RU2841745C1 - Ester compound - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a cyclic compound (A) of formula (1):

where each of m and n is independently integer from 1 to 5, wherein the ratio m + n ≥ 4; each of R¹ and R² independently represents a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms, and when the aryl group is an aryl group containing an oxygen-containing substituent, the number of carbon atoms in the oxygen-containing substituent ranges from 1 to 10; plurality R³, plurality R⁴ and R⁵-R⁸, each of which independently represents a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group containing from 1 to 20 carbon atoms, or a halogen atom; a hydrogen atom, a carbon atom or both R¹-R⁸ are optionally replaced with at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom and a silicon atom; while R³-R⁸ are in mutually independent relations, adjacent groups R³ are optionally directly linked to each other to form a multiple bond; adjacent groups R⁴ are optionally directly linked to each other to form a multiple bond; and a plurality R³, bonded with the same carbon, and a plurality R⁴, bonded with the same carbon are optionally bonded to each other to form a cyclic structure.

EFFECT: preparation of an internal donor component capable of producing a propylene polymer with high output, having extremely high stereoregularity, when used as the solid component of a titanium catalyst.

4 cl, 1 tbl, 15 ex

Description

Field of technology

[0001] The present invention relates to a novel ester compound.

Background of the invention

[0002] With respect to conventional methods relating to ester compounds, there are many disclosures relating to applications as additives, such as additives for resins, cosmetics and external skin preparations, bactericidal compositions, antioxidants and chelators. As one such application, a variant of using a titanium catalyst based on a Mg compound for the polymerization of olefins is known.

[0003] A catalyst for the polymerization of olefins is one of the methods that has been widely developed to date, which was prompted by the discovery of the so-called Ziegler-Natta catalysts, for which Ziegler reported in 1953 that ethylene was polymerized even at low pressures using a combination of titanium tetrachloride and an organoaluminum compound, and Natta subsequently reported the first polymerization of propylene using a combination of titanium trichloride and a halogen-containing organoaluminum compound. Meanwhile, it was found that catalysts containing titanium tetrachloride, a magnesium compound and a Lewis base, which belong to the third generation catalysts, could achieve both high polymerization activity (high productivity) and high stereoregularity in the polymerization of propylene. This made it possible to spread propylene polymers (polypropylene) throughout the world.

[0004] It has been found that the Lewis base (hereinafter also referred to as "internal donor"), one of the main components of the above-mentioned third-generation catalyst component (hereinafter also referred to as "titanium catalyst solid component"), greatly influences the performance of the catalyst, and various Lewis bases have been developed so far.

[0005] As Lewis bases for use in Ziegler-Natta catalysts, for example, ethyl benzoate, phthalic acid esters, 1,3-diketone (Patent Literature 1), malonic ester (Patent Literature 2), succinic ester (Patent Literature 3), 2,4-pentanediol diester (Patent Document 4), such as naphthalenediol diester (Patent Document 5), and catechol diester (Patent Document 6) have been described. Basically, enterprises are actively conducting research and development in this field even today.

As for the elementary reactions for synthesizing various esters, a large number of approaches have been disclosed (e.g., Patent Documents 7-10 and Non-Patent Documents 1-19).

LIST OF LINKS

Patent literature

[0006] Patent Document 1: DP 2005-226076A

Patent Document 2: JP2000-516987 A

Patent Document 3: JP2002-542347 A

Patent Document 4: JP2005-517746 A

Patent Document 5: JP2011-529888 A

Patent Document 6: JP2014-500390 A

Patent Document 7: JP2008-247796 A

Patent Document 8: WO2008/062553

Patent Document 9: US2018/0149973 A1

Patent Document 10: US2002/0162991 A1.

Non-patent literature

[0007] Non-patent literature 1: Journal of Organic Chemistry, 1969, 34, 3579-3582.

Non-patent literature 2: Journal of Organic Chemistry, 1971, 36, 3979-3987.

Non-patent literature 3: Fundamentals of organics, 2004, 6, 1589–1592.

Non-patent literature 4: Journal of the American Chemical Society, 1957, 79, 2822-2824.

Non-Patent Literature 5: Organic Synthesis 1991, 70, 47-53

Non-Patent Literature 6: Organic Synthesis 1997, 75, 153-160

Non-Patent Literature 7: Fundamentals of Catalysis 2012, 142, 124-130

Non-Patent Literature 8: Organic Synthesis 1997, 74, 91-100

Non-Patent Literature 9: Fourth Edition of Experimental Chemistry, Vol. 20, Organic Compound Synthesis II, Alcohols and Amines, p. 39

Non-patent literature 10: Journal of Organic Chemistry 1959, 24, 54-55.

Non-Patent Literature 11: Applied Chemistry. International Edition, 1978, 17, 522–524.

Non-patent Literature 12: Bulletin of the Chemical Society of Japan, 1967, 40, 2380-2382.

Non-patent literature 13: Organic synthesis, 1952, 32, 41.

Non-Patent Literature 14: Macromolecules, 2017, 50, 580-586

Non-patent literature 15: Journal of Organic Chemistry, 1980, 45, 2301-2304.

Non-patent literature 16: Journal of Organic Chemistry, 2009, 74, 405-407.

Non-patent literature 17: Journal of Organic Chemistry, 1988, 53, 2120-2122.

Non-patent literature 18: Journal of Organic Chemistry, 1963, 28, 2572-2577.

Non-Patent Literature 19: European Journal of Organic Chemistry, 2017, 24, 3501–3504.

The essence of the invention

Technical task

[0008] Propylene polymers, although having heat resistance and toughness similar to those of general-purpose engineering plastics, have the advantage of releasing less toxic gas even when processed by combustion, since they consist primarily of only carbon and hydrogen.

[0009] With the recent advances in molding technology, using propylene polymer having higher stereoregularity than before, it is possible to develop higher physical properties (such as rigidity and heat resistance). For this reason, propylene polymers having higher stereoregularity are required in the market. From the viewpoint of resource conservation and environmental protection, methods for producing propylene polymer with high productivity have also been required.

[0010] Thus, the object of the present invention is to provide an internal donor component suitable for a solid titanium catalyst component capable of producing a propylene polymer having extremely high stereoregularity with high productivity (high activity), when used mainly for the solid titanium catalyst component.

SOLUTION TO THE PROBLEM

[0011] As a result of careful studies aimed at solving the above-mentioned problems, the present inventors have found that an ester compound having a specific cyclic structure is suitable as, for example, a Lewis base for a solid titanium catalyst component, and have completed the present invention. The present invention relates to, for example, the following [1] to [4].

[0012] [1] A cyclic compound (A) containing polyether groups, represented by the following formula (1):

[0013] [Formula 1]

where each of m and n independently represents an integer from 1 to 5, and the relation m+n ≥ 4 is satisfied;

each of R ¹ and R ² independently represents a substituted or unsubstituted hydrocarbon group containing from 1 to 20 carbon atoms; the plurality of R ³ , the plurality of R ⁴ and R ⁵ -R ⁸ , each independently, represents a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group containing from 1 to 20 carbon atoms, or a halogen atom; a hydrogen atom, a carbon atom or both of R ¹ -R ⁸ are optionally replaced by at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom and a silicon atom; while R ³ -R ⁸ are in mutually independent relationships, adjacent R ³ groups are optionally directly bonded to one another to form a multiple bond; adjacent R ⁴ groups are optionally directly bonded to one another to form a multiple bond; and a plurality of R ³ , bonded to the same carbon, and a plurality of R ⁴ , bonded to the same carbon, are optionally bonded to each other to form a cyclic structure.

[0014] [2] The ester compound (A) according to [1], wherein m is 2 or more and n is 2 or more.

