JP2023160498A - Cyclic carbonate and method for producing cyclic carbonate - Google Patents

Abstract

To provide a novel cyclic carbonate and a method for producing the same.SOLUTION: The present invention relates to a cyclic carbonate represented by the following formula (1) (where, A is an optionally substituted alicyclic site, L represents a direct bond or a linking group, R1 is an optionally substituted C1-20 aliphatic hydrocarbon group or an optionally substituted C6-20 aromatic hydrocarbon group).SELECTED DRAWING: None

Description

The present invention relates to a cyclic carbonate and a method for producing a cyclic carbonate.

Polycarbonate resin is an engineering plastic with excellent heat resistance, and there is a demand for it to be lightweight and low-cost, as well as having excellent heat resistance and optical properties. In order to meet such demands, special polycarbonate resins based on aromatic skeletons are being actively developed.

On the other hand, polycarbonate resins having an aliphatic structure, particularly an alicyclic structure, are being developed as resins to replace aromatic polycarbonates. Alicyclic polycarbonates tend to have better light resistance and optical properties than polycarbonate resins having aromatic rings such as bisphenol A. For example, Patent Document 1 discloses a polycyclic alicyclic polycarbonate resin that has excellent transparency, heat resistance, and color tone. In addition, polycarbonate is being developed using not only petroleum raw materials but also raw materials derived from biomass such as plants. For example, Patent Document 2 discloses a polycarbonate resin using isosorbide that can be derived from starch as a raw material.

Among such alicyclic polycarbonate resins, poly(cyclohexene carbonate) having a cyclohexane carbonate structure is the simplest polycarbonate having a saturated six-membered carbon ring corresponding to a benzene ring. It is widely known that poly(cyclohexene carbonate) can be synthesized by the reaction of cyclohexene oxide and carbon dioxide, as shown in Patent Document 3, for example. Furthermore, as described in Patent Document 4 and Non-Patent Document 1, it is known that poly(cyclohexene carbonate) can be obtained by ring-opening polymerization of 1,2-cyclohexene carbonate.

Patent No. 4774610 Patent No. 6507495 Patent No. 5403537 JP 2019-108547 Publication

Macromolecules 2014, 47, 4230-4235.

Polycarbonate resins are required to have various physical properties, and new substances are required for cyclic carbonates used as raw materials for the resins.

An object of the present invention is to provide novel cyclic carbonates and methods for producing them.

That is, the present invention is as follows.
<1>
The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting group,
R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. )
A cyclic carbonate represented by
<2>
The cyclic carbonate according to <1>, wherein the A is a cyclohexane-1,2-diyl group.
<3>
The cyclic carbonate according to <1> or <2>, wherein the L is an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group.
<4>
The cyclic carbonate according to any one of <1> to <3>, wherein R ¹ is a cyclohexyl group, an adamantyl group, or a decyl group.
<5>
The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting group,
R ² is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. )
A method for producing a cyclic carbonate represented by
The following formula (2):
(In formula (2), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.)
Cyclic carbonate represented by or the following formula (2'):
(In formula (2'), A' is an optionally substituted unsaturated alicyclic moiety.)
A cyclic carbonate represented by
The following formula (3):
H-S-R ¹ (3)
(In formula (3), R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. .)
A manufacturing method comprising the step of mixing and stirring a mixture containing a thiol compound represented by:

According to the present invention, novel cyclic carbonates and methods for producing them can be provided.

1 shows a ¹ H-NMR spectrum of the cyclic carbonate in Example 1. 1 shows a ¹ H-NMR spectrum of the cyclic carbonate in Example 2. 1 shows a ¹ H-NMR spectrum of the cyclic carbonate in Example 3. ¹ H-NMR spectrum of the cyclic carbonate in Example 4 is shown. ¹ H-NMR spectrum of the polymer in Example 5 is shown. ¹ H-NMR spectrum of the polymer in Example 6 is shown.

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to this embodiment, and can be implemented with various modifications within the scope of the gist.

[Cyclic carbonate]
The cyclic carbonate according to this embodiment is represented by the following formula (1).

