flask is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 50 ° C. The pressure inside the autoclave is gradually reduced and isoamyl acetate and excess acetic anhydride are distilled off to obtain 107.2 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture containing di-n-octyldiacetoxytin and n-octyltriacetoxytin, and the content of di-n-octyldiacetoxytin in the residue was 77.8 wt.%, While the content of n-octyltriacetoxytin is 22.1 wt.%. The resulting mixture is mixed with the previously obtained tri-n-octylacetoxytin and used as a starting material in the next step (11-3).

Stage (11-3). Redistribution of alkyl groups

131.0 g of the reaction liquid are returned using the same method as in step (1-5) of Example 1 under a nitrogen atmosphere, except that instead of the mixture obtained in step (1-4), 132.1 are used g of the mixture obtained in stage (11-2). In the analysis, ¹ H- and ¹¹⁹ Sn-NMR spectrum of the reaction liquid was determined that the reaction liquid is a mixture containing di-n-n-oktildiatsetoksiolovo oktiltriatsetoksiolovo, and the content of di-n-oktildiatsetoksiolova in the mixture was 95.1 wt.% .

Stage (11-4). Alkoxylation of dialkyltin compounds

120.0 g of a Solution containing 94.4% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of Example 1, except for using 130.1 g of the reaction liquid obtained in stage (11-3), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 312 ml of aqueous 0.1 mol / L potassium hydroxide solution and 194.3 g of 3-methyl-1-butanol.

Example 12

Stage (12-1). Tri-n-octyl (3-methylbutyloxy) tin separation

33.2 g of distillate and 109.0 g of the residue in the flask were obtained using the same method as described for step (11-1) of Example 11, except for using 143 g of the composition of deactivated forms obtained by the same method as in steps (7-2) of Example 7. When analyzing ¹ H- and ¹¹⁹ Sn-NMR, it was determined that the distillate was tri-n-octyl (3-methylbutyloxy) tin, and the residue in the flask was a mixture containing 78.1 wt.% 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane and organotin compounds containing tin atoms, demonstrator ruyuschie plurality of chemical shifts of from -240 to -605 ppm according to ¹¹⁹ Sn-NMR.

Stage (12-2). Dialkyltin-based catalyst substitution reaction

32.1 g of the Tri-n-octyl (3-methylbutyloxy) tin obtained in step (12-1) is placed in a 300 ml pear-shaped flask, followed by the addition of 23.2 g of acetic anhydride and 17.7 g of acetic acid and stirring for 1 hour at 25 ° C. Sampling of the solution and analysis by gas chromatography confirmed that isoamyl acetate was formed. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced, isoamyl acetate and an excess of acetic anhydride are distilled off, to obtain 30.5 g of a residue in a flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-octylacetoxytin.

At the same time, 108.8 g of a residue containing 78.1 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane obtained in stage (12-1 ), placed in a 500 ml metal autoclave, then 121.6 g of acetic anhydride and 78.5 g of acetic acid are added and mixed. Then the metal autoclave is immersed in an oil bath heated to 200 ° C and heated for 3 hours. The autoclave was allowed to cool to approximately room temperature (approximately 25 ° C), then its contents were transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, immersing the flask in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced, isoamyl acetate and excess acetic anhydride are distilled off, and 117.2 g of a residue are obtained in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue in the flask, it was determined that the residue was a mixture containing di-n-octyldiacetoxytin and n-octyltriacetoxytin and the content of di-n-octyldiacetoxytin in the residue was 77.6 wt.%, while the content of n-octyltriacetoxytin is 22.3 wt.%. The resulting mixture is mixed with the previously obtained tri-n-octylacetoxytin and used as a starting material in the next step (12-3).

Stage (12-3). Redistribution of alkyl groups

145.3 g of the reaction liquid are returned using the same method as described for step (1-5) of example 1 under a nitrogen atmosphere, except that instead of the mixture obtained in step (1-4) of example 1, 146 is used 5 g of the mixture obtained in stage (12-2). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained reaction liquid, it was determined that the reaction liquid was a mixture of di-n-octyldiacetoxytin and n-octyltriacetoxytin, and the content of di-n-octyldiacetoxytin in the mixture was 95.5 wt.%.

Stage (12-4). Dialkyltin-based catalyst regeneration from dialkyltin compounds

129.1 g of a Solution containing 94.7% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (methylbutyloxy) -distannoxane was obtained using the same method as described for step (1) -6) of example 1, except that instead of the reaction liquid obtained in stage (1-5) of example 1, 144.3 g of the reaction liquid obtained in stage (12-3), 322 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 212.8 g of 3-methyl-1-butanol.

Example 13

Stage (13-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

227.2 g of a Mixture of tri-n-octylpropionyloxytin, di-n-octyldipropionyloxytin and organotin compounds containing tin atoms, exhibiting many chemical shifts from -240 to -605 ppm. according to ¹¹⁹ Sn-NMR, obtained in the same manner as described for stage (2-1) of example 2, except that instead of the composition of the deactivated forms obtained in stage (1-2) of example 1, 215 g of the composition of deactivated forms are used obtained in the same way as in stage (7-2) of example 7, and instead of acetic anhydride, 317.9 g of propionic anhydride are used. The content of tri-n-octylpropionyloxytin in the mixture is 22.8 wt.%, While the content of di-n-octyldipropionyloxytin is 63.4 wt.%.

Stage (13-2). Redistribution of alkyl groups

222.5 g of the reaction liquid was returned using the same method as described for step (2-1) of Example 2, except that instead of the mixture obtained in step (2-1), 223.2 g of the mixture obtained was used. at the stage of (13-1). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained reaction liquid, it was determined that the reaction liquid is a mixture containing di-n-octyldipropionyloxytin, tri-n-octylpropionyloxytin and 1,1,3,3-tetra-n-octyl-1 , 3-dipropionyloxydistannoxane, and the content of di-n-octyldipropionyloxytin is 63.0 wt.%, The content of tri-n-octylpropionyloxytin is approximately 5 wt.% And the content of 1,1,3,3-tetra-n-octyl-1, 3-dipropionyloxydistannoxane is 30.0 wt.%.

Stage (13-3). Alkoxylation of dialkyltin compounds

192.3 g of a Solution containing 92.8% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, except that instead of the mixture obtained in stage (1-6) of example 1, 221.8 g of the mixture obtained in stage (13-2), 322 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 298.8 g of 3-methyl-1-butanol.

Example 14

Stage (14-1). Dealkylation Reaction

238.7 g of a Mixture containing 86.0 wt.% Of di-n-octyldipropionyloxytin was obtained by carrying out the same method as described for step (6-1) of Example 6, except that instead of the deactivated form composition obtained in stage (1-2) of example 1, use 230 g of the composition of the deactivated forms obtained in the same manner as in stage (7-2) of example 7, instead of acetic acid, 195.2 g of propionic acid are used and 340 instead of acetic anhydride are used, 2 g of propionic anhydride.

Stage (14-2). Dialkyl Form Department

191.9 g of distillate was obtained by the same method as described for step (6-2) of Example 6, except that 237.1 g of a mixture containing 86.0 wt.% Of di-n-octyldipropionyloxytin obtained at the stage (14-1), and maintain the temperature of 200 ° C. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained distillate, it was determined that the distillate was di-n-octyldiacetoxytin.

Stage (14-3). Alkoxylation of dialkyltin compounds

211.3 g of a Mixture containing 84.5 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of Example 1, with the exception of using 237.1 g of a mixture containing 86.0 wt.% Of di-n-octyldipropionyloxytin obtained in stage (14-1), instead of the reaction liquid obtained in stage (1-5 ) of Example 1, and using 396 ml of a 0.1 mol / L aqueous solution of potassium hydroxide and 354.5 g of 3-methyl-1-butanol.

Example 15

Stage (15-1). Tri-n-octyl (3-methylbutyloxy) tin separation

43.1 g of distillate and 146.1 g of the residue in the flask were obtained using the same method as described for step (11-1) of Example 11, except that 190 g of the composition of the deactivated forms obtained in the same manner were used as and in step (7-2) of Example 7. A ¹ H- and ¹¹⁹ Sn-NMR analysis ^{of the} obtained distillate and residue in the flask was carried out. The distillate was determined to be tri-n-octyl (3-methylbutyloxy) tin. The remainder in the flask was determined to be a mixture containing 77.6 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane and organotin compounds containing atoms tin, showing many chemical shifts in the region from -240 to -605 ppm according to ¹¹⁹ Sn-NMR.

Stage (15-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

42.2 g of the Tri-n-octyl (3-methylbutyloxy) tin obtained in step (15-1) are placed in a 300 ml pear-shaped flask, then 28.7 g of propionic acid and 51.5 g of propionic anhydride are added and stirred for 1 hour at 25 ° C. Sampling of the solution and analysis by gas chromatography confirm that isoamyl propionate is formed. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced, and isoamyl propionate, an excess of propionic acid and propionic anhydride, are distilled off to obtain 41.1 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained residue, it was determined that the residue was tri-n-octylpropionyloxytin.

At the same time, 145.1 g of a residue containing 77.6 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane obtained in stage (15-1 ) is placed in a 500 ml metal autoclave, then 128.9 g of propionic acid and 226.7 g of propionic anhydride are added and mixed. The metal autoclave is then immersed in an oil bath heated to 200 ° C. and heated for 4 hours. Allow the autoclave to cool to approximately room temperature (approximately 25 ° C) and transfer its contents to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced, and the excess of propionic acid and propionic anhydride are distilled off to obtain 167.7 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained residue, it was determined that the residue was a mixture containing di-n-octyldipropionyloxytin and n-octyltropionyloxytin and the content of di-n-octyldipropionyloxytin in the residue was 77.0 wt.%, Then as the content of n-octyltropropionyloxytin is 22.4 wt.%. The resulting mixture is mixed with the previously obtained tri-n-octylpropionyloxytin and used as a feedstock in the next step (15-3).