[3] The ester compound (A) according to [1], wherein each of R ¹ and R ² independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0015] [4] The ester compound (A) according to [1], wherein each of R ³ to R ⁸ independently represents a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryloxy group.

ADVANTAGEOUS EFFECTS OF THE INVENTION

[0016] The ester compound of the present invention can be used, for example, in resin additives, cosmetics and preparations for external use on the skin, bactericidal compositions, antioxidants, chelators and Ziegler-Natta catalysts.

Description of embodiments

[0017] The ester compound of the present invention will now be described in detail.

The ester compound of the present invention (hereinafter also referred to as “ester compound (A)”) is represented by the following general formula (1):

[0018] [Formula 2]

[0019] wherein each of R ¹ and R ² independently represents a substituted or unsubstituted hydrocarbon group containing from 1 to 20 carbon atoms. A hydrogen atom, a carbon atom, or both of R ¹ and R ² may be replaced by at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom (hereinafter sometimes referred to as heteroatoms). The heteroatom group is preferably a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, and a silicon atom, more preferably a group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, and still more preferably a group consisting of an oxygen atom and a silicon atom.

[0020] The substituent containing a heteroatom is, for example, a heteroatom-containing hydrocarbon group, a preferred example is a heteroatom-containing aryl group, and a particularly preferred example is an oxygen-containing aryl group. Examples of the heteroatom-containing aryl group include a group with a basic skeleton having a structure in which the aryl structure itself contains a heteroatom, such as a pyrrole ring or a pyran ring, and a group in which a substituent such as a heteroatom-containing hydrocarbon group, for example, an alkoxy group, is bonded to a benzene ring.

[0021] Each of R ¹ and R ² is preferably a hydrocarbon group having 2 to 20 carbon atoms, and the lower limit of the number of carbon atoms is more preferably 4 and still more preferably 6. A more detailed structure will be described later.

[0022] In the present invention, the term "atom", such as a halogen atom or a hydrogen atom in the description of a substituent, may of course refer to bonded aspects such as "H-" or "Cl-" when expressed in a structural formula.

[0023] Examples of the hydrocarbon group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0024] Examples of the heteroatom-containing hydrocarbon group (hereinafter sometimes referred to as a heteroatom-containing hydrocarbon group) may include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.

[0025] Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. These groups preferably contain 1 to 20 carbon atoms. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, a preferred lower limit in the case of an aryl group is 6. On the other hand, the upper limit is preferably 18, more preferably 15, still more preferably 10, and particularly preferably 6. The heteroaryl group preferably has one or more 5-membered ring structures, more preferably has one or more 5 to 7-membered ring structures, and still more preferably has one or more 5-membered ring or 6-membered ring structures.

[0026] Preferably, each of R ¹ -R ² independently represents a group selected from a substituted or unsubstituted alkyl group containing from 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group containing from 4 to 20 carbon atoms, a substituted or unsubstituted alkenyl group containing from 4 to 20 carbon atoms, a substituted or unsubstituted alkynyl group containing from 4 to 20 carbon atoms, a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group containing from 4 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group with 4-20 carbon atoms.

[0027] More preferred are R ¹ and R ² , each of which independently represents a group selected from a substituted or unsubstituted alkyl group having from 4 to 10 carbon atoms, a substituted or unsubstituted aryl group having from 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having from 4 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group containing from 4 to 15 carbon atoms.

[0028] Particularly preferred are R ¹ and R ² , each of which independently represents a substituted or unsubstituted aryl group containing from 6 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group containing from 4 to 10 carbon atoms, and a group selected from substituted or unsubstituted aryl groups containing from 6 to 10 carbon atoms is particularly preferred.

R ¹ and R ² of the present invention may be bonded to R ³ -R ⁸ , which will be described later, to form a monocyclic structure or a polycyclic structure. R ¹ and R ² may be bonded to each other to form a cyclic structure.

[0029] <R ³ - R ⁸ >

In formula (1), for example, each of R ³ -R ⁸ is independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

[0030] A preferable example of a heteroatom group is a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. The heteroatom group is more preferably a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, and a silicon atom, still more preferably a group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, and particularly preferably a group consisting of an oxygen atom and a silicon atom. The substituent containing an oxygen atom is preferably an ether type substituent (a substituent containing a COC type structure), and a structure containing an oxygen double bond is preferably avoided.

[0031] Examples of the hydrocarbon group may include substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0032] Examples of the heteroatom-containing hydrocarbon group may include substituted or unsubstituted heteroatom-containing alkyl groups and heteroatom-containing aryl groups, such as substituted or unsubstituted heteroaryl groups. Examples of the heteroatom-containing aryl group include a group with a basic skeleton having a structure in which the aryl structure itself contains a heteroatom, such as a pyrrole ring or a pyran ring, and a group in which a substituent, such as a heteroatom-containing hydrocarbon group, for example, an alkoxy group, is bonded to a benzene ring.

[0033] Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroatom-containing alkyl groups, and heteroaryl groups. These groups preferably contain 1 to 20 carbon atoms. The lower limit is preferably 2 or more, preferably 3. However, a preferred lower limit in the case of an aryl group is 6. On the other hand, the upper limit is preferably 18, more preferably 15, still more preferably 10, and particularly preferably 6. The heteroaryl group preferably has one or more 5-membered ring structures, more preferably has one or more 5- to 7-membered ring structures, and still more preferably has one or more 5-membered ring or 6-membered ring structures.

[0034] Preferably, at least one of R ³ to R ⁸ is a substituent in the above preferred embodiments, and more preferably, all are substituents in the above preferred embodiments.

[0035] At least one substituent in ^R3 to ^R8 may preferably be a substituent other than hydrogen. Moreover, two or more substituents may preferably be substituents other than hydrogen. In such a case, two or more kinds of substituents may be present at the same time, or all of the substituents may be of the same kind. Further, one or more carbon atoms constituting the cyclic structure may preferably be a quaternary carbon. More preferably, ^R7 and/or ^R8 may preferably be a substituent other than hydrogen. Particularly preferably, ^R7 and/or ^R8 are a hydrocarbon group or a heteroatom-containing hydrocarbon group, and in particular a hydrocarbon group. In such an embodiment, when the ester compound of the present invention is used as a component of an olefin polymerization catalyst, the balance of performance can be improved. Specific examples of the performance include reaction control performance such as activity, stereospecificity, and molecular weight controllability.

[0036] A plurality of R ³ may be present. In such a case, while the R ³ groups bonded to different carbon atoms are in a mutually independent relationship, the R ³ groups bonded to adjacent carbon atoms may be directly bonded to each other to form a multiple bond. Here, being in an independent relationship means that the plurality of R ³ groups can be clearly distinguished from each other in terms of the structural formula, and in particular refers to, for example, a structure in which a plurality of R ³ groups that are bonded to different carbon atoms are not bonded to each other to form a ring structure having three or more ring members.

[0037] A plurality of R ⁴ may be present. In such a case, although the R ⁴ groups bonded to different carbon atoms are in a mutually independent relationship, the R ⁴ groups bonded to adjacent carbon atoms may be directly bonded to each other to form a multiple bond. Here, being in an independent relationship is the same as defined for R ³ and means that a plurality of R ⁴ groups can be clearly distinguished from each other in terms of the structural formula, and specifically refers to, for example, a structure in which a plurality of R ⁴ groups are not bonded to each other to form a ring structure having three or more ring members. The R ³ groups bonded to the same carbon may be bonded to each other to form a monocyclic or polycyclic ring. In addition, the R ⁴ groups bonded to the same carbon may be bonded to each other to form a monocyclic or polycyclic ring.