In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting group,
R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms.

The cyclic carbonate according to the present embodiment has the above-mentioned structure, and thereby a material exhibiting excellent heat resistance can be obtained. This factor is considered to be as follows, but the factor is not limited to this.

Conventional cyclic carbonates with an alicyclic structure have a cyclic skeleton, but due to their highly rigid structure, there is steric space around the relatively unstable carbonate group, which is susceptible to hydrolysis etc. easy to receive.
On the other hand, since the cyclic carbonate of this embodiment and the polycarbonate resin obtained by polymerizing it have sulfide groups, the carbonate group and the sulfide group interact between molecules, and the area around the carbonate group becomes sterically crowded, resulting in hydration. It is presumed that heat resistance has improved as a result of being less susceptible to decomposition, etc.

In formula (1), A is an optionally substituted divalent alicyclic moiety. The alicyclic moiety is not particularly limited, but includes, for example, a cyclopropane-1,2-diyl group, a cyclobutane-1,2-diyl group, a cyclopentane-1,2-diyl group, and a cyclohexane-1,2-diyl group. , cycloheptane-1,2-diyl group, cyclooctane-1,2-diyl group, cyclononane-1,2-diyl group, and cyclodecane-1,2-diyl group. Among these A, cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, cycloheptane-1,2-diyl group, cyclooctane-1,2 -diyl group is preferred, and cyclobutane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1,2-diyl group, and cycloheptane-1,2-diyl group are more preferred, and cyclohexane-1,2-diyl group is preferred. ,2-diyl group is more preferred.

Alicyclic moiety A may have an unsaturated bond at any position. A may have a plurality of unsaturated bonds.

Furthermore, the alicyclic moiety A may be substituted with any substituent. Substituents include, but are not particularly limited to, hydroxyl groups, phosphoric acid groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 6 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and 1 to 30 carbon atoms. a silyl group having 1 to 30 carbon atoms, a silylalkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or a linear, branched, or cyclic group having 1 to 30 carbon atoms. It is an alkyl group. There may be a plurality of substituents for A, and in that case, each substituent may be the same or different.

The substituent of the alicyclic moiety A is preferably a hydroxyl group, a phosphoric acid group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a C 1 to 20 alkoxy group. ~30 silyl group, silylalkoxy group having 1 to 30 carbon atoms, ester group having 1 to 11 carbon atoms, acyl group having 1 to 11 carbon atoms, or linear, branched, or cyclic carbon number 1 to 30 30 alkyl group, more preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an ester group having 1 to 11 carbon atoms, an acyl group having 1 to 11 carbon atoms, or a linear, branched, or A cyclic alkyl group having 1 to 30 carbon atoms, more preferably a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. More preferably, it is an alkoxy group having 1 to 20 carbon atoms, or a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms.

The phosphate group may be unsubstituted or substituted. That is, it may be a mono-substituted phosphoric acid group or a di-substituted phosphoric acid group. From the viewpoint of achieving the effects of the present invention more effectively and reliably, when the phosphoric acid group is substituted, the substituent is an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. It is preferable that there be. From the same viewpoint, the phosphoric acid group in this embodiment is preferably unsubstituted.

The aryl group having 6 to 20 carbon atoms is not particularly limited, but includes, for example, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, propylphenyl group. , an aryl group that is unsubstituted or has an alkyl group such as a diisopropylphenyl group, an aryl group that has an alkoxy group such as a 4-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a biphenyl group, a naphthyl group, etc. , anthracenyl group.

Examples of the aralkyl group having 6 to 20 carbon atoms include, but are not particularly limited to, unsubstituted or aralkyl groups having an alkyl group such as benzyl group, 4-methylbenzyl group, and phenethyl group, and 4-methoxybenzyl group. , an aralkyl group having an alkoxy group such as a 3,5-dimethoxybenzyl group, and examples thereof include a diphenylmethyl group, a naphthylmethyl group, an anthracenylmethyl group, and the like.

