TWI624469B - Spiro-compounds synthesized from bisphenol a, their diacid and dianhydride derivatives, polymers of the derivatives, and process for making the same - Google Patents

Abstract

The present invention discloses a series of spiro compounds, dibasic acids and dibasic anhydride derivatives thereof, and polymers thereof, and methods for their preparation. The method for producing a spiro compound of the present invention comprises synthesizing a bisphenol A (BPA) and a compound having the following formula (i) in the presence of an acid catalyst to synthesize a spiro compound having the following formula (I) . The method for producing a dibasic acid and a dibasic acid anhydride derivative of the compound of the above formula (I) comprises subjecting the compound of the formula (I) to an autoxidation step in the presence of an oxidizing agent, and synthesizing the formula (II) and formula (III) A dibasic acid/dibasic anhydride derivative. The present invention further provides a polymer of the formula (IV) prepared by the derivatives and a process for producing the same.

Description

Spiro compound prepared from bisphenol A, dibasic acid and dibasic anhydride derivative, polymer of the same, and preparation method thereof

The present invention relates to a series of spiro compounds prepared from bisphenol A as a raw material, which are subjected to auto-oxidation reaction to form dibasic acids and dibasic anhydride derivatives from the dibasic acids and dibasic anhydrides. Polymers having a spiro structure prepared from derivatives, and methods for their preparation.

Polymers of intrinsic microporosity (PIMs) generally refer to polymers with poor micromolecular properties due to poor stacking of molecular chains, which constitute a microporous property. The polymer prepared according to this concept can be used as a polymer. The gas separation membrane is used, and the inherent microporous polymer has the advantages of good solubility and convenient processing compared to other types of materials. ¹ is a micropore property, and a polymer having a rigid main chain and high heat resistance is generally used as a substrate (such as polyimine ² , polyamine ^3, etc.) to fix the formed micropores. And by introducing structures with non-planar properties (such as spiro rings ^{1, 3, 4,} etc.), hindering the molecular chain stacking and increasing the free volume. Therefore, it has been one of the important development directions to try to synthesize a spiro compound which can be used to prepare polyamine or polyimine.

⁵ in 2004, Dai team bisphenol A as a raw material, which acid was stirred at room temperature, subjected to acid cleavage reaction of bisphenol A formed IPP (p -Isopropenylphenol) cations, further generates dimerization reaction scheme as follows The reaction intermediates 3a to 3c are shown, and as the reaction time is elongated and the solvent is selected, a spiro bisphenol monomer compound 5 can be obtained:

However, the spiro compound and a bisphenol monomer can not be directly used in polyimide manufacturing process, and therefore, many scholars through a two step reaction and nitrification hydrogenated bisphenol directly above monomer compound is modified diamine monomer compound ^{4 , 6,7} , the structure is as shown in the following formula (A). However, with such a two-step reaction, a plurality of nitro-substituted isomers are formed after the nitration step, which is still purified by column chromatography and has a low yield, so it is limited in industrial applications.

^8, 2013, J. Lee improvements for the above process, the proposed monomeric compound of bisphenol A hydroxy protecting group substitution after nitration, in order to reduce the generation isomers, the purification process of high purity can be obtained through a simple washing step The product has a high yield and the reaction scheme is as shown in the following formula.

Despite this, the cumbersome synthesis steps leave considerable room for improvement.

In recent years, ^9-12 , Xiao team used spirobichroman bisphenol as raw material to synthesize bisamine, dibasic acid anhydride and dibasic acid monomer compound through nucleophilic substitution reaction, as shown in the following formulas (B) to (E). It is used to prepare polyimine and polyamide materials, and exhibits excellent organic solubility due to the introduction of a spiro structure. However, the monomer compound prepared by this method has a soft ether bond, and thus the polymer material obtained from the monomer compound exhibits poor mechanical properties and thermal properties.

In order to improve the technical problems of the above-mentioned synthesis steps and the poor mechanical properties and thermal properties of the materials, the applicant of the present invention managed to prepare a dibasic acid compound and a dibasic acid anhydride compound having a spiro ring structure and having no soft chain by simple synthesis. In order to improve the polymer material, the physical properties such as mechanical properties, heat resistance and organic solubility are improved.

It is an object of the present invention to provide a compound having a spiro structure.

Another object of the present invention is to provide dibasic acids and dibasic acid anhydride derivatives of such compounds having a spiro structure.

Still another object of the present invention is to provide a spirocyclic polymer material such as polyimine or polyamine which is obtained from such derivatives, which has high heat resistance and high organic solubility.

Still another object of the present invention is to provide a compound of the above-described spiro structure, a dibasic acid thereof and a dibasic acid anhydride derivative, and a process for preparing a polyimine or polyamine material.

Spiro compounds and their dibasic acids and dibasic anhydride derivatives

The present invention provides a spiro compound having the following formula (I):

Wherein R ₁ and R ₂ are each independently H, a C ₁ -C ₆ alkyl group or a carboxylic acid group (COOH), or R ₁ and R _{2 are} combined into an acid anhydride; and X is N, O or S.

When the compound of the above formula (I) is R _{1 and} H ₂ is a methyl group, the spiro compound is a compound of the formula (Ii).