Stage (15-3). Redistribution of alkyl groups

205.9 g of the reaction liquid is returned by carrying out in the nitrogen atmosphere the same method as described for stage (1-5) of example 1, except for using 207.2 g of the mixture obtained in stage (15-2), instead of the mixture obtained at the stage (1-4) of example 1. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained reaction liquid, it was determined that the reaction liquid is a mixture of di-n-octyldipropionyloxytin and the content of di-n-octyldipropionyloxytin in the mixture is 91.0 wt.%.

Stage (15-4). Alkoxylation of dialkyltin compounds

171.5 g of a Solution containing 90.8% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, except for using 204.6 g of the reaction liquid obtained in stage (15-3), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 332 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 284.1 g of 3-methyl-1-butanol.

Example 16

Stage (16-1). Obtaining a catalyst based on dialkyltin

893 g (2.48 mol) of di-n-octyltin oxide (Sankyo Organic Chemicals Co., Ltd., Japan) and 2403 g (23.6 mol) of 2-ethyl-1-butanol are placed in a 5000 ml pear-shaped flask. The flask is connected to an evaporator to which an oil bath is attached, equipped with a temperature controller, a vacuum pump and a vacuum controller. The outlet of the purge valve of said evaporator is connected to a line containing nitrogen gas supplied at normal pressure. After closing the purge valve of the evaporator to reduce the pressure inside the system, the purge valve is gradually opened to allow nitrogen to enter the system and return to normal pressure. The temperature of the oil bath was set to approximately 165 ° C, the flask was immersed in an oil bath and the evaporator started to rotate. After heating for about 40 minutes at atmospheric pressure of nitrogen, the evaporator is left open and the distillation of 2-ethyl-1-butanol containing water begins. After maintaining in this state for 7 hours, the purge valve is closed, the pressure in the system is gradually reduced, and the excess of 2-ethyl-1-butanol is distilled at a pressure in the system from 74 to 35 kPa. After distillation of the specified fraction, the flask is removed from the oil bath. The flask was allowed to cool to approximately room temperature (25 ° C), the purge valve was gradually opened and the pressure in the system restored to atmospheric. 1114 g of reaction liquid was obtained in a flask. An analysis of ¹¹⁹ Sn-, ¹ H- and ¹³ C-NMR determined that 1,1,3,3-tetra-n-octyl-1,3-bis (3-ethylbutyloxy) -distannoxane was obtained in 99% yield, calculated on di-n-octyltin oxide. The described procedure is repeated 12 times and a total of 13380 g of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane is obtained.

Stage (16-2). Obtaining carbonic ester and returning the composition of deactivated forms of the catalyst based on dialkyltin

The carbonic ester is obtained in continuous devices similar to those shown in FIG. 2, 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane obtained by the method described above is fed with 6074 g / h from transfer line 4 to a column type reaction vessel 102 filled with Metal Gauze CY Packing with a diameter of 151 mm and an effective length of 5040 mm, and 2-ethyl-1-butanol, purified in a distillation column 101, is fed at a speed of 12260 g / hour from line 2 transfer. The temperature of the liquid inside the reaction vessel 102 was maintained at 160 ° C. with a heater and reboiler 112, and the pressure was adjusted to approximately 120 kPa-G by a pressure regulating valve. The residence time in the reaction vessel is approximately 17 minutes. For distillation purification, a 2-ethyl-1-butanol containing water is pumped from the top of the reaction vessel at a rate of 12344 g / hour through a transfer line 6 to a distillation column 101 filled with Metal Gauze CY Packing and equipped with a reboiler 111 and a condenser 121. 2-ethyl-1-butanol at a rate of 958 g / h via feed line 1. In the upper part of the distillation column 101, a fraction containing high concentration of water is condensed by a condenser 121 and returned from the return line 3. The purified 2-ethyl-1-butanol is pumped to a column type reaction vessel 102 through a transfer line 2 located at the bottom of the distillation column 101. An alkyltin alkoxide catalyst composition comprising di-n-octyl bis (2-ethylbutyloxy) tin and 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane, obtained from the bottom of the reaction vessel 102 of the column type and fed to a thin-film evaporator 103 via transfer line 5. 2-Ethyl-1-butanol is distilled off in a thin film evaporator 103 and returned to the column type reaction vessel 102 through a condenser 123, transfer line 8 and transfer line 4. The alkyltin alkoxide catalyst composition is pumped from the bottom of the thin film evaporator 103 through a transfer line 7 and fed to the autoclave 104, while the flow rate of di-n-octyl bis (2-ethylbutyloxy) tin and 1,1,3,3- tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane to about 6945 g / hour. Carbon dioxide is fed into the autoclave via transfer line 9 at a speed of 973 g / h and the pressure in the autoclave is maintained at 4 MPa-G. The temperature was set in an autoclave to 120 ° C, the residence time in the reaction vessel was adjusted to approximately 4 hours, the carbon dioxide was reacted with the alkyltin alkoxide composition to produce a reaction liquid containing bis (2-ethylbutyl) carbonate. The resulting reaction liquid is transferred to a decarbonization tank 105 through a transfer line 10 and a control valve to remove the remaining carbon dioxide and carbon dioxide are returned from the transfer line 11. The reaction liquid is then transferred to a thin film evaporator 106, where a temperature of approximately 142 ° C. and a pressure of approximately 0.5 kPa are set, and 1,1,3,3-tetra-n-octyl-1,3-bis is transferred via transfer line 12 ( 2-ethylbutyloxy) -distannoxane, adjusting the flow rate to approximately 6074 g / hr, and a fraction containing bis (2-ethylbutyl) carbonate is obtained. On the other hand, the evaporation residue is circulated through the column type reactor 102 via transfer line 13 and transfer line 14, while the flow rate of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) is adjusted ) distannoxane to about 6074 g / hour. The fraction containing bis (2-ethylbutyl) carbonate is fed to a distillation column 107 filled with a Metal Gauze CY filler and equipped with a reboiler 117 and a condenser 127, through a condenser 126 and a transfer line 14 at a speed of 959 g / hour, followed by purification by distillation to obtain 99 wt.% bis (2-ethylbutyl) carbonate from line 16 return at a speed of 1075 g / hour. When analyzing ¹¹⁹ Sn-, ¹ H- and ¹³ C-NMR of the alkyltin alkoxide-based catalyst composition in transfer line 13, it was determined that it contains 1,1,3,3-tetra-n-octyl-1,3-bis ( 2-ethylbutyloxy) -distannoxane, but does not contain di-n-octyl-bis (2-ethylbutyloxy) tin. After performing the aforementioned continuous operation for 220 hours, the alkyltin alkoxide-based catalyst composition is removed from the extraction line 16 at a rate of 18 g / h, 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy ) the distanoxane obtained by the above method is fed from the feed line 17 at a rate of 18 g / h and 180 g of a catalyst composition based on 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy ) distanoxane is removed from extraction line 16. An analysis of ¹¹⁹ Sn-NMR determined that along with approximately 55 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane and tri-n-octyl (2 There are many NMR peaks of the deactivated components of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane with chemical shifts in the range from -240 to -605 ppm. The resulting catalyst composition is used as a composition of deactivated forms.

Stage (16-3). Exchange of substituents of deactivated forms of a dialkyltin catalyst

174.5 g of a Mixture of tri-n-octylacetoxytin, di-n-octyldiacetoxytin and organotin compounds containing tin atoms, exhibiting many chemical shifts from -240 to -605 ppm. according to ¹¹⁹ Sn-NMR, obtained by performing the same method as described for stage (2-1) of example 2, except for using 180 g of the composition of the deactivated forms obtained in stage (16-2), instead of the composition of the deactivated forms obtained in stage (1-2) of example 1, and the use of 202.1 g of acetic anhydride. The content of tri-n-octyl acetoxy tin in the mixture is 26.4 wt.%, And the content of di-n-octyl diacetoxy tin is 57.9 wt.%.

Stage (16-4). Redistribution of alkyl groups

172.0 g of the reaction liquid was returned using the same method as described for step (2-1) of example 2, except that instead of the mixture obtained in step (2-1) of example 2, 173.1 g of the mixture was used obtained in stage (16-3). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained reaction liquid, it was determined that the reaction liquid is a mixture containing di-n-octyldiacetoxytin, tri-n-octylacetoxytin and 1,1,3,3-tetra-n-octyl- 1,3-diacetoxydistannoxane; and the di-n-octyl diacetoxytin content in the mixture is 57.8% by weight, the tri-n-octyl acetoxytin content is about 3% by weight, and the content of 1,1,3,3-tetra-n-octyl-1,3- diacetoxydistannoxane is 37.8 wt.%.

Stage (16-5): Alkoxylation of dialkyltin compounds

165.2 g of a Solution containing 95.6% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, except that instead of the reaction liquid obtained in stage (1-5) of example 1, 171.1 g of the mixture obtained in stage (16-4) are used, and 255 ml of 0 are also used 1 mol / L aqueous potassium hydroxide solution and 303.7 g of 2-ethyl-1-butanol.

Example 17

Stage (17-1). Dealkylation Reaction

202.6 g of the Mixture containing 83.8 wt.% Of di-n-octyldiacetoxytin is obtained using the same method as described for step (6-1) of Example 6, except that 215 g of the composition of the deactivated forms are used, obtained in the same manner as described for stage (16-2) of example 16, instead of the composition of the deactivated forms obtained in stage (1-2) of example 1, 141.9 g of acetic acid and 241.2 g of acetic anhydride are also used.

Stage (17-2). Dialkyl Form Department

195.1 g of distillate is obtained using the same method as described for step (6-2) of Example 6, except that 200.5 g of a mixture containing 83.8% by weight of di-n-octyldiacetoxytin obtained at the stage (17-1), at a temperature of 200 ° C. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained distillate, it was determined that the distillate was di-n-octyldiacetoxytin.