[0038] The carbon chain structure, including the CR ³ structure and the CR ⁴ structure of formula (1), may be a structure consisting of any of a single bond, a double bond and a triple bond, and preferably consists essentially of a single bond. A heteroatom may be present between the bonds of the carbon chain. Examples of such chain structures include (bivalent) structural formulas as shown below:

[0039] [Formula 3]

[0040] There is one substituent present in each of R ⁵ -R ⁸ . While R ⁵ -R ⁸ , like R ³ and R ⁴ , are in an independent relationship, the substituents (R ³ -R ⁸ ) bonded to adjacent carbon atoms can be directly bonded to each other, so that R ⁵ -R ⁸ can form a multiple bond.

[0041] In formula (1), each m and n are independently selected from an integer from 1 to 5, while the relation m+n ≥ 4 is satisfied.

m and n are numerical values related to the size and balance of the cyclic structure. The preferred lower limit of m and n is 2. In addition, m and n are both 2 or more in a preferred embodiment. The upper limit of m and n is 5, and the preferred upper limit is 4. The numerical values of m and n may be the same or different.

[0042] Examples of a halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, a thexyl group, a cumyl group, and a trityl group.

[0043] Examples of the substituted or unsubstituted alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group.

[0044] Examples of the substituted or unsubstituted alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group.

[0045] Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a cyclopentadienyl group, an indenyl group, and a fluorenyl group.

[0046] Examples of the substituted or unsubstituted aryl group include aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a diisopropylphenyl group, a dimethylisopropylphenyl group, an n-propylphenyl group, an n-butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a naphthyl group, a tetrahydronaphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group and an anthracenyl group, and heteroatom-substituted aryl groups such as a methoxyphenyl group, a dimethylaminophenyl group, a nitrophenyl group and a trifluoromethylphenyl group.

[0047] The heteroatom-containing substituent is preferably an aryl group having an oxygen-containing substituent, and a preferable example is, in particular, a structure in which an oxygen-containing substituent such as an alkoxy group, an aryloxy group, an alkoxyalkyl group, an aryloxyalkyl group, and a substituent in which the oxygen of the above substituent is replaced by a carbonyl group or a carboxyl group is bonded to an aromatic skeleton. Among such substituents, a substituent in which an alkoxy group or an aryloxy group is bonded to an aromatic skeleton is preferable, and a substituent in which an alkoxy group is bonded to an aromatic skeleton is more preferable. The number of carbon atoms in the oxygen-containing substituent is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6. More specifically, preferable examples other than the methoxyphenyl group include an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, and a phenoxyphenyl group. An aryl group having such an oxygen-containing substituent can be particularly preferably used for R ¹ and R ² .

[0048] Examples of the substituted or unsubstituted heteroatom-containing hydrocarbon group include heteroatom-containing alkyl groups such as a methoxymethyl group, a methoxyethyl group, a benzyloxy group, an ethoxymethyl group, an ethoxyethyl group, an acetyl group, a benzoyl group, and heteroaryl groups such as a furyl group, a pyrrolyl group, a thienyl group, a pyrazolyl group, a pyridyl group, a carbazolyl group, an imidazolyl group, a dimethylfuryl group, an N-methylpyrrolyl group, an N-phenylpyrrolyl group, a diphenylpyrrolyl group, a thiazolyl group, a quinolyl group, a benzofuryl group, a triazolyl group and a tetrazolyl group.

[0049] R ³ -R ⁸ , when they are substituents other than hydrogen, may be selected from the substituents exemplified for R ³ -R ⁸ above. R ³ -R ⁸ are more preferably substituents selected from hydrocarbon groups and heteroatom-containing hydrocarbon groups, and are in particular hydrocarbon groups.

[0050] <Specific Examples of Ester Compound (A)>

Although specific examples of the ester compound (A) of the present invention are shown below, the ester compound (A) of the present invention is not limited to them.

[0051] [Formula 4]

[0052] [Formula 5]

[0053] [Formula 6]

[0054] [Formula 7]

[0055] [Formula 8]

[0056] [Formula 9]

[0057] [Formula 10]

[0058] [Formula 11]

[0059] [Formula 12]

[0060] [Formula 13]

[0061] In the above structural formulas, the methyl group is denoted as "Me", the ethyl group is denoted as "Et", the propyl group is denoted as "Pr", the butyl group is denoted as "Bu", and the phenyl group is denoted as "Ph". In addition, [n] represents "normal", [i] represents "iso", and "t" represents "tertiary".

[0062] In the ester compound of the present invention, the OCOR ¹ group and the OCOR ² group bonded to the alicyclic structure may form a cis structure or a trans structure derived from the alicyclic structure, and the ester compound of the cis structure is preferably a major component. The major component here means that the content of the compound with the cis structure exceeds 50 mol% and is preferably 70 mol% or more.

[0063] One suitable application of the ester compound (A) of the present invention is a Lewis base component (internal donor) of a solid titanium catalyst component. Although the reason why the ester compound (A) of the present invention is suitable as an internal donor component is currently unclear, the present inventors suggest the following reason.

[0064] The ester compound (A) used in the present invention has a specific multicyclic structure as described above, and thus it is assumed that the compound has suitable rigidity as a compound, and the structural displacement is relatively small. On the other hand, the structure can be understood as simultaneously having also fragments that allow a rather flexible movement. Accordingly, it is believed that when the ester compound (A) is coordinated with a titanium compound or a magnesium compound, which will be described later, it maintains a stable structure, and changes in the stereospecificity and reactivity of the polymerization as a catalyst during the olefin polymerization reaction are small. It is expected that the flexible structural fragments will reduce the stress resulting from the cyclic structure, and thus can have a buffer function against changes in the reaction environment. From these points of view, it is believed that a highly stereoregular polymer can be obtained in a highly active manner. Moreover, from such points of view, it can be assumed that the ester compound (A) potentially provides a component even with a high molecular weight.

[0065] On the other hand, in the case of a stable structure with a small structural bias, there were initially concerns about a narrow molecular weight distribution, but as shown in the examples below, the process of the present invention allows for a polymer to be produced having a broad molecular weight distribution. This is believed by the inventors to be due to the possibility that, in the case of the ester compound (A), small variations in the cyclic structures and combinations of such variations in the corresponding ring structures greatly affect the molecular weight of the resulting polymer, and the presence of several ring structures leads to a variety of combinations of stereoisomeric structures that the corresponding rings can adopt (e.g., a chair conformation and a boat conformation).

[0066] <Method for producing an ester compound (A)>

The method for producing the ester compound (A) of the present invention is not particularly limited. For example, the ester compound (A) can be produced by a dihydroxylation reaction of an appropriate olefin followed by esterification of a diol obtained by the dihydroxylation. In addition, the ester compound (A) can also be produced by a sequential reaction of introducing a carbonate group into a specific polycyclic compound such as cyclohexadiene, hydrolyzing the carbonate group, and then esterifying the diol obtained by the hydrolysis. More specifically, the ester compound (A) can be produced as follows.

[0067] <<Olefin Synthesis>>

The olefin can be synthesized, for example, by the Diels-Alder reaction of cyclohexadiene and methyl vinyl ketone (Non-Patent Literature 1). For the diene, a diene dimer (e.g. dicyclopentadiene), which is a precursor, can also be used as a starting material.

[0068] <<Diol Synthesis>>

The diol form, which is a precursor of the ester, can be obtained by using the corresponding olefin as a raw material. For example, the reaction of the olefin with potassium permanganate (Non-patent Document 4) or osmium tetroxide (Non-patent Document 5) can directly obtain the diol form.