When X of the compound of the above formula (Ii) is O, the spiro compound is a compound of the formula (Iia)

When R ₁ and R ₂ of the compound of the above formula (I) are methyl, the spiro compound is a compound of the formula (I-ii)

When X of the compound of the above formula (I-ii) is O, the spiro compound is a compound of the formula (I-ii-a)

When R ₁ of the compound of the above formula (I) is H and R ₂ is a carboxylic acid group, the spiro compound is a dibasic acid derivative having the formula (II)

When X of the compound of the above formula (II) is O, the dibasic acid derivative is a compound having the formula (II-a)

When R ₁ and R _{2 of the} compound of the above formula (I) are combined into an acid anhydride, the spiro compound is a dibasic anhydride derivative having the formula (III)

When X of the compound of the above formula (III) is O, the dibasic anhydride derivative is a compound of the formula (III-a)

The above-mentioned compound disclosed in the present invention is a novel monomer compound. Compared with the monomer compound (D) in the prior art, the above-mentioned monomer compounds disclosed in the present invention are polymerized by polymerization of the monomer compounds because they have no soft ether bond. The material may have better thermal properties and thermal stability.

Preparation method of spiro compound and its dibasic acid and dibasic acid anhydride derivative

The present invention provides a process for producing a spiro compound of the above formula (I), which comprises reacting bisphenol A with an excess of a compound of the formula (i) to give a compound of the above formula (I)

In the above method of the present invention, it can be carried out under acid catalyst catalysis.

The invention further provides a method for preparing the dibasic acid/dibasic acid anhydride of the compound of the above formula (I), which comprises: oxidizing the compound of the above formula (I) with an oxidizing agent to obtain a spiro ring of the above formula (II), (III) Compound.

In the above process of the present invention, R ₁ and R _{2 of the} compound of the formula (i) may each be H, C ₁ -C ₆ alkyl, wherein when one of R ₁ or R ₂ is hydrogen, the other is C. ₁ -C ₆ alkyl; X can be N, O or S.

In the above process for producing a compound of the formula (I) of the present invention, the molar ratio of the bisphenol A to the compound of the formula (i) is from about 1:5 to 1:20, preferably from about 1:5 to 1:10.

The acid catalyst used in the above method for producing the compound of the formula (I) of the present invention is selected from the group consisting of organic acids such as Methanesulfonic acid (MSA), p-Toluenesulfonic acid (p-TSA), and the like. Or inorganic acids such as sulfuric acid, oxalic acid, etc., may also be combined in any mixing ratio of the above acid catalysts.

In the above process for producing a compound of the formula (I) of the present invention, the reaction is carried out at a temperature of from about 50 ° C to about 100 ° C, preferably from about 60 ° C to about 90 ° C, more preferably from 70 ° C to about 80 ° C.

In the above process for producing a compound of the formula (I) of the present invention, the reaction time is about 1 to 24 hours, preferably about 1 to 5 hours.

In the above process for preparing a dibasic acid/dibasic acid anhydride of the compound of the formula (I), the oxidation of the compound of the formula (I) is autoxidation, that is, an oxidation reaction of an alkyl group on a benzene ring, which is converted. It is an acid group or an acid anhydride group. The oxidizing agent added to convert them to an acid group or an acid anhydride group is cobalt acetate (Co(OAc) ₂ ) or manganese acetate (Mn(OAc) ₂ ), and combinations thereof. In the method, a radical initiator may be further added to further promote the auto-oxidation reaction, and the radical initiator may be selected from Di-tert-butyl peroxide and Dicumyl peroxide. And a peroxide such as tert-Butyl cumyl peroxide, and combinations thereof, preferably tert-butylperoxy cumene.

The above method for preparing a dibasic acid/dibasic acid anhydride of the compound of the formula (I) of the present invention The reaction is carried out under a normal pressure or a high pressure oxygen atmosphere, preferably a high pressure environment having a pressure of about 250 to 300 psi. The above process can be carried out in a solvent selected from the group consisting of acetic acid and acetic anhydride, preferably acetic acid. The above process can be carried out at a temperature of from about 100 to 200 ° C, preferably at a temperature of from 140 to 180 ° C.

Spiro polymer

The invention further provides a polymer of formula (IV),

Wherein X is as defined above; A is an amide group or an imide group; and B is selected from a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₇ cycloalkyl group, and The following groups: , , ,and m is selected from an integer from 1 to 100, and n is selected from an integer from 1 to 100.

When A of the above formula (IV) polymer is a guanamine group, the polymer is a polyamidoamine of the formula (IV-i)

Wherein X, B and n are as defined above.

When X of the above formula (IV-i) polyamine is an oxygen atom, B is When the polymer is a polyamine of the formula (IV-ia)

When A of the polymer of the above formula (IV) is a quinone imine group, the polymer is a polyimine material of the formula (IV-ii)

Wherein X, B and n are as defined above.

When the poly(imine) of the above formula (IV-ii) is an oxygen atom, B is When the polyimine is a polyimine of the formula (IV-ii-a), wherein n is as defined above

Preparation method of spiro ring polymer

The present invention further provides a method for producing the spirocyclic polymer of the above formula (IV), which comprises the above dibasic acid derivative having the formula (II) or a dibasic anhydride derivative having the formula (III) and having the following formula ( The diamine monomer compound of F) is subjected to polymerization reaction H ₂ NB-NH ₂ (F) to obtain the polyamidamine of the above formula (IV-i) and the poly(imine) of the above formula (IV-ii), respectively. F) The B chain of the diamine monomer compound is as defined above.

The above reaction can be carried out in an air atmosphere, preferably under a nitrogen atmosphere, at a temperature of from about 90 ° C to about 220 ° C, preferably from about 100 ° C to about 200 ° C, more preferably from about 110 ° C to 170 ° C.