Stage (17-3). Alkoxylation of dialkyltin compounds

181.0 g of 1,1,3,3-Tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane was prepared using the same procedure as described for step (1-6) of Example 1, except the use of 193.6 g of di-n-octyldiacetoxytin obtained in stage (17-2), instead of the reaction liquid obtained in stage (1-5) of example 1, and the use of 311 ml of 0.1 mol / l aqueous solution of potassium hydroxide and 365.9 g of 2-ethyl-1-butanol.

Example 18

Stage (18-1). Tri-n-octyl (2-ethylbutyloxy) tin separation

36.2 g of distillate and 110.6 g of the residue in the flask were obtained using the same method as described for step (11-1) of Example 11, except that 148 g of the composition of deactivated forms obtained in the same way as described for stage (16-2) of example 16, and an oil bath at a temperature of 250 ° C. As determined, the distillate is tri-n-octyl (2-ethylbutyloxy) tin, and the residue in the flask is a mixture containing 72.8 wt.% 1,1,3,3-tetra-n-octyl-1, 3-bis (2-ethylbutyloxy) -distannoxane and organotin compounds containing tin atoms, exhibiting many chemical shifts from -240 to -605 ppm. according to NMR data of ¹¹⁹ Sn.

Stage (18-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

35.1 g of the Tri-n-octyl (2-ethylbutyloxy) tin obtained in step (18-1) are placed in a 300 ml pear-shaped flask, then 23.3 g of propionic acid and 40.9 g of propionic anhydride are added and stirred for 1 hour at 25 ° C. Sampling of the solution and their analysis by gas chromatography confirm that isoamyl propionate is formed. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced, and isoamyl propionate, an excess of propionic acid and propionic anhydride, are distilled off to obtain 33.3 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-octylpropionyloxytin.

At the same time, 110.1 g of the residue containing 72.8 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) distannoxane obtained in stage (18-1 ), placed in a 500 ml metal autoclave, then 95.2 g of propionic acid and 167.2 g of propionic anhydride are added and mixed. Then the metal autoclave is immersed in an oil bath heated to 200 ° C and heated for 3.5 hours. The autoclave is allowed to cool to approximately room temperature (approximately 25 ° C), the contents of the autoclave are transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced and the excess of propionic anhydride and propionic acid and the like are distilled off to obtain 123.4 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue is a mixture containing di-n-octyldipropionyloxytin and n-octyltropionyloxytin and the content of di-n-octyldipropionyloxytin in the residue is 73.6 wt.%, While the content of n-octyltropropionyloxytin is 26.1 wt.%. The resulting mixture is mixed with the previously obtained tri-n-octylpropionyloxytin and used as a starting material in the next step (18-3).

Stage (18-3). Redistribution of alkyl groups

153.8 g of the reaction liquid is returned using the same method as described for step (1-5) of example 1 under nitrogen, except that instead of the mixture obtained in step (1-4) of example 1, 154 5 g of the mixture obtained in stage (18-2). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it was a mixture of di-n-octyldipropionyloxy tin and n-octyl tripropionyloxy tin, and the content of di-n-octyldipropionyloxy tin in the resulting mixture was 90.5 wt.%.

Stage (18-4). Alkoxylation of dialkyltin compounds

131.5 g of a Solution containing 90.5% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, with the exception of using 152.2 g of the reaction liquid obtained in stage (18-3), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 286 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 244.9 g of 2-ethyl-1-butanol.

Example 19

Stage (19-1). Dealkylation Reaction

219.4 g of the Mixture containing 84.0 wt.% Of di-n-octyldipropionyloxytin was obtained by the same method as described for step (6-1) of Example 6, except that 220 g of the composition of the deactivated forms were used, obtained in the same way as in stage (16-2) of example 16, instead of the composition of the deactivated forms obtained in stage (1-2) of example 1, and instead of acetic acid, 179.3 g of propionic acid are used, and instead of acetic anhydride, 315.0 g of propionic anhydride.

Stage (19-2). Dialkyl Form Department

212.4 g of distillate is obtained by carrying out the same method as described for step (6-2) of example 6, except for using 217.4 g of a mixture containing 84.0 wt.% Of di-n-octyldipropionyloxytin obtained in step ( 19-1), at a temperature of 220 ° C. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the distillate, it was determined that the residue was di-n-octyldipropionyloxytin.

Stage (19-3). Alkoxylation of dialkyltin compounds

194.4 g of a Mixture containing 81.7 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of Example 1, with the exception of using 211.3 g of a mixture containing 86.0 wt.% Of di-n-octyldipropionyloxytin obtained in stage (19-1), instead of the reaction liquid obtained in stage (1-5 ) of Example 1, using 411 ml of a 0.1 mol / L aqueous solution of potassium hydroxide and 318.0 g of 2-ethyl-1-butanol.

Example 20

Stage (20-1). Tri-n-octyl (2-ethylbutyloxy) tin separation

48.3 g of distillate and 138.8 g of the residue in the flask were obtained using the same method as described for step (11-1) of Example 11, except that 188 g of the composition of deactivated forms obtained in the same way as and in step (16-2) of Example 16, and the bath temperature is set at 250 ° C. The distillate was found to be tri-n-octyl (2-ethylbutyloxy) tin, and the residue in the flask was a mixture containing 74.0 wt.% 1,1,3,3-tetra-n-octyl-1 , 3-bis (2-ethylbutyloxy) -distannoxane and organotin compounds containing tin atoms, exhibiting many chemical shifts from -240 to -605 ppm. according to ¹¹⁹ Sn-NMR.

Stage (20-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

47.2 g of the tri-n-octyl (2-ethylbutyloxy) tin obtained in step (20-1) is placed in a 300 ml pear-shaped flask, then 80.3 g of hexanoic acid and 92.6 g of hexanoic anhydride are added and stirred for 1 hour at 25 ° C. Sampling of the solution and their analysis by gas chromatography confirm that the formation of isoamyl propionate takes place. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and the gas inside the vessel is replaced with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel was gradually reduced and distilled off (2-ethylbutyloxy) hexanoate, an excess of hexanoic acid and hexanoic anhydride and the like, to obtain 48.3 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-octylhexanonyloxytin.

At the same time, 137.2 g of a residue containing 74.0 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane obtained in stage (20-1 ), placed in a 500 ml metal autoclave, then 130.8 g of hexanoic acid and 331.0 g of propionic anhydride are added and mixed. Then the metal autoclave is immersed in an oil bath heated to 200 ° C, and heated for 6.2 hours. The autoclave is allowed to cool to approximately room temperature (approximately 25 ° C), the contents of the autoclave are transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced and the excess hexane anhydride and hexanoic acid and the like are distilled off to obtain 185.3 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture containing di-n-octyldihexanonyloxytin; and the content of di-n-octyldihexanonyloxytin in the residue is 71.5% by weight, while the content of n-octyltrihexanonyloxytin is 28.5% by weight. The resulting mixture is mixed with the previously obtained tri-n-octylhexanonyloxytin and used as a starting material in the next step (20-3).

Stage (20-3). Redistribution of alkyl groups

229.6 g of the reaction liquid was returned in the same manner as described for step (1-5) of example 1 under nitrogen, except for using 230.5 g of the mixture obtained in step (20-2) instead of the mixture obtained in steps (1-4) of Example 1. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it was a mixture containing di-n-octyldihexanonyloxy tin and a content of di-n-octyldihexanonyloxy tin in the mixture is 88.3 wt.%.

Stage (20-4). Alkoxylation of dialkyltin compounds

193.4 g of a Solution containing 88.1% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, with the exception of using 225.1 g of the reaction liquid obtained in stage (20-3), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 280 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 327.7 g of 2-ethyl-1-butanol.

Example 21

Stage (21-1). Dealkylation Reaction

274.7 g of the Mixture containing 77.4 wt.% Of di-n-octyldihexanonyloxy tin was obtained by the same method as described for step (6-1) of Example 6, except that 217 g of the composition of the deactivated forms were used, obtained in the same manner as in stage (16-2) of example 16, instead of the composition of the deactivated forms obtained in stage (1-2) of example 1, 266.2 g of hexanoic acid are used instead of acetic acid, and 204.6 g of hexanoic anhydride instead of acetic anhydride.

Stage (21-2). Dialkyl Form Department

202.1 g of distillate was obtained by the same method as described for step (6-2) of Example 6, except that 273.9 g of a mixture containing 77.4 wt.% Of di-n-octyldihexanonyloxytin obtained at the stage of (21-1) at a temperature of 220 ° C. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was di-n-octyldihexanonyloxytin.

Stage (21-3). Alkoxylation of dialkyltin compounds

194.4 g of a Mixture containing 81.7% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for step ( 1-6) of example 1, except that 211.3 g of the mixture of di-n-octyldihexanonyloxytin obtained in stage (21-2) are used instead of the reaction liquid obtained in stage (1-5) of example 1, and used 411 ml of a 0.1 mol / L aqueous solution of potassium hydroxide and 318.0 g of 2-ethyl-1-butanol.

Example 22

Stage (22-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

The excess maleic anhydride is distilled off to obtain 232.1 g of a mixture of organotin compounds containing tin atoms, showing many chemical shifts from -240 to -605 ppm, at about -150 ppm. and at about 100 ppm, as determined by ¹¹⁹ Sn-NMR, performing the same method as described for step (2-1) of Example 2, except for using 210 g of the deactivated form composition obtained in the same manner as in the step (16-2) of Example 16, instead of the composition of the deactivated forms obtained in Step (1-2) of Example 1, and using 362.2 g of maleic anhydride instead of acetic anhydride.

Stage (22-2): Reaction of the redistribution of alkyl groups

228.3 g of the reaction liquid was returned using the same method as described for step (2-1) of example 2, except that instead of the mixture obtained in step (2-1) of example 2, 230.8 g was used the mixture obtained in stage (22-1). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that the reaction liquid is a mixture of organotin compounds containing tin atoms, showing many chemical shifts from -240 to -605 ppm, from -140 to -200 m .d. and approximately 100 ppm, as determined by ¹¹⁹ Sn-NMR. Specifically, the ratio of the magnitude of the integral of the plurality of peaks is approximately 100 ppm. and the ratio of the magnitude of the peak integral in the region from -240 to -605 ppm to the integral value of all peaks is much lower than the ratio of the integrals in the composition obtained in stage (22-1).