The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, Examples include octyloxy group, nonanyloxy group, decyloxy group, phenoxy group, benzyloxy group, vinyloxy group, and allyloxy group.

Examples of the silyl group having 1 to 30 carbon atoms include, but are not particularly limited to, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, triphenylsilyl group, tert-butyldimethylsilyl group, di-tert-butylisobutylsilyl group. , and tert-butyldiphenylsilyl group.

Examples of the silylalkoxy group having 1 to 30 carbon atoms include, but are not particularly limited to, a trimethylsilylmethoxy group, a trimethylsilylethoxy group, a trimethylsilylphenoxy group, a trimethylsilylbenzyloxy group, a triethylsilylmethoxy group, a triethylsilylethoxy group, and a triethylsilylphenoxy group. , triethylsilylbenzyloxy group, triisopropylsilylmethoxy group, triisopropylsilylethoxy group, triisopropylsilylphenoxy group, triisopropylsilylbenzyloxy group, triphenylsilylmethoxy group, triphenylsilylethoxy group, triphenylsilylphenoxy group, Triphenylsilylbenzyloxy group, tert-butyldimethylsilylmethoxy group, tert-butyldimethylsilylethoxy group, tert-butyldimethylsilylphenoxy group, tert-butyldimethylsilylbenzyloxy group, di-tert-butylisobutylsilylmethoxy group, Di-tert-butylisobutylsilylethoxy group, di-tert-butylisobutylsilylphenoxy group, di-tert-butylisobutylsilylbenzyloxy group, tert-butyldiphenylsilylmethoxy group, tert-butyldiphenylsilylethoxy group, tert-butyl Examples include diphenylsilylphenoxy group and tert-butyldiphenylsilylbenzyloxy group.

Examples of the ester group having 1 to 11 carbon atoms include, but are not limited to, a methyl ester group, an ethyl ester group, a propyl ester group, a butyl ester group, a pentyl ester group, a cyclopentyl ester group, a hexyl ester group, a cyclohexyl ester group, Examples include heptyl ester group, octyl ester group, nonanyl ester group, decyl ester group, phenyl ester group, benzyl ester group, vinyl ester group, and allyl ester group.

Examples of the acyl group having 1 to 11 carbon atoms include, but are not limited to, a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a benzoyl group.

Examples of linear, branched, or cyclic alkyl groups having 1 to 30 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, 1-norbornyl group, 2-norbornyl group, n-octyl group, 1-bicyclo[2.2.2]octyl group, 2 -bicyclo[2.2.2]octyl group, n-nonanyl group, n-decyl group, 1-adamantyl group, 2-adamantyl group, decahydronaphthyl group, and tetracyclododecyl group.

In formula (1), L is a direct bond or a connecting group. Examples of the linking group include divalent alkylene groups that may be linear, branched, or cyclic. The number of carbon atoms in the linking group is preferably 1 to 30, more preferably 1 to 20. The divalent alkylene group is not particularly limited, but includes, for example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, Decylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, norbornylene group, bicyclo[2.2.2]octylene group, deca Examples include hydronaphthylene group and decahydro-1,4:5,8-dimethanonaphthylene group. Among these, L is preferably a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, or a cyclopropylene group. group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, norbornylene group, bicyclo[2.2.2]octylene group, decahydronaphthylene group, Decahydro-1,4:5,8-dimethanonaphthylene group, more preferably methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, hexylene group, cyclobutylene group. group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, norbornylene group, bicyclo[2.2.2]octylene group, decahydronaphthylene group, decahydro-1, 4:5,8-dimethanonaphthylene group, more preferably ethylene group, norbornylene group, or decahydro-1,4:5,8-dimethanonaphthylene group.

In formula (1), R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. R ¹ is not particularly limited, but includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, and a heptyl group. , octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group, norbornyl group, bicyclo[2.2.2]octyl group, decahydronaphthyl group, decahydro-1,4:5,8-dimethanonaphthyl group, Examples include phenyl group, benzyl group, and 3-(2-methyltetrahydro)furyl group. R ¹ is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, Cyclooctyl group, cyclononyl group, cyclodecyl group, adamantyl group, norbornyl group, bicyclo[2.2.2]octyl group, decahydronaphthyl group, decahydro-1,4:5,8-dimethanonaphthyl group, phenyl group, benzyl group , 3-(2-methyltetrahydro)furyl group, more preferably a cyclohexyl group, an adamantyl group, or a decyl group.