Wherein the polyamine of the formula (IV-i) is obtained by polymerizing a compound of the above formula (II) with a diamine monomer compound of the above formula (F) in a nitrogen atmosphere at a temperature of 110 ° C; -ii) Polyimine is obtained by carrying out a polymerization reaction of a compound of the above formula (III) with a diamine monomer compound of the above formula (F) in a nitrogen atmosphere at a temperature of 170 °C.

The polyamines and polyimines obtained by the above methods have a relatively high glass transition temperature, excellent organic solubility, and excellent thermal stability and good dimensional stability. The improved processability of these materials has a very good development prospect for its application in the field of intrinsic microporous polymers (PIM).

Figure 1 is a single crystal X-ray diffraction pattern of the compound (I-i-a).

Fig. 2 is a ¹ H-NMR spectrum chart of the compound (I-ii-a).

Figure 3 is a single crystal X-ray diffraction pattern of the compound (III-a).

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and any modifications and variations which may be obtained without departing from the spirit of the invention are range.

The above-described implementation of the present invention can be expressed by the following Reaction Scheme 1 and Reaction Scheme 2, and the applicant will be described in the following specific examples.

Reaction Scheme 1 Preparation of a spirocyclic monomer compound of the formula (I-i), a spiro bibasic acid derivative of the formula (II) and a polydecylamine of the formula (IV-i)

Reaction Scheme 2 Preparation of a spirocyclic monomer compound of the formula (I-ii), a spiro bibasic acid derivative of the formula (III) and a polydecylamine of the formula (IV-ii)

Reaction material

The following compounds of Examples listed applicant applied to the case of the embodiment and its suppliers: bisphenol A (bisphenol A, BPA), commercially available from Alfa; inter - methyl phenol (m -cresol), commercially available from Lancaster; 3,4- 3,4-dimethylphenol, purchased from Acros; 4,4'-diaminodiphenylmethane (DDM), purchased from Chriskev, and recrystallized via methanol; methanesulfonic acid (methane sulfonic acid, MSA), available from Fluka; t-butyl cumyl peroxide (t -butyl cumyl peroxide, TBCP) , commercially available from Acros; anhydrous manganese (manganese (II) acetate) acetate, available From Alfa; anhydrous cobalt acetate (Cobalt (II) acetate), purchased from Alfa; sodium bromide, available from Showa; triphenyl phosphite (TPP), purchased from Alfa; anhydrous calcium chloride (calcium chloride), purchased from Showa; anhydrous pyridine (pyridine), purchased from Acros; N-methyl-2-pyrrolidone (NMP), purchased from Macron, under reduced pressure and calcium hydride (purchased from Acros) was purified by distillation and stored in molecular sieves.

The other solvents of the present invention are all commercial products (HPLC grade) and are used without further purification.

Example 1

Synthesis of a compound of the formula (I-i-a) (X of the formula (I-i) in the reaction scheme 1 is an oxygen atom)

The compound (Iia) is obtained by reacting bisphenol A with an excess of m-methylphenol under acid catalyst catalysis. The synthesis procedure is as follows: 60.00 g (0.26 mol) is added to a 0.5 liter three-neck reactor. (mol)) bisphenol A, 198.95 g (0.26 x 7 moles (mol), the molar number is 7 times bisphenol A) between -methylphenol, heated to 80 ° C under nitrogen atmosphere and The mixture was stirred until fully dissolved, and 12.00 g of methanesulfonic acid was added in an amount of 0.2% by weight (wt%) based on the weight of bisphenol A, and the reaction was maintained at 80 ° C for 3 hours. After the reaction is over, the solution is cooled to It is dissolved in toluene at room temperature, and extracted with 10% by weight aqueous NaOH solution to remove excess methylphenol and methanesulfonic acid. The organic layer is concentrated under reduced pressure and distilled at 180-200 ° C to obtain white ( Iia) crude product. The crude product was recrystallized by dissolving in methanol, and after filtration by suction, the filter cake was dried in a vacuum oven at 50 ° C to obtain a white crystal product with a yield of about 17%.

The compound of formula (Iia) was dissolved in DMSO- d ₆ solvent, and the chemical shift was analyzed by superconducting nuclear magnetic resonance spectrometry ( ¹ H-NMR) as follows: 7.3 ppm ( d , 2H, H ₄ ), 6.7 ppm ( d , 2H, H ₅ ), 6.4 ppm ( s , 2H, H ₇ ), 2.2 ppm ( s , 6H, H ₆ ), 1.9-2.1 ppm (4H, H ₁ ), 1.6 ppm ( s , 6H, H ₃ ), _1.3 ppm ( s , 6H, H ₂ ). The melting point of the compound of formula (Iia) was about 120 ° C as measured by a melting point apparatus. The compound of the formula (Iia) was analyzed by a high-resolution mass spectrometer as follows: HR-MS (EI) m/z: calcd. for C ₂₃ H ₂₈ O ₂ 336.2089; anal., 336.2082 for C ₂₃ H ₂₈ O ₂ . The results of the analysis of the compound of the formula (Iia) by elemental analysis were as follows: E _LEM. A _NAL. C _ALCD. C, 82.10%; H, 8.39%; O, 9.51% Found: C, 81.90%; H, 8.44%; 9.25%. The compound (Iia) can be recrystallized from methanol to obtain a single crystal, and the structure of the single crystal diffraction analysis is as shown in FIG.