Stage (22-3). Alkoxylation of dialkyltin compounds

168.1 g of a Solution containing 87.4% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, except that using 220.1 g of the mixture obtained in stage (22-2), instead of the reaction liquid obtained in stage (1-5) of example 1, 255 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 303.6 g of 2-ethyl-1-butanol.

Example 23

Stage (23-1). Dealkylation Reaction

Carry out the same method as described for stage (6-1) of example 6, except that instead of the composition of the deactivated forms obtained in stage (1-2) of example 1, use 197 g of the composition of the deactivated forms obtained in the same way as in step (16-2) of Example 16, and instead of acetic acid and acetic anhydride, 152.7 g of maleic acid and 129.5 g of maleic anhydride are used. Excess maleic acid and maleic anhydride and the like. distilled off, resulting in 214.8 g of a mixture. When conducting analysis of ¹¹⁹ Sn-NMR, it was determined that the resulting mixture was a mixture of organotin compounds containing tin atoms, showing many chemical shifts from -240 to -605 and from -140 to -200 ppm.

Stage (23-2). Alkoxylation of dialkyltin compounds

164.3 g of a Solution containing 81.2 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane, obtained by performing the same method as described for stage (1-6) of example 1, except that instead of the reaction liquid obtained in stage (1-5) of example 1, 213.1 g of di-n-octyldiacetoxytin obtained in stage (23-1) are used, and 443 ml of a 0.1 mol / L aqueous solution of potassium hydroxide and 296.8 g of 2-ethyl-1-butanol.

Example 24

Stage (24-1). Obtaining tetraalkyl dialkoxydistannoxane

692 g (2.78 mol) of di-n-butyltin oxide and 2000 g (27 mol) of 1-butanol (Wako Pure Chemical Industries, Ltd., Japan) were placed in a 3,000-ml pear-shaped volumetric flask. A flask containing a white mixture similar to a suspension is connected to an evaporator to which an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller is connected. The outlet of the purge valve of said evaporator is connected to a line containing nitrogen gas supplied at normal pressure. After closing the purge valve of the evaporator to reduce the pressure inside the system, the purge valve is gradually opened to allow nitrogen to enter the system and return to normal pressure. The temperature of the oil bath was set to approximately 126 ° C, the flask was immersed in an oil bath and the evaporator started to rotate. After rotation and heating for approximately 30 minutes at normal pressure with the evaporator valve open, the mixture boils and distillation of the low boiling component begins. After maintaining this state for 8 hours, the purge valve is closed, the pressure in the system gradually decreases and the excess of low-boiling component is distilled off at a pressure in the system from 76 to 54 kPa. After distillation of the entire low-boiling component, the flask is removed from the oil bath. The reaction liquid is a clear liquid. The purge valve is gradually opened and the pressure in the system is restored to normal. In the flask receive 952 g of the reaction liquid. Based on the analysis of ¹¹⁹ Sn, ¹ H and ¹³ C-NMR, it was determined that the reaction liquid was 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) distannoxane and its yield was 99% based on di-n-butyltin oxide. The described procedure is repeated 12 times and a total of 11488 g of 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) distannoxane is obtained.

Stage (24-2): Obtaining a carbonic ester and obtaining a composition of deactivated forms of the catalyst based on alkyltin alkoxide containing deactivated forms

The carbonic acid ester is obtained in a continuous apparatus similar to that shown in FIG. The 1,1,3,3-tetrabutyl-1,3-bis (butyloxy) -distannoxane obtained in step 1 is fed at a rate of 4201 g / h from transfer line 4 to a column type reaction vessel filled with Mellapak 750Y filler with an inner diameter 151 mm and an effective length of 5040 mm, and 1-butanol, purified on a distillation column 101, is fed into the reaction vessel 102 of the column type at a rate of 24717 g / h from the supply line 2. The temperature of the liquid in the reaction vessel of 160 ° C. is controlled by a heater and reboiler 112, and the pressure is adjusted to approximately 250 kPa-G by a pressure regulating valve. The residence time in the reaction vessel is approximately 10 minutes. 1-Butanol containing water from the upper part of the reaction vessel at a speed of 24715 g / h through transfer line 6, and 1-butanol at a speed of 824 g / h through feed line 1, is pumped to a distillation column 101 filled with Metal Gauze CY filler and equipped with a reboiler 111 and a condenser 121 for conducting distillation cleaning. In the upper part of the distillation column 101, a fraction with a high concentration of water is condensed by a condenser 121 and returned via transfer line 3. The purified 1-butanol is pumped through a transfer line 2 located at the bottom of the distillation column 101. An alkyltin alkoxide catalyst composition comprising dibutyltin dibutoxide and 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) ) distannoxane, obtained from the lower part of the reaction vessel 102 of the column type and served in a thin-film evaporator 103 through the transfer line 5. 1-butanol is distilled off in a thin-film evaporator 103 and returned to the column type reaction vessel 102 through a condenser 123, transfer line 8 and transfer line 4. The alkyltin alkoxide catalyst composition is pumped from the bottom of the thin film evaporator 103 via transfer line 7 and fed to the autoclave 104, while the flow rate of the active components in the form of dibutyltin dibutoxide and 1,1,3,3-tetra-n-butyl-1 is adjusted 3-di (butyloxy) -distannoxane to about 4812 g / hour. Carbon dioxide is fed into the autoclave through a feed line 9 at a speed of 973 g / hr, and a pressure of 4 MPa-G is maintained in the autoclave. The temperature was set in an autoclave to 120 ° C., the residence time was adjusted to about 4 hours, and the carbon dioxide was reacted with the alkyltin alkoxide catalyst composition to give a reaction liquid containing dibutyl carbonate. The resulting reaction liquid is transferred to the carbonization tank 105 through the transfer line 10 and a control valve to remove the remaining carbon dioxide, and carbon dioxide is returned via the transfer line 11. The reaction liquid is then transferred to a thin film evaporator 106, in which a temperature of approximately 140 ° C. and a pressure of approximately 1.4 kPa are set, through the transfer line 12 and at the same time 1,1,3,3-tetra-n-butyl-1 is fed , 3-di (butyloxy) -distannoxane, while adjusting the flow rate to about 4201 g / hr to give a fraction containing dibutyl carbonate. At the same time, the evaporation residue is circulated to the reaction vessel 102 of the column type via transfer line 13 and transfer line 4, with a flow rate of 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) distannoxane adjusted to approximately 4201 g / hour. The fraction containing dibutyl carbonate is fed to a distillation column 107 filled with a Metal Gauze CY filler and equipped with a reboiler 117 and a condenser 127, through a condenser 126 and a transfer line 14 at a speed of 830 g / h, then purified by distillation to obtain 99 wt.% Bis (3 -methylbutyl) carbonate from return line 16 at a rate of 814 g / h. When analyzing ¹¹⁹ Sn, ¹ H and ¹³ C-NMR of the alkyltin alkoxide catalyst composition in transfer line 13, it was determined that it contains 1,1,3,3-tetra-n-butyl-1,3-di ( butyloxy) distannoxane, but does not contain dibutyltin dibutoxide. After performing the aforementioned continuous operation for 600 hours, the alkyltin alkoxide-based catalyst composition is removed from the extraction line 16 at a rate of 16 g / hour, while 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy ) the distanxane obtained in stage 1 is fed via a feed line 17 at a speed of 16 g / hour. Approximately 120 g of liquid was taken from extraction line 16 and ¹¹⁹ Sn-NMR was analyzed; it was determined that the liquid contains approximately 60 wt.% 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) distannoxane, as well as tributyltin butoxide and a high boiling point component that exhibit many NMR shifts from -240 up to -605 ppm

Stage (24-3). Obtaining dialkyltin dialkoxide from a composition of deactivated forms of a catalyst based on alkyltin alkoxide containing deactivated forms

The starting materials in the form of 120 g of an alkyltin alkoxide-based catalyst composition containing heat-denatured forms obtained in step 2 and 332.5 g (1.91 mol) of the dibutyl carbonate obtained in step 2 are mixed in a 500 ml pear-shaped volumetric flask in protective box with gloves in a nitrogen atmosphere and close the cork. The flask containing the resulting mixture is attached to an evaporator connected to an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller. The outlet of the purge valve of said evaporator is connected to a line containing a stream of gaseous nitrogen at normal pressure. After closing the purge valve of the evaporator to reduce the pressure in the system, the purge valve is gradually opened to allow nitrogen to enter the system and return to normal pressure to fill the reaction device with nitrogen. The temperature of the oil bath is set to approximately 150 ° C, the flask is immersed in the oil bath and the evaporator starts to rotate. After rotation and heating for about 3 hours at normal pressure with the evaporator's purge valve open, the purge valve is closed, the pressure in the system is gradually reduced and the remaining reactants are distilled off at a pressure in the system of 20 to 30 kPa. After the cessation of the distillate, the flask was removed from the oil bath and 140.5 g of reaction liquid was obtained.

Distillation of the reaction liquid

Then 135.3 g of the reaction liquid are placed in a 200 ml three-necked flask equipped with a three-way valve and a distillation column filled with Helipack No. 3 and a length of 45 cm, with a fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and thermometer through a three-way valve using a gas tight syringe (Hamilton Inc.), while gaseous nitrogen can flow at a rate of 0.3 l / min. The flask is immersed in an oil bath heated to approximately 175 ° C. After stirring and heating for approximately 20 minutes, the temperature of the reaction liquid is approximately 167 ° C. The pressure in the device is gradually reduced and distillation is carried out at a pressure of approximately 0.2 kPa. Distillate 1 is distilled off at a rate of approximately 0.5 ml / min. After the cessation of the appearance of the distillate, the pressure in the device is further reduced to approximately 0.03 kPa and the distillation is continued by distilling off the distillate 2 at a rate of approximately 0.5 ml / min. After approximately 2 hours, the distillate no longer appears, the pressure drop in the device and heating are stopped to complete the distillation. The amounts of distillate 1 obtained, distillate 2, and the residue in the flask were 31.8 g, 72.9 g, and 30.6 g, respectively. An NMR analysis of distillate 1, distillate 2, and the residue in the flask is performed. In distillate 1, 81.2 wt.% Of tri-n-butylbutoxytin and 18.2 wt.% Of dibuticarbonate were obtained, while in distillate 2, 99.0 wt.% Of di-n-butyldibutoxytin was obtained. The residue in the flask contains approximately 1 wt.% 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) distannoxane, and many NMR shifts of the high boiling component are observed from -240 to -605 ppm.