[0069] As another method, a diol form can be obtained by epoxidizing an olefin moiety using m-chloroperoxybenzoic acid (Non-Patent Literature 6); tert-butyl peroxide (Non-Patent Literature 7); dimethyldioxirane (Non-Patent Literature 8); a solution of formic acid and hydrogen peroxide (Non-Patent Literature 9); a solution of hydrogen peroxide and a molybdenum catalyst; or a solution of hydrogen peroxide and a tungsten catalyst (Non-Patent Literature 10), followed by an acidic or alkaline hydrolysis reaction.

The diol compound can also be obtained after hydrolysis of the cyclic carbonate obtained from the diene. The details are as follows.

[0070] A cyclic carbonate, which is a precursor of a diol, can be obtained by the Diels-Alder reaction of a corresponding diene and vinylene carbonate (Non-Patent Literature 19). As described above, a diene dimer, which is a precursor, can also be used as a starting material for the diene.

Acid or alkaline hydrolysis of the cyclic carbonate yields the diol (Non-patent literature 19).

[0071] <<Ester Synthesis>>

An ester corresponding to the formula (1) can be synthesized by reacting a diol and an acid chloride in the presence of a base. Examples of the base that can be used include, but are not limited to, sodium hydroxide, potassium hydroxide and amine bases. The ester can also be synthesized by a synthesis method in which a diol and a carboxylic acid are reacted in the presence of an acid catalyst or using a condensing reagent such as DCC (Non-Patent Literature 11). When one equivalent of an acid chloride or carboxylic acid is allowed to react with a diol form, an isomer may be formed, but then eliminating the reaction of the acid chloride or carboxylic acid provides a compound corresponding to the formula (1). At this time, R ¹ and R ² may be the same or different. The ester can also be synthesized by allowing the diol form to react with a carboxylic acid in the presence of an azocarboxylic acid ester of triphenylphosphine (Non-Patent Literature 12).

[0072] The ester compound (A) of the present invention is suitable as a Lewis base component of a solid titanium catalyst component as mentioned above, but is not limited to this application. Needless to say, the ester compound is possibly applicable in known additive applications such as additives for various resins, cosmetics and preparations for external use on skin, bactericidal compositions, antioxidants, and chelators.

EXAMPLES

[0073] The methods for synthesizing the ester compound of the present invention will be illustrated in the following examples. The compounds disclosed in the following examples are some stereoisomers and may include other stereoisomers.

In the structural formulas, “Me” represents a methyl group, “n-Pr” represents a normal propyl group, “iPr” represents an isopropyl group, “n-Bu” represents a normal butyl group, “tBu” represents a tertiary butyl group, and “Ph” represents a phenyl group.

[0074] In case of measurement¹H-NMR (nuclear magnetic resonance) A JNM-EX270 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used, and a small amount of tetramethylsilane was added to the deuterated solvent chloroform.

The conditions included a measurement temperature of room temperature, an observed nucleus of ¹ H (270 MHz), a sequence of one pulse, a 45° pulse, a repetition time of 5.5 seconds or more, and an integrated frequency of 16 to 64 times or more. As a reference chemical shift, the hydrogen of tetramethylsilane was set to 0 ppm. Peaks, such as ¹ H, derived from an organic acid compound were determined by the usual method.

[0075] [Example 1] (Synthesis of ester compound)

<Synthesis of compound 1>

Compound 1 shown below was synthesized by the method described below.

[0076] [Formula 14]

[0077] Under a nitrogen atmosphere, 8.0 g of 1,3-cyclohexadiene and 8.6 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating so that the internal temperature was 220°C, and stirring was continued for 6 hours. After cooling the mixture to room temperature, 5 ml of hexane was added, stirred, and the solids were filtered off. The resulting solids were washed with hexane and then dried to obtain 8.5 g of compound 1.

[0078] <Synthesis of Compound 2>

Compound 2 shown below was synthesized by the method described below.

[0079] [Formula 15]

[0080] First, 16.6 g of compound 1, 40.0 g of sodium hydroxide and 100 ml of pure water were added to a 500 ml three-neck flask, stirred under heating until the internal temperature reached 100°C, and continued stirring for 6 hours. After cooling the mixture to room temperature, 12 mol/L of concentrated hydrochloric acid at 50°C or lower was added for neutralization. The reaction solution was extracted three times with ethyl acetate, the organic layer was dried over sodium sulfate and concentrated to obtain 14.0 g of compound 2.

[0081] <Synthesis of Compound 3>

Compound 3 shown below was synthesized by the method described below.

[0082] [Formula 16]

[0083] In a 200 ml three-necked flask under nitrogen atmosphere, 14.0 g of compound 2, 42.2 g of benzoyl chloride and 200 ml of pyridine were added and stirred while heating to an internal temperature of 60°C, and then continued with stirring for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was recrystallized from hexane to obtain 13.1 g of compound 3.

[0084]¹H NMR (270 MHz, CDCl₃, TMS in as an internal standard): 7.83-7.80 (m, 4H), 7.44-7.41 (m, 2H), 7.28-7.20 (m, 4H), 6.41-6.39 (m, 2H), 5.35 (s, 2H), 3.00 (s, 2H), 1.71-1.40 (m, 4H).

[0085] The melting point of the obtained compound 3 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 95°C.

[0086] [Example 2] (Synthesis of ester compound)

Compound 4 shown below was synthesized by the method described below.

[0087] [Formula 17]

[0088] Under a nitrogen atmosphere, 7.0 g of compound 3 obtained in Example 1, 3.6 g of Pd/C (manufactured by Evonik, 5% Pd, water content: 58.6%), and 100 ml of ethyl acetate were added to a 300 ml three-necked flask and stirred at room temperature. Hydrogen under 1 atm pressure was introduced into the reaction vessel to change the nitrogen atmosphere to hydrogen atmosphere, and stirring was continued for 15 hours. After the mixture was filtered through celite, the filtrate was concentrated. The filtrate was recrystallized from hexane to obtain 6.6 g of compound 4.

[0089]¹H NMR (270 MHz, CDCl3, TMS in as internal standard): 7.91-7.88 (m, 4H), 7.49-7.42 (m, 2H), 7.30-7.24 (m, 4H), 5.34 (s, 2H), 3.00 (s, 2H), 2.09-2.05 (m, 4H), 1.71 (br.s, 4H), 1.54-1.52 (m, 2H).

[0090] The melting point of the obtained compound 4 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 105°C.

[0091] [Example 3] (Synthesis of ester compound)

<Synthesis of compound 5>

Compound 5 shown below was synthesized by the method described below.

[0092] [Formula 18]

[0093] Under a nitrogen atmosphere, 13.6 g of α-terpinene and 8.6 g of vinylene carbonate were added to a 30 ml pressure-resistant vessel and stirred with heating so that the internal temperature was 220°C, and stirring was continued for 6 hours. After cooling the mixture to room temperature, 5 ml of hexane was added, stirred, and the solids were filtered off. The resulting solids were washed with hexane and then dried to obtain 14.7 g of compound 5.

[0094] <Synthesis of Compound 6>

Compound 6 shown below was synthesized by the method described below.

[0095] [Formula 19]

[0096] First, 4.5 g of compound 5, 8.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-neck flask, stirred under heating until the internal temperature reached 100°C, and continued stirring for 6 hours. After cooling the mixture to room temperature, 12 mol/L of concentrated hydrochloric acid at 50°C or lower was added for neutralization. The reaction solution was extracted three times with ethyl acetate, the organic layer was dried over sodium sulfate and concentrated, and solids were recovered to obtain 3.9 g of compound 6.

[0097] <Synthesis of Compound 7>

Compound 7 shown below was synthesized by the method described below.

[0098] [Formula 20]

[0099] Under a nitrogen atmosphere, 3.9 g of compound 6, 8.4 g of benzoyl chloride and 100 ml of pyridine were added to a 200 ml three-necked flask and stirred while heating to an internal temperature of 60°C, and stirring was continued for 6 hours. After pyridine was distilled off, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentrating the organic layer, the solids were filtered, washed with hexane and dried to obtain 3.0 g of compound 7.