Comparative Example 1-1

Referring to the prior art document J. Org. Chem. 1997, 62, 1058, the experimental procedure is as shown in Example 1, except that the ratio of reactants, the amount of catalyst, the reaction temperature and the reaction time are changed as follows: bisphenol A and m- The molar ratio of methyl phenol was 1:20, the amount of methyl sulfonic acid was 0.4% by weight based on the weight of bisphenol A, the reaction temperature was 150 ° C, the reaction time was 10 hours, and the yield of the product was less than 1%.

Comparative Example 1-2

The experimental procedure is as shown in Example 1, except that the ratio of reactants, the amount of catalyst, the reaction temperature and the reaction time are changed as follows: the molar ratio of bisphenol A to m-methylphenol is 1:20, and the amount of methylsulfonic acid is 0.4 wt% based on the weight of bisphenol A, a reaction temperature of 150 ° C, and a reaction time of 24 hours, and finally the compound of the formula (Iia) could not be obtained.

Comparative Example 1-3

The experimental procedure is as shown in Example 1, except that the ratio of the reactants, the amount of the catalyst, the reaction temperature and the reaction time are changed as follows: the molar ratio of bisphenol A to m-methylphenol is 1:3, and the amount of methylsulfonic acid is 0.4 wt% of bisphenol A, a reaction temperature of 150 ° C, and a reaction time of 24 hours, and finally the compound of the formula (Iia) could not be obtained.

Comparative Example 1-4

The experimental procedure is as shown in Example 1, except that the ratio of the reactants, the reaction temperature and the reaction time are changed as follows: the molar ratio of bisphenol A to m-methylphenol is 1:10, the reaction temperature is 100 ° C, and the reaction time is 24 The yield of the obtained product was less than 1% in an hour.

Comparative Example 1-5

The experimental procedure is as shown in Example 1, except that the ratio of the reactants and the reaction time are changed as follows: the molar ratio of bisphenol A to m-methylphenol is 1:10, the reaction time is 24 hours, and the yield of the obtained product is about 8%. .

Comparative Example 1-6

The experimental procedure is as shown in Example 1, except that the ratio of the reactants and the reaction time are changed as follows: the molar ratio of bisphenol A to m-methylphenol is 1:5, the reaction time is 24 hours, and the yield of the obtained product is about 6%. .

Comparative Example 1-7

The experimental procedure was as shown in Example 1, except that the reaction time was changed to 24 hours and the yield of the obtained product was about 8%.

Example 2

Synthesis of a compound of the formula (II-a) (in the reaction scheme 1, the X of the formula (II) is an oxygen atom)

Compound (II-a) is obtained by oxidizing a compound (I-i-a) synthesized as described above, which is obtained. The synthesis procedure is as follows: in a high pressure reactor, 1.54 g (4.5 mmol) of compound (Iia), 0.15 g (1 wt% by weight of the compound of formula (Iia)) of manganese acetate, 0.15 g (by formula (Iia)) The weight of the compound is 1% by weight of cobalt acetate, 0.15 g (1% by weight based on the weight of the compound of the formula (Iia)) of sodium bromide, and 0.31 g (2% by weight based on the weight of the compound of the formula (Iia)). Tert-butylperoxybenzene benzoate was dissolved in 10 ml of acetic acid and subjected to an oxidation reaction at 150 ° C for 200 hours under an oxygen atmosphere of 200 to 250 psi. After the reaction was completed, it was cooled to room temperature, and after the solution was filtered by suction, the obtained cake was dried in a vacuum oven at 80 ° C to obtain a yellow powder, yielding about 52%.

The compound of the formula (II-a) was dissolved in a DMSO- d ₆ solvent, and the chemical shift was analyzed by a superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR) as follows: 12.9 ppm (2H, H6), 7.6-7.4 ppm (4H, H). ₄ and H ₅ ), 6.9 ppm ( s , 2H, H ₇ ), 2.0-2.2 ppm (4H, H ₁ ), 1.6 ppm ( s , 6H, H ₃ ), _1.3 ppm ( s , 6H, H ₂ ). The compound of the formula (II-a) was analyzed by a high-resolution mass spectrometer as follows: HR-MS (EI) m/z: calcd. for C ₂₃ H ₂₄ O ₆ 396.1573; anal., 396.1567 for C ₂₃ H ₂₄ O ₆ . The compound of the formula (II-a) was analyzed by an elemental analyzer as follows: E _LEM. A _NAL. C _ALCD. C, 68.45%; H, 4.73%; O, 26, 82% Found: C, 67.99%; H, 4.37 %; O, 26.46%.

Comparative example 2

The experimental procedure was as shown in Example 2, except that the reaction pressure was changed to normal pressure, and the yield of the obtained product was about 30%.

Example 3

Synthesis of a compound of the formula (I-ii-a) (in the reaction scheme 2, X of the formula (I-ii) is an oxygen atom)

The compound of formula (I-ii-a) is based on bisphenol A and an excess of 3,4-dimethylphenol The reaction was carried out by the following steps: in a 0.5 liter three-necked reactor, 20.60 g (0.09 mol) of bisphenol A and 77.14 g (0.09 x 7 mol) of 3,4-dimethylphenol were added in a nitrogen atmosphere. The mixture was heated to 80 ° C and stirred until fully dissolved, and 4.12 g of methanesulfonic acid was added in an amount of 0.2 wt% based on the weight of bisphenol A, and the reaction was maintained at 80 ° C for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and dissolved in toluene to remove excess 3,4-dimethylphenol and methanesulfonic acid with 10% by weight aqueous NaOH solution, and the organic layer was concentrated under reduced pressure to give a dark brown color. I-ii-a) crude product of the compound. The crude product was washed with hot methanol, and after suction filtration, the obtained cake was dried in a vacuum oven at 60 ° C to obtain a white powder product in a yield of about 20%.