Stage (24-4). Exchange of substituents of deactivated forms of a dialkyltin catalyst

30.2 g of Distillate 1 obtained in step (24-3) are placed in a 300 ml pear-shaped flask, then 34.7 g of acetic anhydride are added and stirred for 1 hour at 25 ° C. A sample of the solution was taken and analyzed by gas chromatography, confirming that butyl acetate was formed. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and after replacing the gas in the vessel with nitrogen under reduced pressure, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced, the excess of acetic anhydride, etc., is distilled off. and 29.2 g of residue are obtained in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture of tri-n-butyl (butyloxy) tin and dibutyl carbonate.

On the other hand, 29.5 g of the residue in the flask obtained in step (24-3) is placed in a 500 ml metal autoclave, then 57.3 g of acetic anhydride are added and mixed. A metal autoclave is immersed in an oil bath heated to 200 ° C and heated for 5.3 hours. The metal autoclave was allowed to cool to approximately room temperature (approximately 25 ° C), and the contents of the autoclave were transferred to a 500 ml pear-shaped flask. A fractionation nozzle is attached to the flask, equipped with a reflux condenser connected to a distillate receiver and a thermometer, and the vessel is filled with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced and the excess of acetic anhydride and the like is distilled off to obtain 39.0 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture containing di-n-butyldiacetoxytin and n-butyldiacetoxytin in the mixture was 28.0 wt.%, Whereas the content of n-butyltriacetoxytin is 72.0 wt.%. The resulting mixture is mixed with the previously obtained tri-n-butylacetoxytin and used as a starting material in the next step (24-5).

Stage (24-5): Reaction of the redistribution of alkyl groups

65.5 g of the reaction liquid is returned using the same method as described for step (1-5) of example 1 under nitrogen, except for using 66.5 g of the mixture obtained in step (24-4) instead of the mixture, obtained in stage (1-4) of example 1. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the above reaction liquid, it was determined that it was a mixture containing di-n-butyldiacetoxytin and n-butyltriacetoxytin, and the content of di-n- butyl diacetoxytin in the mixture is 87.2 wt.%.

Stage (24-6). Alkoxylation of dialkyltin compounds

46.7 g of a Solution containing 95.1 wt.% 1,1,3,3-tetra-n-butyl-1,3-di (butyloxy) -distannoxane was obtained using the same method as described for step (1) -6) of example 1, except for the use of 65.1 g of the reaction liquid obtained in stage (24-5) instead of the reaction liquid obtained in stage (1-5) of example 1, and 72 ml of a 0.1 mol / L aqueous solution potassium hydroxide and 107.1 g of 1-butanol.

Example 25

Stage (25-1). Obtaining dialkyltin dialkoxide from dialkyltin compounds containing deactivated forms

380 g of the composition of the deactivated forms obtained in the same manner as described for stage (7-1) of example 7, served in the device for molecular distillation (Model MS-300, Sibata Scientific Technology Ltd., Japan) at a speed of 300 g / hour, and volatile components are distilled off at a temperature of approximately 230 ° C and a pressure of approximately 0.02 kPa. 83.5 g of the low boiling component are recovered. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the aforementioned low boiling component, it was determined that it contained 99% by weight of tri-n-octyl (3-methylbutyloxy) tin (see FIG. 3). 295.5 g of a high-boiling component are obtained, and when analyzing ¹ H- and ¹¹⁹ Sn-NMR, it was determined that in addition to the peaks of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane there are many peaks of heat-denatured forms with chemical shifts in the range from -240 to -605 ppm. The content of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane contained in the high boiling component is 76.9 wt.%. 264.3 g of the high boiling component and 717.5 g (3.55 mol) of the bis (3-methylbutyl) carbonate obtained in step (7-2) of Example 7 are mixed in a flask under a nitrogen atmosphere and allowed to react for 2 hours at 140 ° C in the presence of nitrogen at atmospheric pressure. Then, the reaction liquid is supplied to the molecular distillation apparatus at a rate of 300 g / h, and the remaining carbonic ester is separated off at a temperature of about 150 ° C. and a pressure of about 0.5 kPa to obtain a high boiling point component in the form of about 656 g of liquid. The high boiling component is supplied to the molecular distillation apparatus at a speed of 300 g / h, then it is separated by distillation at a temperature of approximately 240 ° C. and a pressure of approximately 0.02 kPa, to obtain 251.5 g of a low boiling component. The low boiling component contains 99.3% by weight of di-n-octyl bis (3-methylbutyloxy) tin. On the other hand, in the NMR spectrum of the high-boiling component formed from the high-boiling component (see Fig. 4), there are many peaks with shifts in the region from -240 to -605 ppm.

Stage (25-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

82.2 g of Distillate 1 containing 99% by weight of tri-n-octyl (3-methylbutyloxy) tin obtained in step (25-1) is placed in a 300 ml pear-shaped flask, then 92.3 g of acetic anhydride are added and stirred for 1 hour at 25 ° C. A sample of the solution was taken and analyzed by gas chromatography, confirming that the formation of isoamyl acetate took place. A fractionation nozzle is attached to the flask, equipped with a reflux condenser connected to the distillate receiver and a thermometer, and after filling the vessel with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced, the excess of acetic anhydride, etc., is distilled off. and get 78.0 g of residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-octylacetoxytin (see FIG. 5).

At the same time, 97.4 g of the high-boiling component obtained in stage (25-1) is placed in a 500 ml metal autoclave, then 30.1 g of acetic acid and 163.7 g of acetic anhydride are added and mixed. The metal autoclave is then immersed in an oil bath heated to 200 ° C. and heated for 4 hours. The metal autoclave was allowed to cool to about room temperature (approximately 25 ° C), then the contents of the autoclave were transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and after filling the vessel with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 80 ° C. The pressure in the vessel is gradually reduced, the excess of acetic anhydride, etc., is distilled off. and get 90.1 g of residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture containing mainly n-octyltriacetoxytin, and the content of n-octyltriacetoxytin in the mixture was 87.1 wt.% (See FIG. 6). The resulting mixture is mixed with the previously obtained tri-n-octylacetoxytin and used as a starting material in the next step (25-3).

Stage (25-3). Redistribution of alkyl groups

165.8 g of the reaction liquid are returned in the same manner as described for step (1-5) of example 1 under nitrogen, except that instead of the mixture obtained in step (1-4) of example 1, 167.2 is used g of the mixture obtained in stage (25-2). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it was a mixture containing di-n-octyldiacetoxytin and n-octyltriacetoxytin, and the content of di-n-octyldiacetoxytin in the mixture was 91.2 wt.%.

Stage (25-4). Alkoxylation of dialkyltin compounds

120.2 g of a Solution containing 89.9% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, except that instead of the reaction liquid obtained in stage (1-5) of example 1, 166.4 g of the reaction liquid obtained in stage (25-3), as well as 430 ml of 0 are used , 1 mol / l of an aqueous solution of potassium hydroxide and 215.5 g of 3-methyl-1-butanol (see Fig.7).

Example 26

Stage (26-1). The return of the composition of deactivated forms formed upon receipt of the catalyst based on dialkyltin

520 g (2.1 mol) of dibutyltin oxide, 3213 g (31.5 mol) of 2-ethyl butanol and a stirrer for stirring are placed in a 5-liter four-necked flask equipped with a vacuum regulator, a refrigerator connected to a vacuum pump and a Dean-Stark tube . After filling the system with nitrogen, the flask was immersed in an oil bath heated to 146 ° C and stirring was started. After continuing heating for 20 minutes, as the distillate is removed, the pressure in the system is gradually reduced, after which the low-boiling component is further distilled off for approximately 20 minutes at a system pressure of 76 to 30 kPa. After the new distillate no longer appears, the flask is cooled. 722.1 g of reaction liquid was obtained in the flask, and as a result of analysis of ¹ H- and ¹¹⁹ Sn-NMR, it was determined that the reaction liquid contained 76.1% by weight of 1,1,3,3-di-n-butyl tetra ( 2-ethylbutyloxy) tin; and 13.3% by weight of tri-n-butyl (2-ethylbutoxy) tin.

Stage (26-2). Tri-n-butyl (2-ethylbutyloxy) tin separation

A three-way valve, a distillation column filled with Helipack No. 3, with a fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer are attached to the flask containing the reaction liquid, and the system is purged with nitrogen. The flask is immersed in an oil bath heated to approximately 190 ° C and distillation is carried out, gradually reducing the system pressure to 1.3 kPa by a vacuum pump, and distillate 1 is obtained. When the formation of a liquid distillate is no longer observed, heating is stopped and distillation is completed. 93.1 g of distillate 1 was recovered, and upon analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR of the distillate, it was determined that the distillate contained 98% by weight of tri-n-butyl (2-ethylbutyloxy) tin. In addition, 624.7 g of residue was obtained in the flask, and analysis of the ¹ H- and ¹¹⁹ Sn-NMR of the residue determined that the residue contained 87.3 wt.% 1,1,3,3-di-n-butyl- tetra (2-ethylbutyloxy) tin.