[0100]¹H NMR (270 MHz, CDCl₃, TMS_Vas internal standard): 7.79-7.68 (m, 4H), 7.43-7.29 (m, 2H), 7.25-7.07 (m, 4H), 6.28-6.09 (m, 2H), 5.42-5.34 (m, 2H), 2.23-2.12 (m, 1H), 1.63-1.25 (m, 4H), 1.17 (s, 3H), 1.02 (d, J = 7.0 Hz, 3H), 0.92 (d, J = 7.0 Hz, 3H).

[0101] The melting point of the obtained compound 7 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 137°C.

[0102] [Example 4] (Synthesis of ester compound)

<Synthesis of compound 8>

Compound 8 shown below was synthesized by the method described below.

[0103] [Formula 21]

[0104] Under a nitrogen atmosphere, 4.5 g of compound 5, 4.3 g of Pd/C (manufactured by Evonik, 5% Pd, water content: 58.6%), and 100 ml of ethyl acetate were added to a 200 ml three-necked flask and stirred at room temperature. Hydrogen under 1 atm pressure was introduced into the reaction vessel to change the nitrogen atmosphere to hydrogen atmosphere, and stirring was continued for 15 hours. After filtering the mixture through celite, the filtrate was concentrated and the solids were recovered to give 4.5 g of compound 8.

[0105] <Synthesis of Compound 9>

Compound 9 shown below was synthesized by the method described below.

[0106] [Formula 22]

[0107] First, 4.5 g of compound 8, 8.0 g of sodium hydroxide and 30 ml of pure water were added to a 50 ml three-neck flask, stirred under heating until the internal temperature reached 100°C, and continued stirring for 6 hours. After cooling the mixture to room temperature, 12 mol/L of concentrated hydrochloric acid at 50°C or lower was added for neutralization. The reaction solution was extracted three times with ethyl acetate, and the organic layer was dried over sodium sulfate and concentrated to obtain 3.8 g of compound 9.

[0108] <Synthesis of Compound 10>

Compound 10 shown below was synthesized by the method described below.

[0109] [Formula 23]

[0110] Under a nitrogen atmosphere, 2.0 g of compound 9, 3.2 g of benzoyl chloride and 50 ml of pyridine were added to a 200 ml three-necked flask and stirred with heating until the internal temperature reached 60°C and stirred for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 3.6 g of compound 10.

[0111]¹H NMR (270 MHz, CDCl3, TMS in as an internal standard): 7.87-7.74 (m, 4H), 7.45-7.12 (m, 6H), 5.49-5.46 (m, 1H), 5.26-5.25 (m, 1H), 2.10-0.82 (m, 18H).

[0112] The melting point of the obtained compound 10 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 107°C.

[0113] [Example 5] (Synthesis of ester compound)

<Synthesis of compound 11>

Compound 11 shown below was synthesized by the method described below.

[0114] [Formula 24]

[0115] Under a nitrogen atmosphere, 4.0 g of compound 9, 9.3 g of 4-methylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml three-necked flask and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 2.9 g of compound 11.

[0116]¹H NMR (270 MHz, CDCl₃, TMS in as an internal standard): 7.76 (d, J = 7.8 Hz, 2H), 7.66 (d, J = 7.8 Hz, 2H), 7.09 (d, J = 8.6 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H), 5.47-5.23 (m, 2H), 2.36 (s, 3H), 2.30 (s, 3H), 2.09-1.26 (m, 11H), 0.95-0.81 (m, 6H).

[0117] [Example 6] (Synthesis of ester compound)

<Synthesis of compound 12>

Compound 12 shown below was synthesized by the method described below.

[0118] [Formula 25]

[0119] In a 200 ml three-necked flask under a nitrogen atmosphere, 4.0 g of compound 9, 11.0 g of 4-n-propylbenzoyl chloride and 50 ml of pyridine were added and stirred while heating to an internal temperature of 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 2.3 g of compound 12.

[0120]¹H NMR (270 MHz, CDCl₃, TMS in as internal standard): 7.76 (d, J = 8.4 Hz, 2H), 7.67 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 6.93 (d, J = 8.1 Hz, 2H), 5.47-5.23 (m, 2H), 2.51-2.48 (m, 4H), 2.10-1.26 (m, 16H), 0.94-0.80 (m, 12H).

[0121] The melting point of the obtained compound 12 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 70°C.

[0122] [Example 7] (Synthesis of ester compound)

<Synthesis of compound 13>

Compound 13 shown below was synthesized by the method described below.

[0123] [Formula 26]

[0124] Under a nitrogen atmosphere, 4.0 g of compound 9, 11.8 g of 4-n-butylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml three-necked flask and stirred while heating to an internal temperature of 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 7.9 g of compound 13.

[0125]¹H NMR (270 MHz, CDCl3, TMS as internal standard): 7.76 (d, J = 7.8 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 7.08 (d, J = 7.8 Hz, 2H), 6.93 (d, J = 8.4 Hz, 2H), 5.47- 5.23 (m, 2H), 2.64-2.51 (m, 4H), 2.10-1.23 (m, 20H), 0.96-0.81 (m, 12H).

[0126] [Example 8] (Synthesis of ester compound)

<Synthesis of compound 14>

Compound 14 shown below was synthesized by the method described below.

[0127] [Formula 27]

[0128] In a 200 ml three-necked flask, 4.0 g of compound 9, 11.8 g of 4-tert-butylbenzoyl chloride and 50 ml of pyridine were added under nitrogen atmosphere and stirred while heating to 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 1.7 g of compound 14.

[0129]¹H NMR (270 MHz, CDCl₃, TMS in as internal standard): 7.79 (d, J = 8.6 Hz, 2H), 7.68 (d, J = 8.6 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 5.47-5.23 (m, 2H), 2.09-1.24 (m, 30H), 0.85-0.81 (m, 6H).

[0130] The melting point of the obtained compound 14 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 137°C.

[0131] [Example 9] (Synthesis of ester compound)

<Synthesis of compound 15>

Compound 15 shown below was synthesized by the method described below.

[0132] [Formula 28]

[0133] Under a nitrogen atmosphere, 4.0 g of compound 9, 10.2 g of 4-methoxybenzoyl chloride and 50 ml of pyridine were added to a 200 ml three-necked flask and stirred with heating until the internal temperature reached 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 4.7 g of compound 15.

[0134]¹H NMR (270 MHz, CDCl3, TMS in as an internal standard): 7.82 (d, J = 8.9 Hz, 2H), 7.73 (d, J = 8.6 Hz, 2H), 6.78 (d, J = 8.9 Hz, 2H), 6.65 (d, J = 8.9 Hz, 2H), 5.44-5.20 (m, 2H), 3.82 (s, 3H), 3.77 (s, 3H), 2.54-0.79 (m, 18H).

[0135] The melting point of the obtained compound 15 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 60°C.

[0136] [Example 10] (Synthesis of ester compound)

<Synthesis of compound 16>

Compound 16 shown below was synthesized by the method described below.

[0137] [Formula 29]

[0138] In a 200 ml three-necked flask, 4.0 g of compound 9, 10.1 g of 3,4-dimethylbenzoyl chloride and 50 ml of pyridine were added under a nitrogen atmosphere, and stirred while heating to an internal temperature of 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 1.2 g of compound 16.

[0139]¹H NMR (270 MHz, CDCl3, TMS in as an internal standard): 7.65-7.45 (m, 4H), 7.09-6.94 (m, 2H), 5.46-5.23 (m, 2H), 2.67-1.30 (m, 24H), 0.84-0.75 (m, 6H).