The compound of the formula (I-ii-a) was dissolved in a DMSO- d ₆ solvent and analyzed by a superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR) as shown in Fig. 2, and the chemical shift was as follows: 7.1 ppm ( s , 2H, H ₄ ), 6.3 ppm ( s , 2H, H ₇ ), 2.1 ppm ( s , 6H, H ₅ ), 2.0 ppm ( s , 6H, H ₆ ), 1.8-2.1 ppm (4H, H ₁ ), 1.5 ppm ( s , 6H, H ₃ ), 1.2 ppm ( s , 6H, H ₂ ). The compound of formula (I-ii-a) has a melting point of about 180 ° C as measured by a melting point apparatus. The compound of the formula (I-ii-a) was analyzed by a high-resolution mass spectrometer as follows: HR-MS (EI) m/z: calcd. for C ₂₅ H ₃₂ O ₂ 362.2402; anal., 364.2393 for C ₂₅ H ₃₂ O ₂ . The compound (I-ii-a) was analyzed by elemental analysis as follows: E _LEM. A _NAL. C _ALCD. C, 82.37%; H, 8.85%; O, 8.78% Found: C, 82.60%; H, 9.05% ;O, 8.32%.

Comparative Example 3-1

The experimental procedure is as shown in Example 3. The reaction ratio, reaction temperature and reaction time are changed as follows: the molar ratio of bisphenol A to 3,4-dimethylphenol is 1:20, and the reaction temperature is 100 ° C. The compound of the formula (I-ii-a) could not be obtained for 24 hours.

Comparative Example 3-2

The experimental procedure is as shown in Example 3. The reaction ratio, reaction temperature and reaction time are changed as follows: the molar ratio of bisphenol A to 3,4-dimethylphenol is 1:10, and the reaction temperature is 100 ° C. The compound of the formula (I-ii-a) could not be obtained for 24 hours.

Comparative Example 3-3

The experimental procedure is as shown in Example 3, except that the ratio of the reactants and the reaction time are changed as follows: the molar ratio of bisphenol A to 3,4-dimethylphenol is 1:20, the reaction time is 24 hours, and the yield of the obtained product is obtained. Less than 3%.

Comparative Example 3-4

The experimental procedure is as shown in Example 3, except that the ratio of the reactants and the reaction time are changed as follows: the molar ratio of bisphenol A to 3,4-dimethylphenol is 1:10, the reaction time is 24 hours, and the yield of the obtained product is obtained. Less than 10%.

Comparative Example 3-5

The experimental procedure is as shown in Example 3, except that the ratio of the reactants and the reaction time are changed as follows: the molar ratio of bisphenol A to 3,4-dimethylphenol is 1:5, the reaction time is 24 hours, and the yield of the obtained product is obtained. Less than 10%.

Comparative Example 3-6

The experimental procedure was as shown in Example 3, except that the reaction time was changed to 24 hours, and the yield of the obtained product was about 14%.

Example 4

Synthesis of a compound of the formula (III-a) (in the reaction scheme 2, X of the formula (III) is an oxygen atom)

The compound of the formula (III-a) is obtained by the oxidation reaction of the compound (I-ii-a) synthesized as described above, and the synthesis procedure is as follows: in a high pressure reactor, 5.00 g (0.014 mol) of the formula (I-ii) is added. - a) compound, 0.04 g of manganese acetate (in an amount of 2 wt% based on the weight of the compound of the formula (I-ii-a)), 0.04 g of cobalt acetate (2 wt% based on the weight of the compound of the formula (I-ii-a)) ), 0.04 g of sodium bromide (2 wt% by weight of the compound of the formula (I-ii-a)), 0.08 g of t-butyl peroxidation Cumene (4 wt% based on the weight of the compound of the formula (I-ii-a)), dissolved in 40 ml of acetic acid, was subjected to an oxidation reaction at 170 to 180 ° C and an oxygen atmosphere of 250 to 300 psi for 11 hours. After the reaction was completed, the solution was cooled to room temperature, and after filtration by suction, the filtrate was poured into water, and after filtration by suction, the cake was dried in a vacuum oven at 80 ° C to obtain a pale yellow powder. The crude product was heated under reflux with acetic anhydride under nitrogen to give a closed-loop, then cooled to room temperature and then recrystallized to give crystals of pale yellow crystals with a yield of about 11%.

The compound of the formula (III-a) was dissolved in a DMSO- d ₆ solvent, and the chemical shift was analyzed by a superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR) as follows: 8.3 ppm ( s , 2H, H ₄ ), 7.3 ppm ( s , 2H, H ₅ ), 2.2-2.4 ppm (4H, H ₁ ), 1.7 ppm ( s , 6H, H ₃ ), 1.4 ppm ( s , 6H, H ₂ ). The compound of the formula (III-a) was analyzed by a high-resolution mass spectrometer as follows: HR-MS (EI) m/z: calcd. for C ₂₅ H ₂₀ O ₈ 448.1158; anal., 448.1154 for C ₂₅ H ₂₀ O ₈ . The compound of the formula (III-a) was analyzed by an elemental analyzer as follows: E _LEM. A _NAL. C _ALCD. C, 66.96%; H, 4.50%; O, 28.54% Found: C, 65.01%; H, 4.38%; O, 29.30%. The compound of the formula (III-a) can be recrystallized from acetic anhydride to obtain a single crystal, and the structure of the single crystal diffraction analysis is as shown in FIG.