Stage (26-3). Exchange of substituents of deactivated forms of a dialkyltin catalyst

92.0 g of the Distillate obtained in step (26-2), 71.4 g of acetic acid and 145.7 g of acetic anhydride are placed in a 500 ml pear-shaped flask and the flask is placed in a water bath, the temperature is brought to 30 ° C, then stirred for 2 hours. The flask is connected to a rotary evaporator, which is connected to an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller. The outlet of the purge valve of said evaporator is connected to a line containing a stream of gaseous nitrogen at normal pressure. After purging the system with nitrogen, the temperature of the oil bath is set equal to 40 ° C, the flask is immersed in the oil bath and the rotation of the rotary evaporator begins. After distilling off the excess of acetic acid and acetic anhydride under reduced pressure of 0.1 kPa, 82.3 g of residue are obtained in the flask. When conducting analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR, it was determined that the residue contains 99 wt.% Tri-n-butylacetoxytin.

At the same time, 153.2 g of the residue in the flask obtained in stage (26-2) are placed in a 500 ml metal autoclave and 82.1 g of acetic acid and 232.7 g of acetic anhydride are added. The metal autoclave is then immersed in an oil bath heated to 250 ° C. and heated for 5 hours. The metal autoclave was allowed to cool, and the contents of the autoclave were transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the flask is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced, and the excess of acetic anhydride and the like is distilled off to obtain 159.9 g of a residue in the flask. The same procedure is carried out on the remaining 470.3 g of the residue in the flask and a total of 650.8 g of the residue is obtained. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that it was a mixture containing n-butyl triacetoxy tin and di-n-butyl bis (2-ethylbutyloxy) tin; the content of n-butyl triacetoxy tin in the mixture is 13.6 wt.%, while the content of di-n-butyl bis (2-ethylbutyloxy) tin is 86.2 wt.%.

The resulting mixture is mixed with the previously obtained tri-n-butylacetoxytin and used as a starting material in the next step (26-4).

Stage (26-4). Redistribution of alkyl groups

726.5 g of the reaction liquid was returned using the same method as described for step (1-5) of example 1 under a nitrogen atmosphere, except that instead of the mixture obtained in step (1-4) of example 1, 728 was used , 2 g of the mixture obtained in stage (26-3). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it was a mixture containing di-n-butyldiacetoxytin and n-butyltriacetoxytin and the content of di-n-butyldiacetoxytin in the mixture was 95.2 wt.%.

Stage (26-5). Alkoxylation of dialkyltin compounds

742.6 g of a Solution containing 97.1% by weight of 1,1,3,3-tetra-n-butyl-1,3-bis (2-ethylbutyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of Example 1, except for using 724.6 g of the reaction liquid obtained in stage (26-4), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 830 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 1951 g of 2-ethyl-1-butanol.

Example 27

Stage (27-1). The return of the composition of the deactivated forms formed upon receipt of the catalyst based on dialkyltin

562 g (1.56 mol) of dioctyltin oxide, 3015 g (23.2 mol) of 2-ethyl-1-hexanol and a stirrer for stirring are placed in a 5-liter four-necked volumetric flask equipped with a vacuum regulator, a refrigerator connected to a vacuum pump and Dean-Stark tube. After filling the system with nitrogen, the flask is immersed in an oil bath heated to 180 ° C and stirring is started. Stirring is continued for approximately 5 hours as the distillate is removed, the pressure is gradually reduced, then the low-boiling component is further distilled off for 5 hours at a system pressure of 76 to 30 kPa. After the formation of distillate is no longer observed, the flask is cooled. 778.3 g of the reaction liquid in the flask were obtained, and when analyzing ¹ H- and ¹¹⁹ Sn-NMR, it was determined that the reaction liquid contained 40.1 wt.% 1,1,3,3-di-n-octyl tetra ( 2-ethylhexyloxy) tin; 16.9 wt.% Di-n-octyl-bis (2-ethylhexyloxy) tin; and 25.8 wt.% Tri-n-octyl (2-ethylhexyloxy) tin.

Stage (27-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

775.8 g of the reaction liquid obtained in stage (27-1), 298.1 g of acetic acid and 544.3 g of acetic anhydride are placed in a 2 liter pear-shaped flask and the flask is immersed in a water bath set at 50 ° C, then stirred for 2 hours. The flask is connected to a rotary evaporator, which is connected to an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller. The outlet of the purge valve of said evaporator is connected to a line containing a stream of gaseous nitrogen at normal pressure. After purging the system with nitrogen, the temperature of the oil bath is set to 50 ° C, the flask is immersed in the oil bath and the rotation of the rotary evaporator begins. After distilling off the excess of acetic acid and acetic anhydride under reduced pressure of 0.1 kPa, 685.9 g of residue are obtained in the flask. When conducting analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR, it was determined that the residue is a mixture containing tri-n-octylacetoxytin and di-n-octyldiacetoxytin, and the content of tri-n-octylacetoxytin in the mixture is 25.8 mass %, while the content of di-n-octyldiacetoxytin is 58.9% by weight.

Stage (27-3). Redistribution of alkyl groups

680.8 g of the reaction liquid was returned using the same method as described for step (1-5) of example 1 under nitrogen, except for using 682.2 g of the mixture obtained in step (27-2) instead of the mixture obtained in stage (1-4) of example 1. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it was a mixture containing di-n-octyldiacetoxytin and tri-n-octylacetoxytin; and the di-n-octyl diacetoxytin content in the mixture is 58.9% by weight, the tri-n-octyl acetoxytin content is 2.1% by weight, and the content of 1,1,3,3-tetra-n-octyldiacetoxydistannoxane is 37.8 mass%.

Stage (27-4). Alkoxylation of dialkyltin compounds

710.8 g of a Solution containing 96.3% by weight of 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylhexyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of example 1, except that 678.3 g of the reaction liquid obtained in stage (27-3) are used instead of the reaction liquid obtained in stage (1-5) of example 1, as well as 833 ml 0 , 1 mol / l of an aqueous solution of potassium hydroxide and 1917 g of 2-ethyl-1-hexanol.

Example 28

Stage (28-1). The return of the composition of deactivated forms formed upon receipt of the catalyst based on dialkyltin

522 g (1.45 mol) of dioctyltin oxide, 944 g (5.08 mol) of 1-dodecanol and a stirrer for stirring are placed in a 5-liter four-necked volumetric flask equipped with a vacuum regulator, a refrigerator connected to a vacuum pump and a Dean-Stark tube . After filling the system with nitrogen, the flask was immersed in an oil bath heated to 190 ° C and stirring was started. Heating is continued for about 10 hours while removing the distillate, the pressure is gradually reduced, then the low-boiling component is distilled off for an additional 3 hours at a system pressure of 76 to 20 kPa. After the distillate is no longer observed, the flask is cooled. 823.6 g of the reaction liquid in the flask are obtained, and when analyzing ¹ H- and ¹¹⁹ Sn-NMR, it was determined that the reaction liquid contains 19.0 wt.% 1,1,3,3-di-n-octyltetra-dodecyl tin, 20, 2% by weight of di-n-octyldylodecyloxytin; and 36.3% by weight of tri-n-octyldylodecyloxytin.

Stage (28-2). Exchange of substituents of deactivated forms of a dialkyltin catalyst

819.3 g of the reaction liquid obtained in step (28-1) and 887.3 g of acetic anhydride were placed in a 2 liter pear-shaped flask and the flask was placed in a water bath at 50 ° C, then stirred for 2 hours. The flask is connected to a rotary evaporator, which is connected to an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller. The outlet of the purge valve of the rotary evaporator is connected to a line containing a stream of nitrogen gas at normal pressure. After filling the system with nitrogen, the temperature of the oil bath is set to 50 ° C, the flask is immersed in the oil bath and the rotation of the rotary evaporator begins. After distilling off the excess acetic anhydride and the like. under reduced pressure of 0.1 kPa, 701.2 g of a residue are obtained in a flask. When conducting analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR, it was determined that the residue is a mixture containing tri-n-octylacetoxytin and di-n-octyldiacetoxytin, and the content of tri-n-octylacetoxytin in the mixture is 37.3 mass %, while the content of di-n-octyldiacetoxytin is 39.4 wt.%.

Stage (28-3). Redistribution of alkyl groups

698.4 g of the reaction liquid was returned using the same method as described for step (1-5) of example 1 under nitrogen, except that 700 was used instead of the mixture obtained in step (1-4) of example 1 5 g of the mixture obtained in stage (28-2). When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it was a mixture containing di-n-octyldiacetoxytin and tri-n-octylacetoxytin; and the di-n-octyl diacetoxytin content in the mixture is 39.4% by weight, the tri-n-octyl acetoxytin content is 3.7% by weight, and the content of 1,1,3,3-tetra-n-octyl diacetoxydistannoxane is 53 6 wt.%.

Stage (28-4). Alkoxylation of dialkyltin compounds

711.8 g of a Solution containing 92.2 wt.% 1,1,3,3-tetra-n-octyl-1,3-didodecyloxydistannoxane was obtained using the same method as described for step (1-6) of the example 1, with the exception of using 695.9 g of the reaction liquid obtained in stage (28-3), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 821 ml of a 0.1 mol / L aqueous solution of potassium hydroxide and 1925 g of 1-dodecanol.

Example 29

Stage (29-1). The return of the composition of deactivated forms formed in the process of obtaining a catalyst based on dialkyltin

662.0 g of the reaction liquid was obtained using the same method as described for step (27-1) of Example 27, except for the use of 479 g (1.33 mol) of dioctyltin oxide and 2594 g (20.0 mol) of 2-ethyl -1-hexanol. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that it contains 41.6 wt.% 1,1,3,3-di-n-octyl-tetra (2-ethylhexyloxy) tin, 15.7 mass % di-n-octyl-bis (2-ethylhexyloxy) tin and 25.9% by weight tri-n-octyl (2-ethylhexyloxy) tin.