The cyclic carbonate according to this embodiment is preferably represented by the following formula (X1).

Preferable L and R ¹ in formula (X1) are the same as those in formula (1).

The cyclic carbonate according to this embodiment is preferably a compound represented by the following formula (X1-1), (X1-2), (X1-3), or (X1-4).

In formula (X1-1), m is an integer of 0 to 18, and R ¹ is the same as in formula (1).

In formula (X1-2), m is an integer of 0 to 18, and R ¹ is the same as in formula (1).

In formula (X1-3), n is an integer of 0 to 3, and R ¹ is the same as in formula (1).

In formula (X1-4), n is an integer of 0 to 3, and R ¹ is the same as in formula (1).

In formulas (X1-1) and (X1-2), m is preferably an integer of 0 to 5, more preferably 1.

In formulas (X1-3) and (X1-4), n is an integer of 0 to 2, preferably 0 or 1.

[Method for producing cyclic carbonate]
The method for producing a cyclic carbonate according to the present embodiment includes a cyclic carbonate (B1) represented by the following formula (2) or a cyclic carbonate (B2') represented by the following formula (2'), and a cyclic carbonate (B2') represented by the following formula (3). It is preferable to have a step of mixing and stirring a mixture containing at least the thiol compound (B2) represented by the following.

In formula (2), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.

In formula (2'), A' is an optionally substituted unsaturated alicyclic moiety.

H-S-R ¹ (3)

In formula (3), R ¹ is the same as in formula (1).

One type of cyclic carbonate (B1) may be used, or a combination of multiple types may be used. In formula (2), A and R ¹ are as described in formula (1) above.

In formula (2), E is an optionally substituted alkenyl group having 1 to 20 carbon atoms. The alkenyl group may be linear, branched, or cyclic. The alkenyl group having 1 to 20 carbon atoms is not particularly limited, but includes, for example, methylene group, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group. group, decenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclohebutenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalene Nyl group, octahydro-1,4:5,8-dimethanonaphthalenyl group. The alkenyl group in formula (2) is preferably a vinylidene group, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, cyclo Propenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclohebutenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalenyl group, octahydro-1 ,4:5,8-dimethanonaphthalenyl group, more preferably vinylidene group, ethenyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group. group, cyclopentenyl group, cyclohexenyl group, cyclohebutenyl group, cyclooctenyl group, cyclononenyl group, cyclodecenyl group, norbornenyl group, bicyclo[2.2.2]octenyl group, octahydronaphthalenyl group, octahydro-1,4:5 , 8-dimethanonaphthalenyl group.

In formula (2'), A' is an optionally substituted unsaturated alicyclic moiety. The unsaturated alicyclic moiety preferably has a carbon-carbon double bond in the alicyclic moiety.

In the method for producing a cyclic carbonate according to the present embodiment, the cyclic carbonate (B1) is preferably represented by the following formula (Y1).

In the method for producing a cyclic carbonate according to the present embodiment, E in formula (Y1) is the same as in formula (2).

In the method for producing a cyclic polycarbonate according to the present embodiment, the cyclic carbonate (B1) is preferably a compound represented by the following formulas (Y1-1) and (Y1-2).

In formula (Y-1), m is the same as in formula (X1-1).

In formula (Y-2), n is the same as in formula (X1-3).

In formula (3), R ¹ is the same as in formula (1). One type of thiol compound (B2) may be used, or a combination of multiple types may be used.

In the mixture containing the cyclic carbonate (B1) and the thiol compound (B2), the mass ratio of the cyclic carbonate (B1) to the thiol compound (B2) is preferably 1:100 to 100:1, and 1: More preferably, the ratio is 50 to 50:1.