Comparative example 4

The experimental procedure was as shown in Example 4. Only the reaction pressure was changed to normal pressure, and the compound of the formula (III-a) could not be obtained.

Example 5

Preparation of polyamine (IV-i-a) (in the reaction scheme 1, X of the formula (IV-i) is an oxygen atom)

The polyamine of the formula (IV-ia) is obtained by polymerizing the compound of the above formula (II-a) with 4,4'-diaminodiphenylmethane, and the synthesis procedure is as follows: in a 125 ml three-neck reactor Add 2.00 g (5 mmol) of the compound of the formula (II-a), 1.00 g (5 mmol) of 4,4'-diaminodiphenylmethane, 3.13 g (5 x 2 mmol) of triphenyl phosphite, 0.72 g of anhydrous chlorine Calcium, dissolved in 12.00 g (solid content 20 wt%) of N-methylpyrrolidone / anhydrous pyridine co-solvent in a mixing ratio of 2:1 by weight, heated to 110 ° C under a nitrogen atmosphere, and stirred for 20 hours. After the reaction was completed, the solution was added dropwise to methanol to precipitate, and washed with hot water and hot methanol. After suction filtration, the cake was dried in a vacuum oven at 80 ° C to obtain a white fibrous solid.

The polyamine of formula (IV-ia) was dissolved in DMSO- d ₆ solvent, and the chemical shift was analyzed by superconducting nuclear magnetic resonance spectrometry ( ¹ H-NMR) as follows: 10.0 ppm (-CON H ), 7.6-7.0 ppm (Ar _{- H), 3.8ppm (H 4} ), 2.1ppm (H 3), 1.6ppm (H 1), 1.3ppm (H 2). The molecular weight of the compound (IV-ia) polyamine was dissolved in N-methylpyrrolidone by gel permeation chromatography (GPC), and the analysis results were as follows: M _n = 7.1 × 10 ⁴ ; M _w = 15.2 × 10 ⁴ ; PDI = 2.13.

Example 6

Preparation of poly(imine) of formula (IV-ii-a) (in process 2, X of formula (IV-ii) is an oxygen atom)

The poly(imine) of the formula (IV-ii-a) is obtained by polymerizing a compound of the above formula (III-a) with 4,4'-diaminodiphenylmethane, and the synthesis steps are as follows: a 100 ml three neck In the reactor, 0.4342 g (2.19 mmol) of 4,4'-diaminodiphenylmethane was added, dissolved in 8.03 g (solid content: 15 wt%) of m-methylphenol, and maintained under nitrogen for 30 minutes until completely dissolved. plus 0.9821 g (2.19 mmol) of the compound of formula (III-a) and a small amount of isoquinoline were added. The reaction was carried out by heating to 170 ° C, and after the reaction was completed, the solution was poured into methanol to precipitate. After repeated washing for several times, it was dried in a vacuum oven at 70 ° C to obtain a product.

The poly(imine) of the formula (IV-ii-a) was dissolved in a DMSO- d ₆ solvent, and the chemical shift was analyzed by a superconducting nuclear magnetic resonance spectrometer ( ¹ H-NMR) as follows: 8.0 ppm (H ₅ ), 7.3 ppm (H) _{6 and H 7), 7.1ppm (} H 1), 4.1ppm (H 8), 2.2ppm (H 4), 1.8ppm (H 2), 1.4ppm (H 3). The molecular weight of the formula (IV-ii-a) polyimine dissolved in N-methylpyrrolidone was analyzed by gel permeation chromatography (GPC), and the analysis results were as follows: M _n = 7.02 × 10 ⁴ ; M _w = 17.2 × 10 ⁴ ; PDI = 2.45.

In order to confirm that the polyimine synthesized in the present case does have a breakthrough in thermal properties, the above formula (IV-ii-a) polyimine is additionally coated into a film, and the properties are related to the polyimine of the prior art literature. The film preparation step is as follows: the poly(imine) of the formula (IV-ii-a) is formulated into a 25 wt% solution with N-methylpyrrolidone, and then coated onto a glass substrate by an automatic coater to control the film thickness. At 30 μm, most of the solvent was removed by heat treatment at 80 ° C for 12 hours in a circulating oven. The temperature was raised to 100 ° C for 1 hour and 200 ° C for 1 hour, and after cooling, it was bubbled into water to remove the film.

Analytical method

Superconducting nuclear magnetic resonance spectrometer (400 MHz Nuclear Magnetic Resonance, NMR), model: Varian Unity Inova-400, DMSO- d ₆ chemical shift was δ = 2.49 ppm.

Elemental Analyzer (EA), brand and model: Elementar vario EL III.

Mass Spectroscopy (MS), brand and model: Finnigan/ Thermo Quest MAT 95XL, LTQ Orbitrap XL (Thermo Fisher Scientific).

X-ray Single Crystal Diffractometer, brand and model: Bruker D8 VENTURE.

Gel permeation chromatography (GPC), brand and model: Hitachi LaChrom Elite, flow rate set to 0.6mL / min, column temperature constant 60 ° C.