Stage (29-2). Dealkylation Reaction

660.1 g of the reaction liquid obtained in step (29-1), 402.0 g of acetic acid and 434.1 g of acetic anhydride are placed in a 2 liter pear-shaped flask, the flask is placed in a water bath (150 ° C), then heated and stirred for 10 hours. The flask is connected to a rotary evaporator, which is connected to an oil bath equipped with a temperature controller, a vacuum pump and a vacuum controller. The outlet of the purge valve of said evaporator is connected to a line containing a stream of gaseous nitrogen at normal pressure. After filling the system with nitrogen, the temperature of the oil bath is set to 50 ° C, the flask is immersed in the oil bath and the rotation of the rotary evaporator begins. After distilling off the excess of acetic acid and acetic anhydride under reduced pressure of 0.1 kPa in a flask, 568.2 g of a residue are obtained. In the analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR, the residue was determined to be a mixture containing di-n-octyldiacetoxytin and the content of di-n-octyldiacetoxytin in the mixture was 84.2 wt.%.

Stage (29-3). Alkoxylation of dialkyltin compounds

577.8 g of a Solution containing 81.1 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylhexyloxy) -distannoxane was obtained using the same method as described for the step (1-6) of Example 1, except for using 565.9 g of the reaction liquid obtained in stage (29-2), instead of the reaction liquid obtained in stage (1-5) of example 1, and using 833 ml of 0.1 mol / l of an aqueous solution of potassium hydroxide and 1558 g of 2-ethyl-1-hexanol.

Example 30

Stage (30-1). The return of the composition of deactivated forms formed in the process of obtaining a catalyst based on dialkyltin

851.5 g of the reaction liquid was obtained by the same procedure as described for step (28-1) of Example 28, except that 539 g (1.50 mol) of dioctyltin oxide and 1670 g (8.98 mol) were used 1-dodecanol. The reaction liquid contains 6.6 wt.% 1,1,3,3-di-n-octyltetradodecyloxytin, 21.4 wt.% Di-n-octyldidodecyloxytin and 43.0 wt.% Tri-n-octyldodecyloxytin.

Stage (30-2). Dealkylation Reaction

The residue (603.6 g) was obtained in a flask using the same method as described for step (29-2) of Example 29, except that 848.3 g of the reaction liquid obtained in step (30-1) were used, 449.1 g of acetic acid and 488.6 g of acetic anhydride. In the analysis of ¹ H-, ¹³ C- and ¹¹⁹ Sn-NMR, the residue was determined to be a mixture containing di-n-octyldiacetoxytin and the content of di-n-octyldiacetoxytin in the mixture was 71.1 wt.%.

Stage (30-3). Alkoxylation of dialkyltin compounds

704.0 g of a Solution containing 65.8 wt.% 1,1,3,3-tetra-n-octyl-1,3-didodecyloxydistannoxane was obtained using the same method as described for step (1-6) of the example 1, except for the use of 600.3 g of the reaction liquid obtained in stage (30-2), instead of the reaction liquid obtained in stage (1-5) of example 1, and the use of 880 ml of 0.1 mol / l aqueous solution of potassium hydroxide and 2635 g of 1-dodecanol.

Comparative Example 1

Heating a composition of deactivated forms of a dialkyl tin catalyst

175 g of the composition of the deactivated forms obtained in stage (16-2) of example 16, is placed in a 500 ml pear-shaped flask in the presence of nitrogen at atmospheric pressure. A Dimroth refrigerator and a three-way valve are connected to the flask, which is connected to a line containing nitrogen gas at normal pressure.

The flask is immersed in an oil bath preheated to 220 ° C and heated for 90 hours. Then the flask was cooled and 174.2 g of solution in the flask was obtained. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the solution, it was determined that the peak corresponding to 1,1,3,3-tetra-n-octyl-1,3-bis (2-ethylbutyloxy) -distannoxane disappeared, and a peak was observed, the corresponding tri-n-octyl (2-ethylbutyloxy) tin and a plurality of peaks ranging from -220 to -600 ppm.

Reference Example 2

175 g of the composition of the deactivated forms obtained in the same manner as described for step (16-2) of Example 16 are placed in a 500 ml pear-shaped flask under a nitrogen atmosphere, then 191.0 g of phenol are added (to extract nucleic acid, Wako Pure Chemical Industries, Ltd., Japan) and stirred for 1 hour at 40 ° C. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced and the excess of phenol, etc. distilled off to obtain 189.9 g of a residue in a flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that it was a mixture of tri-n-octylphenoxytin, di-n-octyl diphenoxytin and organotin compounds containing tin atoms, showing many chemical shifts from -240 to -605 m. d. according to ¹¹⁹ Sn-NMR. The content of tri-n-octylphenoxytin in the mixture is 25.2 wt.%, And the content of di-n-octylphenoxytin is 59.3 wt.%.

188.6 g of the Mixture was placed in a 200 ml metal autoclave in a nitrogen atmosphere. A metal autoclave is immersed in an oil bath heated to 250 ° C and heated for 6 hours. The autoclave was allowed to cool to approximately room temperature and 187.5 g of reaction liquid was recovered. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the obtained reaction liquid, it was determined that the content of tri-n-octylphenoxytin in the reaction liquid was 36.4 wt.%, And the content of di-n-octyl diphenoxytin was 41.1 wt.%.

Reference Example 3

Stage (III-1). Tri-n-octyl (3-methylbutyloxy) tin separation

66.5 g of distillate in the form of tri-n-octyl (3-methylbutyloxy) tin is obtained by carrying out the same method as described for step (11-1) of Example 11 using 300 g of a composition of deactivated forms obtained in the same manner as and in step (7-2) of Example 7. The residue in the flask contains 77.1 wt.% 1,1,3,3-tetra-n-octyl-1,3-bis (3-methylbutyloxy) distannoxane and according to ¹¹⁹ Sn -NMR, 232.5 g of a mixture of organotin compounds containing tin atoms, showing many chemical shifts from -240 to -605 ppm

Stage (III-2). The exchange of substituents of tri-n-octyl (3-methylbutyloxy) tin

65.3 g of the Tri-n-octyl (3-methylbutyloxy) tin obtained in step (III-1) are placed in a 300 ml pear-shaped flask, then 61.1 g of acetic anhydride is added and stirred for 1 hour at 25 ° C. A fractionation nozzle equipped with a reflux condenser connected to a distillate receiver and a thermometer is attached to the flask, and the vessel is filled with nitrogen in a vacuum, then the flask is immersed in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced and isoamyl acetate and the excess of acetic anhydride are distilled off to obtain 65.3 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was tri-n-octyl acetoxy tin, and the content of tri-n-octyl acetoxy tin was 99% by weight.

Stage (III-3). Heat treatment of tri-n-octyl acetoxy tin

62.4 g of the reaction product was returned following the same method as described for step (1-5) of example 1, except for using 63.3 g of the tri-n-octyl acetoxytin obtained in step (III-2), instead of the mixture, obtained in stage (1-4) of example 1. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that the reaction product contains 98 wt.% tri-n-octylacetoxytin.

Reference Example 4

Stage (IV-1). Exchange of substituents of deactivated forms of a dialkyltin catalyst

232.1 g of the residue in the flask obtained in stage (III-1) of comparative example 3 is placed in a 500 ml metal autoclave, then 187.6 g of acetic anhydride are added and mixed. A metal autoclave is immersed in an oil bath heated to 200 ° C and heated for 3 hours. The metal autoclave was allowed to cool to approximately room temperature (approximately 25 ° C), and the contents of the autoclave were transferred to a 500 ml pear-shaped flask. A fractionation nozzle equipped with a reflux condenser connected to the distillate receiver and a thermometer is attached to the flask, and after filling the vessel with nitrogen in a vacuum, the flask is immersed in an oil bath heated to 50 ° C. The pressure in the vessel is gradually reduced, and the excess of acetic anhydride and the like is distilled off to obtain 248.2 g of a residue in the flask. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the residue, it was determined that the residue was a mixture containing di-n-octyldiacetoxytin and n-octyltricetoxytin; and the di-n-octyl diacetoxytin content in the mixture is 77.8% by weight, while the n-octyl triacetoxytin content is 22.1% by weight.

Stage (IV-2). Heat treatment of deactivated forms of dialkyltin catalyst with substituted substituents

244.8 g of the Reaction Product was returned following the same method as described for step (1-5) of Example 1, except for using 245.4 g of the mixture obtained in step (IV-1) instead of the mixture obtained in step ( 1-4) of Example 1. When analyzing ¹ H- and ¹¹⁹ Sn-NMR of the reaction liquid, it was determined that the reaction liquid is a mixture containing di-n-octyldiacetoxytin and n-octyltricetoxytin; and the di-n-octyl diacetoxytin content in the mixture is 77.7% by weight, while the n-octyl triacetoxytin content is 22.1% by weight.

Industrial applicability

Since the method for producing dialkyltin compounds of the present invention can be used in areas such as the production of carbonic acid esters and ester exchange reactions, it makes it possible to obtain and reuse dialkyltin compounds and dialkyltin catalysts useful as catalysts from deactivated compositions forms of dialkyltin catalysts that previously could only be discarded, the production method of the present invention is extremely useful n from the viewpoint of industrial production, and has high commercial value.