[0140] The melting point of the obtained compound 16 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 92°C.

[0141] [Example 11] (Synthesis of ester compound)

<Synthesis of compound 17>

Compound 17 shown below was synthesized by the method described below.

[0142] [Formula 30]

[0143] In a 200 ml three-necked flask, 4.0 g of compound 9, 11.7 g of 5,6,7,8-tetrahydronaphthalene-2-carbonyl chloride and 50 ml of pyridine were added under a nitrogen atmosphere and stirred with heating so that the internal temperature was 60°C, and stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, the mixture was washed with 2 mol/L hydrochloric acid and 2 mol/L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the organic layer was purified by silica gel column chromatography and dried to obtain 3.8 g of compound 17.

[0144]¹H NMR (270 MHz, CDCl3, TMS in as an internal standard): 7.63-7.37 (m, 4H), 7.02-6.88 (m, 2H), 5.45-5.22 (m, 2H), 2.76-1.27 (m, 28H), 0.84-0.80 (m, 6H).

[0145] The melting point of the obtained compound 17 was measured using a differential scanning calorimeter (DSC-60A manufactured by SHIMADZU CORPORATION, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 133°C.

[0146] [Example 12] (Synthesis of an ester compound)

<Synthesis of Compound 18 and Compound 19>

Compounds 18 and 19 shown below were synthesized by the method described below.

[0147] [Formula 31]

[0148] Under nitrogen atmosphere, 3.3 g of anhydrous aluminum chloride and 25 ml of anhydrous toluene were added to a 50 ml two-neck flask and stirred at room temperature. An aluminum chloride solution was prepared by slowly adding 4 ml of anhydrous THF dropwise to dissolve the aluminum chloride. Under nitrogen atmosphere, 8.6 g of methyl vinyl ketone, 20.1 g of α-terpinene and 60 ml of anhydrous toluene were added to a 300 ml three-neck flask and stirred while cooling in an ice bath. The previously prepared aluminum chloride solution was slowly added dropwise to the 300 ml flask, then warmed to room temperature and the mixture was stirred overnight. The mixture was cooled again in an ice bath and 100 ml of water was added to stop the reaction. After separating the mixture into an organic layer and an aqueous layer, the organic layer was washed with 50 ml of water, a saturated aqueous solution of sodium bicarbonate and brine in that order, the organic layer was dried over magnesium sulfate and then concentrated in a rotary evaporator. The resulting crude product was purified by silica gel column chromatography to obtain 18.4 g of an isomeric mixture of compound 18 and compound 19.

[0149] <Synthesis of Compound 20 and Compound 21>

Compounds 20 and 21 shown below were synthesized by the method described below.

[0150] [Formula 32]

[0151] First, 7 g of a mixture of compound 18 and compound 19, 132 ml of tert-butyl alcohol and 33 ml of water were added to a 1000 ml three-necked flask equipped with a dropping funnel and cooled to 0°C. Then, 7.91 g of potassium permanganate, 1.79 g of sodium hydroxide and 165 ml of water were added to another flask to prepare an aqueous permanganate solution, which was then added to the dropping funnel. Potassium permanganate was slowly added dropwise so that the internal temperature did not exceed 5°C. After the dropwise addition was complete, stirring was continued for 1 hour and a saturated aqueous solution of sodium thiosulfate was added dropwise until the reddish-violet color of the aqueous layer disappeared. Then 350 ml of ethyl acetate was added and the mixture was allowed to stand. After extracting the organic layer of the supernatant, 350 ml of ethyl acetate was added to the aqueous layer again, and the mixture was left to stand. After the organic layer of the supernatant was extracted and combined with the previous organic layer, the organic layer was washed with brine, dried over magnesium sulfate, and concentrated on a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 2.1 g of a mixture of compound 20 and compound 21 as an isomeric mixture.

[0152] <Synthesis of Compound 22 and Compound 23>

Compounds 22 and 23 shown below were synthesized by the method described below.

[0153] [Formula 33]

[0154] Under a nitrogen atmosphere, 1.93 g of a mixture of compound 20 and compound 21 and 8 ml of dehydrated pyridine were added to a 50 ml three-neck flask. After cooling the mixture in an ice bath, 2 ml of benzoyl chloride were slowly added dropwise, the temperature was raised to room temperature, and stirring was continued overnight. Dichloromethane and water were added to the reaction solution to separate the organic layer, and the aqueous layer was extracted three times with dichloromethane. The organic layer was washed with brine, dried over magnesium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 2.34 g of a mixture of compound 22 and compound 23 (isomeric mixture mixed in a ratio of 71:29).

[0155]¹H NMR (270 MHz, CDCl₃, TMS as an internal standard): δ 7.87-7.71 (m, 4H), 7.50-7.27 (overlaps with the signal_CHCl3,m, 4H), 7.15-7.09 (m, 2H), 6.20 (dd, J = 7.6 Hz, 1.3 Hz, 1H, major isomer), 5.79 (dd, J = 7.9 Hz, 2.3 Hz, 1H, minor isomer), 5.65-5.63 (m, 1H, minor isomer), 5.49 (dd, J = 7.9 Hz, 2.0 Hz, 1H, major isomer), 3.02 (dd, J = 11.9 Hz, 4.9 Hz, 1H, major isomer), 2.81 (t, J = 9.2 Hz, 1H, minor isomer), 2.27 (s, 3H, major isomer), 2.26 (s, 3H, minor isomer), 2.17–1.23 (m, 7H), 0.94–0.81 (m, 9H)

[0156] [Example 13] (Synthesis of an ester compound)

<Synthesis connections 24 and 25>

Compounds 24 and 25 shown below were synthesized by the method described below.

[0157] [Formula 34]

[0158] Under nitrogen atmosphere, 2.0 g of anhydrous aluminum chloride and 18 ml of anhydrous toluene were added to a 50 ml two-neck flask and stirred at room temperature. An aluminum chloride solution was prepared by slowly adding 2.3 ml of anhydrous THF dropwise to dissolve the aluminum chloride. Under nitrogen atmosphere, 9.4 g of phenyl vinyl ketone, 11.6 g of α-terpinene and 40 ml of anhydrous toluene were added to a 300 ml three-neck flask and stirred while cooling in an ice bath. The previously prepared aluminum chloride solution was slowly added dropwise to the 300 ml flask, then warmed to room temperature and the mixture was stirred overnight. The mixture was cooled again in an ice bath and 150 ml of water was added to stop the reaction. The mixture was separated into an organic layer and an aqueous layer, the organic layer was washed with 100 ml of water, saturated aqueous sodium bicarbonate solution and brine in that order, the organic layer was dried over magnesium sulfate and then concentrated in a rotary evaporator. The resulting crude product was purified by silica gel column chromatography to give 10.9 g of a mixture of isomers of compound 24 and compound 25.

[0159] <Synthesis compounds 26 and 27>

Compounds 26 and 27 shown below were synthesized by the method described below.

[0160] [Formula 35]

[0161] First, 10.8 g of a mixture of compound 24 and compound 25, 200 ml of tert-butyl alcohol and 40 ml of water were added to a 1000 ml three-necked flask equipped with a dropping funnel and cooled to 0°C. Then, 6.98 g of potassium permanganate, 1.93 g of sodium hydroxide and 160 ml of water were added to another flask to prepare an aqueous permanganate solution, which was then added to the dropping funnel. Potassium permanganate was slowly added dropwise so that the internal temperature did not exceed 6°C. After the dropwise addition was complete, stirring was continued for 1 hour and a saturated aqueous solution of sodium thiosulfate was added dropwise until the reddish-violet color of the aqueous layer disappeared. Then, 350 ml of ethyl acetate was added, and the mixture was stirred and left to stand. After the organic layer of the supernatant was extracted, 350 ml of ethyl acetate was again added to the aqueous layer, and the mixture was stirred and left to stand. After the organic layer of the supernatant was extracted and combined with the previous organic layer, the organic layer was washed with brine, dried over magnesium sulfate, and concentrated on a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 4.0 g of an isomeric mixture of compound 26 and compound 27.