Melting Point Apparatus, label and model: Fargo Melting Point Apparatus MP-2D.

Thermogravimetric Analysis (TGA), model: Thermo Cahn Versa Therm, nitrogen and air flow rate of 20 mL / min, heating rate of 20 ° C / min.

Thermal Mechanical Analysis (TMA), model: Perkin-Elmer Pyris Diamond, at a ramp rate of 5 °C/min.

Discussion on the synthesis of spiro compounds of formula (I-i-a)

It is disclosed in the prior art document J. Org. Chem . 1997, 62 , 1058 that the bisphenol A and the excess m-methyl phenol will form a structure of the following formula (G) under acid catalyst catalysis, in which the formula (Iia) The spiro compound is regarded as a reaction intermediate, and will decompose and continue to react in an acidic environment to form a compound of the formula (G), and thus it is quite difficult to obtain the spiro monomer compound. In the present invention, the preparation of the spiro compound of the formula (Iia) is carried out by the method described in the literature. The synthesis step is as shown in Comparative Example 1-1. However, as described in the literature, only about 1% of the snail of the formula (Iia) can be obtained. Ring compound.

The applicant in this case is looking for the best conditions for preparing the (I-i-a) spiro compound. Many improvements and attempts have been made to summarize the reaction conditions as shown in Table 1. Based on the conditions provided in the previous literature, the reaction time was elongated (as in Comparative Example 1-2). It was found that the spiro compound of the formula (Iia) could not be obtained, and the spiro compound of the formula (Iia) was proved to be in an acidic environment. The intermediate will decompose and continue to react to form a compound of the above formula (G).

Even if the bisphenol A and m-methylphenol molar ratio were changed to 1:3 (Comparative Example 1-3), the molecular weight collision probability was increased, and the spiro compound of the formula (I-i-a) could not be obtained. In Comparative Examples 1-4, the Applicant improved the decomposition of the (Iia) spiro compound by the concept of lowering the temperature and lowering the acidity, which did improve the decomposition, but the yield, relative to the reaction at a high temperature. Still low.

After continuously lowering the temperature (Comparative Example 1-5), the yield was significantly improved. Therefore, the reaction conditions were selected in this case, the ratio of the reactants was changed, and the yield change was observed (Comparative Examples 1-6, 1-7). Too little meta-methylphenol is also detrimental to product formation, and the molar ratio of bisphenol A to m-methylphenol is preferably from 1:7 to 1:10.

After the fixed reactant ratio was 1:7, the effect of the reaction time on the reaction was traced by a nuclear magnetic resonance spectrometer. The results showed that the (Iia) spiro compound was formed in the initial stage (1 to 3 hours) and accounted for the total product. Bulk, which will subsequently decompose to form a compound of formula (G), so shortening the time will increase the yield and yield the highest yield of about 17%.

Discussion on Synthesis of Spiro Compounds of Formula (I-ii-a)

The prior art document J. Org. Chem. 1997, 62 , 1058 mentions that when bisphenol A and excess 3,4-dimethylphenol are catalyzed by acid catalyst, a structure of the following formula (H) will be produced. In this case, various reaction conditions were also tried, and the conditions were optimized, and the experimental results were summarized in Table 2.

The reaction conditions in the prior art documents (Comparative Example 3-1) were repeated, and the obtained compounds were all the compounds of the formula (H), and the desired spiro compound could not be obtained. After reducing the amount of 3,4-dimethylphenol (Comparative Example 3-2), the situation did not improve. The temperature was lowered (Comparative Example 3-3) under the conditions of the prior art literature to obtain a trace amount of the (I-ii-a) spiro compound in a yield of less than 3%. The ratio of the reactants was adjusted again under these conditions (Comparative Examples 3-4 to 3-6), and it was shown that a decrease in the amount of 3,4-dimethylphenol would contribute to the formation of the compound of the formula (I-ii-a), but The low amount of 3,4-dimethylphenol will reduce the molecular collision probability, making the product difficult to produce, which has a negative impact, so the preferred molar ratio of bisphenol A to 3,4-dimethylphenol is about 1:7. 1:10, and the best yield was obtained under 1:7 conditions.

Taking the above optimal conditions (Comparative Example 3-6), the influence of the reaction time on the reaction was also observed by a nuclear magnetic resonance spectrometer. The results showed that the (I-ii-a) spiro compound was formed in the initial stage (1 to 3 hours). And the bulk of the total product, which will subsequently decompose to form the compound of formula (H), the trend is the same as that of the formula (Iia) spiro compound, so shortening the time will increase the yield, and the highest yield is about 20%.

Table 2. Synthesis conditions of spiro compounds of formula (I-ii-a)

Discussion of material properties

In the present invention, the obtained poly(imine) of the formula (IV-ii-a) is prepared into a film, and then subjected to thermal properties, thermal stability, and organic solubility analysis, and is related to the prior art document Macromol. Chem. Phys., 1997, 198, 2181 . The polyimine prepared by the structure of the formula (B) (sample code 6a-6f) was compared for properties, and the polyethylenimine having no soft chain ether bond in the present case was discussed, compared with the polyphthalamide disclosed in the prior art literature. The difference in the nature of the amine.

From the Thermomechanical Analysis (TMA) chart measured by the formula (IV-ii-a) polyimine, it can be observed that the material has a relatively high glass transition temperature (T _g ) and can be as high as 343 ° C. Compared with the polyethylenimine prepared by the ether bond spiro bisamine in the prior art literature, the thermal properties are significantly improved (see Table 3), and the measured coefficient of thermal expansion (CTE) is about 41 ppm/ °C, with good dimensional stability.

The thermogravimetric analysis (TGA) chart measured by the poly(imine) material of the formula (IV-ii-a) shows that the thermal cracking temperature (T _d10 ) is greater than 450 ° C (Table 3), and the material properties of the prior art documents. Similarly, it exhibits excellent thermal stability and a coke residual rate of up to 38% at 800 °C.

a was measured by thermomechanical analysis (TMA) at a heating rate of 5 ° C min ^-1 .

b under the nitrogen, at a heating rate of 10 ° C min ^-1 at the baseline drift of the second differential scanning calorimetry (DSC) heating curve

c Coefficient of thermal expansion (CTE), recorded at 50 ° C to 150 ° C.

d 10 wt% cracking temperature, as measured by thermogravimetric analysis at a heating rate of 20 ° C min ^-1 .

e Coke residual ratio (% by weight) under a nitrogen atmosphere of 800 °C.

The organic solubility test of the poly(imine) of the formula (IV-ii-a) was carried out, and the test results were summarized in Table 4. Compared with the polyetherimine containing an ether group in the prior art, the material exhibited superior organic solubility. In addition to being soluble in common polar solvents, it can also be dissolved in non-polar solvents (such as CH ₂ Cl ₂ , CHCl ₃ ), which means that in addition to reducing the soft ether bond, the rigidity of the molecular chain can be improved. The entanglement of the molecular chain is reduced, and a large free volume is formed, thereby increasing the organic solubility.

Based on the above results, the reduction of ether bonds does bring about a breakthrough in the properties of polyimine materials. In addition to the improvement of thermal properties, the increase in free volume also brings about the improvement of processability. l, and it is said that this material has a very good development prospect in the field of intrinsic microporous polymer (PIM).

^a solubility measured as 5 mg of sample in 0.5 mL of solvent

^b ++, soluble at room temperature; +-, partially soluble; +h, heat soluble; ±, partially soluble; -, insoluble.

^c Not measured in the reference.

The following patent claims are intended to define the scope of the invention. It should be understood that the obvious modifications that can be made by the skilled person based on the disclosure of the present invention are also within the scope of the present invention.

references

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Claims (16)

a spiro compound having the formula (I), Wherein: R ₁ and R ₂ are each H, a C ₁ -C ₆ alkyl group, or a carboxylic acid group (COOH), or R ₁ and R _{2 are} combined into an acid anhydride; and X is O or S, and the limiting condition thereof is Compound is not . The spirocyclic compound of claim 1, wherein when R ₁ is H and R ₂ is methyl, the compound has the formula (Ii) The spiro compound of claim 1, wherein when R ₁ and R ₂ are methyl, the compound has the formula (I-ii) The spirocyclic compound of claim 1, wherein when R ₁ is H and R ₂ is a carboxylic acid group, the compound has the formula (II) The spiro compound of claim 1, wherein when R ₁ and R _{2 are} combined into an acid anhydride, the compound has the formula (III) A method of preparing a spiro compound having the formula (I), Wherein: R ₁ and R ₂ are each H, a C ₁ -C ₆ alkyl group, or a carboxylic acid group (COOH), or R ₁ and R _{2 are} combined into an acid anhydride; and X is O or S, which comprises: bisphenol A is heated to react with an excess of the compound of the formula (i) to form a spiro compound having the formula (I), Wherein R ₁ , R ₂ and X are as defined above, wherein the reaction is carried out at 50 ° C to 90 ° C. The method of claim 6 which is carried out under an acid catalyst, wherein the acid catalyst is selected from the group consisting of organic acids, inorganic acids or combinations thereof. The method of claim 7, wherein the acid catalyst is Methanesulfonic acid (MSA), p-Toluenesulfonic acid (p-TSA), sulfuric acid or oxalic acid. The method of claim 6 wherein the molar ratio of bisphenol A to the compound of formula (i) is from 1:5 to 1:20. The method of claim 6, which is carried out at 70 ° C to 80 ° C. A method for preparing a dibasic acid compound having the formula (II) or a dibasic acid anhydride compound having the formula (III), It comprises: oxidizing a spiro compound having the formula (Ii) or the formula (I-ii) with an oxidizing agent Wherein X is O or S to give a dibasic acid compound having the formula (II) or a dibasic acid anhydride compound having the formula (III). a polymer of formula (IV), Wherein X is O or S; A is a guanamine or oximine group; and B is selected from the group consisting of C ₁ -C ₁₀ alkyl, C ₃ -C ₇ cycloalkyl and the following groups: and ; and n is an integer from 1 to 100. The polymer of claim 12, wherein the polymer is a polyamine having the formula (IV-i) Where X, B, and n are as defined in claim 12. The polymer of claim 12, wherein the polymer is a polyimine of the formula (IV-ii) Where X, B, and n are as defined in claim 12. A process for the preparation of the polyamidamine of the formula (IV-i) of claim 13 which is obtained by polymerizing a compound of the formula (II) according to claim 4 with a diamine monomer compound having the following formula (F). , H ₂ NB-NH ₂ (F) , wherein B is as defined in claim 12. A process for preparing a polyimine of the formula (IV-ii) according to claim 14 which is obtained by polymerizing a compound of the formula (III) according to claim 5 with a diamine monomer compound having the following formula (F) Thus, H ₂ NB-NH ₂ (F) , where B is as defined in claim 12.