Claims (37)

1. A method of obtaining a dialkyltin compound, including:
a redistribution reaction of alkyl groups and / or a dealkylation reaction of a composition of a deactivated form of a dialkyl tin catalyst, which is formed upon the production of an ester derivative using a dialkyl tin catalyst, where
the dialkyltin catalyst is a compound of at least one type selected from the group consisting of the dialkyltin compound represented by formula (1) and tetraalkyldistannoxane represented by formula (2):

where each of R ¹ and R ² independently represents a linear or branched alkyl group containing 1-12 carbon atoms,
each of X ¹ and X ² independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,
a and b independently represent an integer from 0 to 2 and a + b = 2, and
c and d independently represent an integer from 0 to 2 and c + d = 2;

where each of R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a linear or branched alkyl group containing 1-12 carbon atoms,
each of X ³ and X ⁴ independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom, and
e, f, g and h independently represent an integer from 0 to 2, e + f = 2 and g + h = 2, wherein the ester derivative is a compound of at least one type selected from the group consisting of a carboxylic acid ester carbamic acid ester and isocyanate. 2. The method according to claim 1, where in the formulas (1) and (2), the number of carbon atoms constituting X ¹ , X ² , X ³ and X ⁴ is a number selected from integers from 0 to 12. 3. The method according to claim 1, where the carboxylic acid ester is a carbonic ester. 4. The method according to claim 3, where the composition of the deactivated form of the catalyst based on dialkyltin is a composition containing the deactivated form of the catalyst based on dialkyltin, formed during the stage of production of carbonic ester from carbon dioxide and a catalyst based on dialkyltin. 5. The method of claim 1, wherein the deactivated form of the dialkyl tin catalyst is a heat deactivated form of the dialkyl tin catalyst. 6. The method according to claim 1, where the deactivated form of the dialkyl tin catalyst is a deactivated form of the dialkyl tin catalyst formed from a dialkyl tin catalyst in which the number of alkyl groups bound to one tin atom differs from the number of alkyl groups bound with one tin atom in a dialkyl tin catalyst. 7. The method according to claim 1, where at least one type of deactivated form of the dialkyltin catalyst is a trialkyltin compound. 8. The method according to claim 1, where the deactivated form of the dialkyltin catalyst is a trialkyltin compound and an organotin compound containing a tin atom exhibiting a chemical shift of from -220 to -610 ppm. relative to tetramethyltin in the analysis of ¹¹⁹ Sn-NMR in a solution of deuterated chloroform. 9. The method of claim 8, further comprising separating the composition of the deactivated form of the dialkyl tin catalyst into a composition containing a trialkyl tin compound and a composition comprising a tin atom compound exhibiting a chemical shift of from -220 to -610 ppm. relative to tetramethyltin in the analysis of ¹¹⁹ Sn-NMR in a solution of deuterated chloroform. 10. The method according to claim 9, where the separation stage is carried out by at least one method selected from the group consisting of distillation separation, extraction separation and membrane separation. 11. The method according to claim 1, where in the case where the pKa of the conjugate acid with respect to at least one substituent from groups associated with tin atoms of a deactivated form of a dialkyltin catalyst and not being alkyl groups formed from a dialkyl tin catalyst, is 0-6.8,
a redistribution of alkyl groups is a reaction in which a deactivated form of a dialkyltin catalyst is subjected to heat treatment. 12. The method according to claim 1, where in the case where the pKa of the acid conjugated to at least one substituent from the groups associated with tin atoms of the deactivated form of the dialkyl tin catalyst and not being alkyl groups formed from the dialkyl tin catalyst is 6.8-25,
the redistribution of alkyl groups includes the steps of:
(A) preparing an organotin compound containing a Sn — Y bond by replacing all or part of the ligands of the deactivated form (with the exception of the alkyl group formed from the dialkyltin catalyst and bound to tin) with the substituent Y; and
(B) heat treating the organotin compound containing the Sn-Y bond and obtained in step (A), where Y is a substituent for which pKa is conjugated with Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6, 8. 13. The method according to item 12, where stage (A) includes obtaining an organotin compound containing a Sn-Y bond, in which three alkyl groups and one Y group formed from an acid and / or acid anhydride are bonded to one tin atom, and an organotin compound containing a Sn-Y bond in which one alkyl group and several Y groups are formed from an acid and / or acid anhydride, the number of Y groups being selected from integers from 1 to 3, are bound to one tin atom by reacting the composition deactivated form of catalyst based f dialkyltin with an acid represented by the formula (3) below and / or an acid anhydride represented by the formula (4) below:

where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8;

where Y represents Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8, and O represents an oxygen atom. 14. The method according to item 13, where stage (A) is carried out when removing the water generated during the use of the acid in stage (A) in at least one method selected from the group consisting of removing water with a dehydrating agent, distillation and membrane separation separation. 15. The method according to claim 1, where the dealkylation reaction includes the formation of Sn-Y bonds by eliminating the alkyl group from the deactivated form of the dialkyl tin catalyst, where Y is Y, for which pKa is conjugated with Y acid, in the form of HY, where the hydrogen atom attached to Y is 0-6.8. 16. The method according to claim 7, where the dealkylation reaction forms one Sn-Y bond by eliminating one alkyl group from the trialkyltin compound contained in the composition of the deactivated form of the dialkyl tin catalyst, and a dialkyl tin compound containing the Sn-Y bond is obtained, where Y represents Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8. 17. The method according to clause 16, where the step of forming the Sn-Y bond includes the interaction of the trialkyltin compound contained in the composition of the deactivated form of the dialkyltin catalyst with the acid represented by the formula (5) and / or the acid anhydride represented by the formula (6) :

where Y is Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8;

where Y represents Y, for which pKa is conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8, and O represents an oxygen atom. 18. The method according to item 13 or 17, where the acid and / or acid anhydride are a liquid or gas at 60 ° C. 19. The method of claim 18, wherein the acid is hydrohalic acid. 20. The method according to p, where the acid is a hydrogen halide. 21. The method according to p, where the acid is an organic acid. 22. The method according to item 21, where the organic acid is a carboxylic acid. 23. The method of claim 18, wherein the standard boiling point of the acid anhydride is 300 ° C. or lower. 24. The method of claim 23, wherein the acid anhydride is acetic anhydride or maleic anhydride. 25. The method according to claim 1, where the dialkyltin compound contains two alkyl groups formed from a dialkyltin catalyst and bonded to one tin atom, and at the same time contains at least one Sn — Y bond, where Y represents Y for which pKa conjugated to Y acid, in the form of HY, where the hydrogen atom is attached to Y, is 0-6.8. 26. The method according A.25, where the dialkyltin compound is a compound of at least one type selected from the group consisting of a dialkyltin compound represented by formula (7) and a tetraalkyldistannoxane compound represented by formula (8):

where R ⁷ and R ⁸ represent a group formed from a dialkyl tin catalyst, and independently represent a linear or branched alkyl group containing 1-12 carbon atoms,
Y represents a group formed from a dialkyltin catalyst, or a group formed from acid (HY) and / or acid anhydride (YOY), pKa of the acid conjugated to Y, in the form of HY, where the hydrogen atom is attached to Y, is 0 -6.8, and
i and j independently represent an integer from 0 to 2 and i + j = 2;

where R ⁹ , R ¹⁰ , R ¹¹ and R ¹² represent a group formed from a dialkyltin catalyst, and independently represent a linear or branched alkyl group containing 1-12 carbon atoms,
Y represents a group formed from a dialkyltin catalyst, or a group formed from acid (HY) and / or acid anhydride (YOY), pKa of the acid conjugated to Y, in the form of HY, where the hydrogen atom is attached to Y, is 0 -6.8, and
k, l, m and n are integers from 0 to 2, k + l = 2 and m + n = 2, respectively. 27. The method according to item 12, further comprising after stage (B), stage (I) substitution of the substituent Y of the dialkyltin compound containing the Sn-Y bond with a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and an atom halogen. 28. The method according to item 27, where stage (I) includes:
stage (I-1) of obtaining a composition containing a dialkyltin oxide by hydrolysis of a dialkyltin compound containing a Sn-Y bond by adding an aqueous alkali solution; and
a step (I-2) of reacting the composition containing the dialkyltin oxide obtained in step (I-1) with a compound of at least one type selected from the group consisting of alcohol, carboxylic acid and hydrogen halide, followed by removal of the component containing water formed from the reaction liquid. 29. The method of claim 28, wherein the aqueous alkali solution is at least one type of aqueous alkali solution selected from the group consisting of an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of potassium carbonate, and an aqueous solution of sodium carbonate. 30. The method according to p. 28 or 29, where stage (I-2) is a stage in which the compound interacting with the composition containing dialkyltin oxide is an alcohol, and dialkyltin alkoxide is obtained. 31. The method according to claim 4, where the stage of obtaining the carbonic acid ester includes:
stage (1) obtaining a reaction liquid containing carbonic ester by reacting carbon dioxide and a dialkyltin catalyst;
a step (2) of obtaining a residual liquid by separating a carbonic ester from a reaction liquid;
a step (3) of regenerating a dialkyltin-based catalyst by reacting the residual liquid with alcohol and removing formed water from the system; and
a step (4) for recycling the dialkyltin catalyst obtained in step (3), in step (1). 32. The method according to p. 31, where the stage of regeneration of the catalyst based on dialkyltin from the composition of the deactivated form of the catalyst based on dialkyltin formed during the stage of obtaining the carbonic ester by the reaction of redistribution of alkyl groups and / or the dealkylation reaction is carried out after stage (2) and / or step (3), and the regenerated dialkyl tin catalyst is returned and reused as the dialkyl tin catalyst in step (4) and / or step (1). 33. The method according to p, where the stage of regeneration of the catalyst based on dialkyltin is a stage in which use the stages according to one of paragraphs.27-30, and where the substituent Y represents an acyloxy group. 34. The method according to claim 1, where the dialkyltin catalyst is a dialkyltin alkoxide compound. 35. The method according to p, where the dialkyltin catalyst is a dialkyltin alkoxide compound and X ¹ , X ² , X ³ and X ^{4 of the} compound represented by formula (1) and / or formula (2) are alkoxy groups:

where each of R ¹ and R ² independently represents a linear or branched alkyl group containing 1-12 carbon atoms,
each of X ¹ and X ² independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,
a and b independently represent an integer from 0 to 2 and a + b = 2, and
c and d independently represent an integer from 0 to 2 and c + d = 2;

where each of R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a linear or branched alkyl group containing 1-12 carbon atoms,
each of X ³ and X ⁴ independently represents a substituent of at least one type selected from the group consisting of an alkoxy group, an acyloxy group and a halogen atom,
e, f, g, and h are integers from 0 to 2, e + f = 2, and g + h = 2, respectively. 36. The method according to clause 35, where the dialkyltin-based catalyst is a dialkyltin alkoxide, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 of the} compounds represented by formula (1) and / or formula (2) simultaneously represent an n-butyl group or an n-octyl group. 37. The method according to p, where the alcohol is an alcohol represented by the formula (9):

where R ¹³ represents a linear or branched alkyl group containing 4-8 carbon atoms.

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