A solvent may be added when mixing and stirring the mixture containing the cyclic carbonate (B1) and the thiol compound (B2). Examples of the solvent include, but are not limited to, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, tert-butyl methyl ether, and propylene. Ether solvents such as glycol monomethyl ether acetate, halogen solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane, saturated hydrocarbon solvents such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane, toluene , xylene, o-xylene, m-xylene, p-xylene, and aromatic hydrocarbon solvents such as cresol, as well as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, cyclohexanone, and methyl. Examples include ketone solvents such as isobutyl ketone.

When mixing and stirring a mixture containing the cyclic carbonate (B1) and the thiol compound (B2), the mass ratio of the cyclic carbonate (B1) to the solvent is preferably 100:1 to 1:100, and 90: More preferably, the ratio is 1 to 1:90.

A radical initiator may be added when mixing and stirring the mixture containing the cyclic carbonate (B1) and the thiol compound (B2). A radical initiator refers to a substance that generates radicals by heat, light, redox reaction, or the like. These include organic peroxides, azo compounds, redox initiators, photoinitiators, and the like.

Examples of the organic peroxide include, but are not limited to, benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, and dicumyl peroxide.

Examples of the azo compound include, but are not limited to, 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo(methylethyl)diacetate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile (AIBN), methyl 2,2'-azobis-2-methylpropionate, 2, 2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, dimethyl 2,2'-azobisisobutyrate, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile , 2,2'-azobis-2-methylvaleronitrile, dimethyl 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis-2,4-dimethylvaleronitrile.

Examples of the redox initiator include, but are not limited to, combinations of hydrogen peroxide-iron(II) salt, organic oxide-dimethylaniline, cerium(IV) salt-alcohol, and the like.

Examples of the photoinitiator include, but are not limited to, alkylphenone photoinitiators, α-aminoalkylketone photoinitiators, and phosphine oxide photoinitiators.

The molar ratio of the thiol compound (B2) and the radical initiator when mixing and stirring the mixture containing the cyclic carbonate (B1) and the thiol compound (B2) is preferably 10:1 to 10,000:1, and 20 :1 to 5000:1 is more preferable.

The temperature when mixing and stirring the mixture containing the cyclic carbonate (B1) and the thiol compound (B2) is preferably 0°C to 150°C, more preferably 20°C to 120°C.

The atmosphere during mixing and stirring may be any of air atmosphere, nitrogen atmosphere, argon atmosphere, etc. Among these, a nitrogen atmosphere or an argon atmosphere is preferable, and a nitrogen atmosphere is more preferable.

[Applications of cyclic carbonate]
The cyclic carbonate according to this embodiment can be used as a raw material for polycarbonate resin. A polycarbonate resin is obtained by ring-opening polymerization of a cyclic carbonate using an initiator such as an anionic polymerization initiator. In addition, cyclic carbonates can be used as electrolytes for lithium ion secondary batteries and as additives to electrolytes.

The present invention will be explained in more detail using Examples and Comparative Examples, but the present invention is not limited by these Examples and the like.

In this specification, various physical properties were measured as follows.

[ ¹ H-NMR measurement]
A ¹ H-NMR spectrum of the cyclic carbonate was obtained by performing NMR measurement using an NMR device manufactured by JEOL Ltd. (product name: ECZ400S) and a TFH probe. Note that the reference peak of the heavy solvent was δ _H =7.26 ppm when chloroform-d was used, and the measurement was performed with the number of integrations set to 32.

[Measurement of thermal decomposition start temperature]
A polycarbonate resin and a polycarbonate resin composition were heated at a rate of 10° C./min in an air stream using a TG-DTA device manufactured by Shimadzu Corporation (product name: DTG-60A) and an aluminum krypton cell. Thermal decomposition (TGA) of the polycarbonate resin and polycarbonate resin composition was measured, and the thermal decomposition onset temperature was obtained from the tangential intersection of the TGA curve.