[0162] <Synthesis connections 28 and 29>

Compounds 28 and 29 shown below were synthesized by the method described below.

[0163] [Formula 36]

[0164] Under a nitrogen atmosphere, 3.6 g of a mixture of compound 26 and compound 27 and 5 ml of dehydrated pyridine were added to a 50 ml three-neck flask. After cooling the mixture in an ice bath, 2.9 ml of benzoyl chloride was slowly added dropwise, the temperature was raised to room temperature, and stirring was continued overnight. Dichloromethane and water were added to the reaction solution to separate the organic layer, and the aqueous layer was extracted three times with dichloromethane. The organic layer was washed with brine, dried over magnesium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 3.42 g of a mixture of compound 28 and compound 29 (isomeric mixture mixed in a ratio of 76:24).

[0165]¹H NMR (270 MHz, CDCl₃, TMS in as internal standard): δ 8.03-7.09 (m, 15H), 6.51 (dd, J = 7.6 Hz, 1.3 Hz, 1H, major isomer), 6.08 (dd, J = 7.9 Hz, 1.6 Hz, 1H, minor isomer), 5.74 (dd, J = 7.9 Hz, 1.0 Hz, 1H, minor isomer), 5.70 (dd, J = 7.6 Hz, 2.0 Hz, 1H, major isomer), 3.84 (dd, J = 11.9 Hz, 4.9 Hz, 1H, major isomer), 3.70 (t, J = 9.2 Hz, 1H, minor isomer), 2.25-1.23 (m, 7H), 0.93-0.75 (m, 9H)

[0166] The melting point of the obtained mixture of compound 28 and compound 29 was measured using a differential scanning calorimeter (DSC 7020 manufactured by Hitachi High-Tech Science Corporation, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 130°C.

[0167] [Example 14]

<Preparation of solid component [α1] titanium catalyst>

After a 1-liter glass vessel was sufficiently purged with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane and 352 g of 2-ethylhexyl alcohol were placed therein and subjected to thermal reaction at 130°C for 3 hours to obtain a homogeneous solution. Then, 241 g of this solution and 6.43 g of ethyl benzoate were added to the glass vessel and stirred at 50°C for 1 hour.

[0168] The resulting homogeneous solution was cooled to room temperature. Then, 38.3 ml of the whole homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C while stirring at 350 rpm for 45 minutes. After the addition was complete, the temperature of this mixture was raised to 80°C for 3.8 hours. When the temperature reached 80°C, 1.26 g of compound 10 was added to the mixture. The temperature was again raised to 120°C over 40 minutes, and the same temperature was maintained with stirring for 35 minutes. After the reaction was completed, the solid portion was recovered by hot filtration. This solid portion was resuspended in 100 ml of titanium tetrachloride, and then the suspension was again subjected to a heating reaction at 120°C for 35 minutes. After completion of the reaction, the solid portion was recovered again by hot filtration and sufficiently washed with decane at 100°C and decane at room temperature until free titanium compound was detected in the decane solution after washing the solid. The solid [α1] titanium catalyst component containing compound 10 and prepared according to the above procedure was kept as a suspension in decane, and a part of it was dried to investigate the composition of the catalyst. The composition of the thus obtained solid [α1] titanium catalyst component included 0.28 wt.% titanium, 1.5 wt.% magnesium, and 0.13 wt.% 2-ethylhexyl alcohol residues.

[0169] <Main polymerization>

After adding 500 g of propylene and 1 nL of hydrogen at room temperature into a 2-liter autoclave, a mixture obtained by mixing 7 ml of heptane, 0.35 mmol of triethylaluminum, 0.07 mmol of cyclohexylmethyldimethoxysilane and 0.0028 mmol of a solid [α1] titanium catalyst component (in terms of titanium atom) was added thereto at 25°C over 10 minutes, and the temperature inside the autoclave was rapidly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped by adding a small amount of methanol, and then propylene was removed. Finally, the obtained polymer particles were dried under reduced pressure at 80°C overnight. Table 1 shows, for example, the activity, volumetric specific gravity, MFR, amount of decane-insoluble component, Tm, Tmf, ΔH and MWD (molecular weight distribution).

[0170] [Table 1]

Table 1

Activity (kg-PP/g-cat.) Specific gravity (g/ml) STR (g/10 min) Content of decane-soluble component (%) Example 14 57.1 0.48 4.4 1.3

Table 1 (continued)

Mw Mw/Mn Mz/Mw Tmf (°C) Tm (°C) Tc (°C) ΔH (J/g) Example 14 424000 8.86 7.41 171.3 161.9 113.5 85.8

[0171] The methods for measuring the physical properties described above are as follows.

(1) Volumetric specific gravity:

The bulk specific gravity was measured in accordance with JIS K-6721.

(2) Melt flow rate (MFR):

According to ASTM D1238E, the measurement temperature of propylene polymer was set to 230°C.

[0172] (3) Amount of soluble (insoluble) component in decane:

About 3 g of propylene polymer (measured with an accuracy of 10-4 g. In the following equation, this weight is denoted by b (g)), 500 ml of decane and a small amount of a heat-resistant stabilizer soluble in decane were added in a glass measuring vessel. Under a nitrogen atmosphere, the temperature was raised to 150 °C for 2 hours while stirring with a stirrer to dissolve the propylene polymer, the temperature was maintained at 150 °C for 2 hours, and then the solution was gradually cooled to 23 °C. over 8 hours. The liquid containing the resulting propylene polymer precipitate was filtered under reduced pressure using a standard 25G-4 glass filter manufactured by Tokyo Garasu Kikai Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the component soluble in decane. Their mass was weighed with an accuracy of ^10-4 g (This mass was designated as a (g) in the following equation.) After this operation, the amount of the decane-soluble component was determined by the following equation.

Decane soluble content = 100 × (500 × a) / (100 × b)

Content of decane-insoluble component = 100 - 100 × (500 × a) / (100 × b).

[0173] (4) Molecular weight distribution:

Gel Permeation Chromatograph: Model HLC-8321 GPC/HT manufactured by Tosoh Corporation

Detector: Differential Refractometer

Column: TSKgel GMH6-HT×2 and TSKgel GMH6-HTL×2 manufactured by Tosoh Corporation were connected in series.

Mobile phase medium: o-dichlorobenzene

Flow rate: 1.0 ml/min

Measurement temperature: 140°C

Method for constructing the calibration curve: a standard polystyrene sample was used.

Sample concentration: 0.1% (w/w)

Sample solution amount: 0.4 ml.

The measurement was carried out under the conditions described above. The resulting chromatogram was analyzed by a known method to calculate the average mass molecular weight (Mw), average number molecular weight (Mn), Z average molecular weight (Mz), as well as the Mw/Mn and Mz/Mw values as molecular mass distribution (MWD) indices. The measurement time for one sample was 60 minutes.

[0174] (5) Melting temperature (Tm) of the polymer:

The melting point (Tm), crystallization temperature (Tc) and heat of fusion (ΔH) of the polymer of the present invention were measured using a differential scanning calorimeter (DSC) in a DSC220C manufactured by Seiko Instruments Inc. 3 to 10 mg of the sample were sealed in an aluminum cup and heated from room temperature to 200°C at a rate of 100°C/minute. The sample was kept at 200°C for 5 minutes and then cooled to 30°C at a rate of 10°C/minute. The peak temperature in this cooling test was determined as the crystallization temperature (Tc). Then, after keeping at 30°C for 5 minutes, the sample was subjected to a second heating to 200°C at a rate of 10°C/minute. In this second heating test, the peak temperature was used as the melting point (Tm) and the amount of heat released was used as the heat of fusion (ΔH).

[0175] The final melting point (Tmf) of the polymer of the present invention was measured using a differential scanning calorimeter (DSC) in a DSC220C manufactured by Seiko Instruments Inc. 3 to 10 mg of sample were sealed in an aluminum crucible and heated from room temperature to 240°C at a rate of 80°C/minute. The sample was held at 240°C for 1 minute and then cooled to 0°C at a rate of 80°C/minute. After holding at 0°C for 1 minute, the sample was heated to 150°C at a rate of 80°C/minute and held for 5 minutes. Finally, the sample was heated to 180°C at a rate of 1.35°C/min, and the intersection of the tangent of the inflection point on the high-temperature side of the peak obtained in this final heating test and the baseline was used as the final melting point (Tmf).

[0176] Tmf can be regarded as one of the parameters for evaluating, for example, the ease of crystallization and the strength of the crystal structure of a polymer in the ultra-high molecular weight region, which is said to be difficult to crystallize, and the strength of the crystal structure of a component having an extremely high degree of crystallinity. More specifically, it can be considered that since this Tmf value is higher, the ultra-high molecular weight polymer component is more likely to form crystals that are strong and have high heat resistance.

[0177] [Example 15] (Synthesis of an ester compound)

<Synthesis of compound 30>

Compound 30 shown below was synthesized by the method described below.

[0178] [Formula 37]

[0179] (Synthesis of precursor (cyclic olefin compound))

Under nitrogen atmosphere, 4.5 g of anhydrous aluminum chloride and 90 ml of anhydrous toluene were added to a 200 ml two-neck flask and stirred at room temperature. Aluminum chloride solution was prepared by slowly adding 5.6 ml of anhydrous THF dropwise to dissolve aluminum chloride. Under nitrogen atmosphere, 24.3 g of phenyl 1-propenyl ketone, 28.0 g of α-terpinene and 170 ml of anhydrous toluene were added to a 500 ml three-neck flask and stirred while cooling in an ice bath. The previously prepared aluminum chloride solution was slowly added dropwise to the 500 ml flask, then warmed to room temperature and the mixture was stirred overnight. The mixture was cooled again in an ice bath and 150 ml of water was added to stop the reaction. The reaction solution was added to a separatory funnel, and then 300 ml of methylene chloride was added. After the organic layer and the aqueous layer were separated, the organic layer was washed with 300 ml of water and separated again. The organic layer was washed with a saturated aqueous solution of sodium bicarbonate and brine, dried over magnesium sulfate, and then concentrated on a rotary evaporator. The resulting crude product was purified by silica gel column chromatography to obtain 12.0 g of Diels-Alder adduct (cyclic olefin compound).

[0180] (Synthesis of diol compound)

First, 12.0 g of Diels-Alder adduct, 167 ml of tert-butanol and 42 ml of water were charged into a 1000 ml three-necked flask, then equipped with a dropping funnel and cooled to 0 °C. Then, 10.0 g of potassium permanganate, 2.2 g of sodium hydroxide and 209 ml of water were added to another flask to prepare an aqueous solution of permanganate, which was then added to the dropping funnel. Potassium permanganate was slowly added dropwise so that the internal temperature did not exceed 5 °C. After the dropwise addition was completed, stirring was continued for 1 hour, and a saturated aqueous solution of sodium thiosulfate was added dropwise until the reddish violet color of the aqueous layer disappeared. After adding 350 ml of ethyl acetate and stirring the mixture, the supernatant was left to stand. After extracting the organic layer of the supernatant, 350 ml of ethyl acetate was added to the aqueous layer, the mixture was stirred, and then the supernatant was left to stand again. The organic layer of the supernatant was extracted in the same manner and combined with the above-mentioned organic layer. The organic layer was washed with brine, dried over magnesium sulfate, and then concentrated on a rotary evaporator to obtain 14.0 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 3.84 g of a diol compound.

[0181] (Synthesis of ester compound 30)

Under nitrogen atmosphere, 3.84 g of the above diol and 12.4 ml of dehydrated pyridine were added to a 50 ml three-neck flask. After cooling the mixture in an ice bath, 2.5 ml of benzoyl chloride were slowly added dropwise, the temperature was raised to room temperature, and stirring was continued overnight. Dichloromethane and water were added to the reaction solution to separate the organic layer, and the aqueous layer was extracted three times with dichloromethane. The organic layer was washed with brine, dried over magnesium sulfate, and then concentrated on a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 2.11 g of compound 30 as the major product.

[0182]¹H NMR (270 MHz, CDCl₃, TMS in as internal standard): δ 8.08–8.01 (m, 2H), 7.91–7.83 (m, 2H), 7.82–7.72 (m, 2H), 7.65–7.23 (m, 7H), 7.20–7.07 (m, 2H), 6.38 (d, J = 7.6 Hz, 1H), 5.72–5.61 (m, 1H), 3.42 (d, J = 5.3 Hz, 1H), 2.16–1.93 (m, 2H), 1.86–1.44 (m, 4H), 1.12 (d, J = 6.9 Hz, 3H), 0.87–0.69 (m, 9H)

[0183] The melting point of the obtained compound 30 was measured using a differential scanning calorimeter (DSC 7020 manufactured by Hitachi High-Tech Science Corporation, initial temperature: 25°C, final temperature: 300°C, heating rate: 10°C/min) and was 60°C.

INDUSTRIAL APPLICABILITY

[0184] The novel ester compound of the present invention is a compound useful for producing additives for resins, cosmetic materials and external preparations for skin, microbicidal compositions, antioxidants, chelators and Ziegler-Natta catalysts. The compound can be used, in particular, as a catalyst component for Ziegler-Natta catalysts, and it enables the production of a catalyst that imparts excellent stereoregularity and productivity in the polymerization of polypropylene. As described above, the ester compound of the present invention has extremely high industrial value.

Claims (7)

1. A cyclic compound (A) containing a polyether group, represented by the following formula (1): where each of m and n independently represents an integer from 1 to 5, and the relation m+n ≥ 4 is satisfied; each of R ¹ and R ² independently represents a substituted or unsubstituted aryl group containing from 6 to 20 carbon atoms, and when the aryl group is an aryl group containing an oxygen-containing substituent, the number of carbon atoms in the oxygen-containing substituent is from 1 to 10; the plurality of R ³ , the plurality of R ⁴ , and R ⁵ -R ⁸ , each independently, represents a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group containing from 1 to 20 carbon atoms, or a halogen atom; the hydrogen atom, the carbon atom, or both of R ¹ -R ⁸ are optionally replaced by at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom; while ^R3 - ^R8 are in mutually independent relationships, adjacent ^R3 groups are optionally directly bonded to each other to form a multiple bond; adjacent ^R4 groups are optionally directly bonded to each other to form a multiple bond; and a plurality of ^R3s bonded to the same carbon and a plurality of ^R4s bonded to the same carbon are optionally bonded to each other to form a cyclic structure. 2. Compound (A) according to claim 1, wherein m is 2 or more, and n is 2 or more. 3. The compound (A) according to claim 1, wherein each of R ³ to R ⁸ independently represents a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryloxy group. 4. The compound (A) according to claim 1, wherein each of R ³ and R ² independently represents a substituted or unsubstituted aryl group having from 6 to 15 carbon atoms, and when the aryl group is an aryl group containing an oxygen-containing substituent, the number of carbon atoms in the oxygen-containing substituent is from 1 to 8.