[Synthesis example 1: NORT]
4-vinyl-trans-1,2-cyclohexene carbonate (501 g, 3 mol) and dicyclopentadiene (2484 g, 18 mol) were added to a 3L autoclave. The reaction was continued for 3 days by heating to an internal temperature of 200°C. After cooling to an internal temperature of 60° C., the contents were collected and poured into chloroform (5.5 L) to dissolve. This solution was slowly poured into methanol (20 L) and stirred for 1 hour, then the precipitate was removed by vacuum filtration and rinsed with methanol (1.5 L). After concentrating the filtrate under reduced pressure, the concentrate was subjected to silica gel column chromatography and divided into two fractions, A and B, with 490 g of concentrate obtained from A and 231 g from B. The concentrate of fraction A (490 g) was subjected to silica gel chromatography again, and the fraction containing the target product was concentrated. A white solid began to precipitate during the concentration, so the concentration was stopped midway and the solid was removed by vacuum filtration. The concentrate (144 g) obtained by concentrating the filtrate after removing the white solid under reduced pressure and the concentrate of fraction B (231 g) were combined and distilled under reduced pressure at 220°C/0.6-2 hPa to obtain 168 g of A distillate was obtained. The obtained distillate was purified by silica gel column chromatography and dried under reduced pressure at 50°C to produce 4-(5-norbornen-2-yl)-trans-1,2-cyclohexene carbonate (hereinafter also referred to as NORT). (102 g) was obtained.

[Example 1: CSVT]
4-vinyl-trans-1,2-cyclohexene carbonate (7.64 g, 45.42 mol) and cyclohexanethiol (7.93 g, 63.81 mmol) were weighed into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. 2,2'-Azobisisobutyronitrile (0.08 g, 0.46 mmol) was weighed out and added to the flask, and the flask was immersed in an 80°C oil bath and stirred with a magnetic stirrer for 3 hours. Heated. After cooling, it is purified by silica gel column chromatography, the fraction containing the target substance is collected, concentrated under reduced pressure, and dried under reduced pressure at 60°C to obtain the formula:

Compounds represented by and formula:

A mixture (10.31 g) of the compound represented by was obtained. ^{The 1} H-NMR spectrum is shown in FIG.

[Example 2: DSVT]
Weigh out 4-vinyl-trans-1,2-cyclohexene carbonate (5.03 g, 29.90 mol) and 1-decanethiol (7.79 g, 44.66 mmol) into a 50 mL three-necked flask, and replace the inside of the flask with nitrogen. did. 2,2'-azobisisobutyronitrile (0.05 g, 0.30 mmol) was weighed out and added to the flask, and the flask was immersed in an oil bath at 80°C for 3 hours while stirring with a magnetic stirrer. Heated. After cooling, it is purified by silica gel column chromatography, and the fraction containing the target product is collected, concentrated under reduced pressure, and dried under reduced pressure at 60°C to obtain the following formula:

A compound represented by, and

A mixture (9.88 g) of the compound represented by was obtained. ^{The 1} H-NMR spectrum is shown in FIG.

[Example 3: ASNT]
NORT (2.02 g, 8.61 mmol) synthesized in Synthesis Example 1 and 1-adamantanethiol (1.52 g, 9.04 mmol) were weighed into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. Toluene (oxygen absorbing grade manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; 4 g) and 2,2'-azobisisobutyronitrile (0.03 g, 0.18 mmol) were weighed and added to the flask, and the flask was heated to 80°C. It was immersed in an oil bath and heated for 6 hours while stirring with a magnetic stirrer. After cooling, it is purified by silica gel column chromatography, the fraction containing the target substance is collected, concentrated under reduced pressure, and then dried under reduced pressure at 60 ° C.
Below formula:

Compound represented by

A mixture (2.68 g) of the compound represented by was obtained. ^{The 1} H-NMR spectrum is shown in FIG.

[Example 4: CSNT]
NORT (5.40 g, 23.05 mmol) synthesized in Synthesis Example 1 and cyclohexanethiol (2.77 g, 23.86 mmol) were weighed into a 50 mL three-necked flask, and the inside of the flask was purged with nitrogen. Toluene (manufactured by Fuji Film Wako Pure Chemical Industries, deoxidizing grade; 4 g) and 2,2'-azobisisobutyronitrile (0.05 g, 0.30 mmol) were weighed out and added to the flask, and the flask was heated at 80°C. It was immersed in an oil bath and heated for 3 hours while stirring with a magnetic stirrer. After cooling, it is purified by silica gel column chromatography, the fraction containing the target substance is collected, concentrated under reduced pressure, and then dried under reduced pressure at 60 ° C.
Below formula:

A compound represented by, and

A mixture of compounds represented by (hereinafter also referred to as CSNT; 7.70 g) was obtained. ^{The 1} H-NMR spectrum is shown in FIG.

[Example 5: p(CSVT)]
CVNT (9.92 g, 34.88 mmol) synthesized in Example 1 and dehydrated m-xylene (39.70 g) were weighed into a 50 mL flask and dehydrated using molecular sieve 4A (monomer solution). After purging the inside of another 50 mL three-necked flask with nitrogen, the monomer solution (26.42 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (300 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to stop the reaction (polymerization liquid).
Subsequently, acetone (50 g) was added to the polymerization solution to dilute it. The diluted solution was added to 1460 g of methanol to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under reduced pressure at 100° C. for 2 hours to obtain a CSVT polymer (hereinafter also referred to as p(CSVT); 4.84 g). ^{The 1} H-NMR spectrum is shown in FIG. As a result of measuring the thermal decomposition start temperature by the above method, the thermal decomposition temperature was 302°C.

[Example 6: p(CSNT)]
CSNT (6.98 g, 19.91 mmol) synthesized in Example 4 and dehydrated m-xylene (28.91 g) were weighed into a 50 mL flask and dehydrated using Molecular Sieve 4A (monomer solution). After purging the inside of another 50 mL three-necked flask with nitrogen, the monomer solution (28.53 g) was extracted and added. The flask was immersed in a constant temperature bath at 25°C, the polymerization initiator solution (400 μL) synthesized in Synthesis Example 4 was added, and the mixture was stirred at 25°C for 1 hour. Acetic acid (0.01 g) was added to stop the reaction (polymerization liquid).
Subsequently, acetone (25 g) was added to the polymerization solution to dilute it. The diluted solution was added to 960 g of methanol to precipitate the polymer. The precipitated polymer was collected by vacuum filtration and washed with methanol. The obtained polymer was dried under reduced pressure at 100° C. for 2 hours to obtain a CSNT polymer (hereinafter also referred to as p(CSNT); 5.21 g). ^{The 1} H-NMR spectrum is shown in FIG. As a result of measuring the thermal decomposition start temperature by the above method, the thermal decomposition temperature was 304°C.

The cyclic carbonate of the present invention can be used as a raw material for polycarbonate resin, and has industrial applicability in the field of various resin materials.

Claims (5)

The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting group,
R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. )
A cyclic carbonate represented by The cyclic carbonate according to claim 1, wherein the A is a cyclohexane-1,2-diyl group. The cyclic carbonate according to claim 1, wherein the L is an ethylene group, a norbornylene group, or a decahydro-1,4:5,8-dimethanonaphthylene group. The cyclic carbonate according to claim ¹ , wherein the R 1 is a cyclohexyl group, an adamantyl group, or a decyl group. The following formula (1):
(In formula (1),
A is an optionally substituted alicyclic moiety,
L is a direct bond or a connecting group,
R ² is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. )
A method for producing a cyclic carbonate represented by
The following formula (2):
(In formula (2), A is an optionally substituted alicyclic moiety, and E is an optionally substituted alkenyl group having 1 to 20 carbon atoms.)
Cyclic carbonate represented by or the following formula (2'):
(In formula (2'), A' is an optionally substituted unsaturated alicyclic moiety.)
A cyclic carbonate represented by
The following formula (3):
H-S-R ¹ (3)
(In formula (3), R ¹ is an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. .)
A manufacturing method comprising the step of mixing and stirring a mixture containing a thiol compound represented by: