Polycarbonate and polycarbonate production method

Abstract

To provide polycarbonate including an ethylene carbonate unit composed of only a carbonate bond.SOLUTION: There is provided polycarbonate of Formula (1). In the formula (1), R1 to R4 are each independently a hydrogen atom, a hydroxyl group, a phosphoric acid group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. Two or more of R1 to R4 may be bonded to each other through at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group and a carbonate group, and may form a cyclic structure.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to polycarbonates and methods for producing polycarbonates. [Background technology]

[0002] Polyethylene carbonate has been known as a material for solid electrolytes, polymer electrolytes, biocompatible materials, and sacrificial agents. As a method for producing polyethylene carbonate, a method for producing it by alternating copolymerization of carbon dioxide and ethylene oxide is known (for example, see Patent Document 1), but this method has problems in that ethylene oxide monomer and oligomer components remain, and also in that decarbonation occurs during polymerization, resulting in the formation of ether bonds in the polymer.

[0003] On the other hand, a method for producing polyethylene carbonate by ring-opening polymerization of ethylene carbonate (EC) is known as a method that does not cause the above problems. However, since ethylene carbonate itself is a stable compound, its reactivity as a carbonate monomer is low, and from a practical standpoint, this polymerization method cannot be said to be favorable.

[0004] In response to this, for example, a method has been disclosed in which a cyclic ester and ethylene carbonate are copolymerized in the presence of a zinc catalyst to obtain polyethylene carbonate (see, for example, Patent Document 2), and a method has been disclosed in which an acid anhydride and ethylene carbonate are copolymerized in the presence of a bis(triphenylphosphoranylidene)ammonium chloride catalyst to obtain polyethylene carbonate (see, for example, Non-Patent Document 1). However, these methods have the problem that the obtained polymer contains an ester component. In addition, a polymerization method using sodium stannate trihydrate as a catalyst (for example, Non-Patent Document 2) has been disclosed, but the polymerization reaction is carried out under high-temperature conditions exceeding 120°C, and this has the problem that ether bonds are contained in the polymer due to decarboxylation. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-214295 A [Patent Document 2] Special Publication No. 2015-518913 [Non-patent literature]

[0006] [Non-Patent Document 1] Angew. Chem. Int. Ed. 2022, 61, e202113152 [Non-Patent Document 2] RSC Adv., 2017, 7, 11786-11795 Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, the conventional methods for producing polycarbonate have the problem that unnecessary bonding units are contained in the polymer.

[0008] In view of the above problems in the prior art, an object of the present invention is to provide a polycarbonate containing desired ethylene carbonate units consisting only of carbonate bonds, and a method for producing the same. [Means for solving the problem]

[0009] Means for Solving the Problems The present inventors have conducted intensive research to solve the above problems and have found that a polycarbonate containing no ether bonds can be obtained by copolymerizing a cyclic carbonate having a specific alicyclic skeleton with ethylene carbonate, thereby completing the present invention. That is, the present invention is as follows.

[0010] [1] A polycarbonate containing a structural unit represented by the following formula (1), which does not contain an ether bond:

[0011] [ka]

[0012] In formula (1), R1 to R4 each independently represent a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. Any two or more of R1 to R4 may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure. x and y are the numbers of repeating units, and the arrangement of the repeating units represented by x and y in the polymer is block or random.

[0013] [2] A method for producing a polycarbonate, comprising a step of copolymerizing a cyclic carbonate having an alicyclic skeleton represented by the following formula (2) with ethylene carbonate:

[0014] [ka]

[0015] In formula (2), R1 to R4 each independently represent a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. Any two or more of R1 to R4 may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure. Effect of the Invention

[0016] According to the present invention, it is possible to provide a polycarbonate containing ethylene carbonate units consisting only of carbonate bonds. [Brief description of the drawings]

[0017] [Figure 1] 1 is a 1H-NMR spectrum of the polymer obtained in Example 1. [Diagram 2] 1 is a 13C-NMR spectrum of the polymer obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, an embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described in detail. It should be noted that the present invention is not limited to the present embodiment, and various modifications can be made within the scope of the present invention. In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit of a numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.

[0019] [Polycarbonate] The polycarbonate of the present embodiment contains a constitutional unit represented by the following formula (1). The polycarbonate of this embodiment is a polycarbonate that does not contain an ether bond.

[0020] [ka]

[0021] In formula (1), R1 to R4 each independently represent a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. Any two or more of R1 to R4 may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure. x and y are the numbers of repeating units, and the arrangement of the repeating units represented by x and y in the polymer is block or random.

[0022] In this specification, the term "carbonate group" refers to a divalent substituent represented by -OC(=O)O-.

[0023] In the formula (1), from the viewpoint of improving the thermal stability of the glass transition point and the thermal weight loss, x is preferably 1 to 10,000, and from the viewpoint of solubility, y is preferably 1 to 10,000. The polycarbonate of the present embodiment preferably has a number average molecular weight Mn measured by gel permeation chromatography (GPC) of 2,000 to 500,000, from the viewpoint of obtaining it as a solid content. The Mn of the polycarbonate of this embodiment can be measured by GPC (gel permeation chromatography), specifically, by the method described in the examples below. The values ​​of x and y and the number average molecular weight can be controlled by adjusting the amounts of the cyclic carbonate and ethylene carbonate added in the polymerization step.

[0024] The polycarbonate of this embodiment contains the desired ethylene carbonate unit consisting of only carbonate bonds. The polycarbonate of this embodiment is characterized in that it does not contain an ether bond in its structure. The term "not containing an ether bond" means that the measured content is less than 1%. The content of the ether bond is1 It can be measured by H-NMR spectroscopy, specifically, by the method described in the Examples below. The polycarbonate of this embodiment having such a structure can be produced by the method described below. The polycarbonate of this embodiment contains the desired ethylene carbonate units as described above, does not contain ether bonds, and is of high quality. By not including ether bonds, for example, in solid electrolytes or polymer electrolytes using lithium salts as electrolyte salts, carbonate bonds have lower water absorption and higher mechanical strength than ether bonds, and are expected to improve the conductivity of lithium ions. In addition, for example, when used as a biocompatible material, carbonate bonds are expected to be more degradable in vivo than ether bonds. Furthermore, when used as a sacrificial agent, carbonate bonds are expected to be more easily decomposed when heated than ether bonds. The polycarbonate of the present embodiment has a structure that does not contain an ether bond, and therefore exhibits the above-mentioned excellent effects.

[0025] [Production method of polycarbonate] The method for producing a polycarbonate according to the present embodiment includes a step of copolymerizing a cyclic carbonate having an alicyclic skeleton represented by the following formula (2) with ethylene carbonate. Cyclic carbonates having an alicyclic skeleton represented by the formula (2) below have a trans-type five-membered ring carbonate structure directly bonded to a cyclohexane skeleton and are characterized by high ring-opening polymerization properties, which allows the production of high-quality polycarbonates that do not contain ether bonds, as described above. The trans-type five-membered cyclic carbonate has a lower bond dissociation energy than the cis-type, so the ring opens easily, and because part of the five-membered cyclic carbonate has a rigid cyclohexane structure that restricts its freedom to a moderate extent, it exists stably as a monomer and is easily polymerized homopolymerically or copolymerized with comonomers (i.e. has high ring-opening polymerization ability).

[0026] [ka]

[0027] In the formula (2), R1 to R4 each independently represent a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. Any two or more of R1 to R4 may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure.

[0028] In the formula (2), the alkoxy group having 1 to 30 carbon atoms in R1 to R4 is not limited to the following, but examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentoxy group, a 1-ethylpropoxy group, a 1-methylbutoxy group, a 2-methylbutoxy group, a 3-methylbutoxy group, a 2,2-dimethylpropoxy group, a 1,1-dimethylpropoxy group, an n-hexyloxy group, a 1-ethylbutoxy group, a 2-ethylbutoxy group, a 3-ethylbutoxy group, a 1-methylpentyloxy group, a 2-methylbut ... n-Heptyloxy, 1-methylhexyloxy, 2-methylhexyloxy, 3-methylhexyloxy, 4-methylpentyloxy, 1,1-dimethylbutyloxy, 2,2-dimethylbutyloxy, 3,3-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,3-dimethylbutyloxy, n-heptyloxy, 1-methylhexyloxy, 2-methylhexyloxy, 3-methylhexyloxy, 4-methylhexyloxy, 5-methylhexyloxy, 1-ethylpentyloxy, 2-ethylpentyloxy, 3-ethylpentyloxy, butyloxy group, 1,1-dimethylpentyloxy group, 2,2-dimethylpentyloxy group, 3,3-dimethylpentyloxy group, 4,4-dimethylpentyloxy group, 1,2-dimethylpentyloxy group, 1,3-dimethylpentyloxy group, 1,4-dimethylpentyloxy group, 2,3-dimethylpentyloxy group, 2,4-dimethylpentyloxy group, 3,4-dimethylpentyloxy group, 2-methyl-3,3-dimethylbutyloxy group, 1-methyl-3,3-dimethylbutyloxy group, 1,2,3-trimethylbutyloxy group, 1,3-dimethyl- 2-pentyloxy group, 2-isopropylbutyloxy group, n-octyloxy group, 2-octyloxy group, 3-octyloxy group, 4-octyloxy group, 2-methylheptyloxy group, 3-methylheptyloxy group, 4-methylheptyloxy group, 5-methylheptyloxy group, 6-methylheptyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 4-ethylhexyloxy group, 5-ethylhexyloxy group, 1,1-dimethylhexyloxy group, 2,2-dimethylhexyloxy group, 3,3-dimethylhexyloxy group, 4,Examples of alkyloxy groups having 1 to 30 carbon atoms include a 4-dimethylhexyloxy group, a 5,5-dimethylhexyloxy group, a 1,2-dimethylhexyloxy group, a 1,3-dimethylhexyloxy group, a 1,4-dimethylhexyloxy group, a 1,5-dimethylhexyloxy group, a 2,3-dimethylhexyloxy group, a 2,4-dimethylhexyloxy group, a 2,5-dimethylhexyloxy group, a 1,1-ethylmethylpentyloxy group, a 2,2-ethylmethylpentyloxy group, a 3,3-ethylmethylpentyloxy group, and a 4,4-ethylmethylpentyloxy group.

[0029] In addition, the alkoxy group having 1 to 30 carbon atoms in R1 to R4 is not limited to the following, but examples thereof include a 1-ethyl-2-methylpentyloxy group, a 1-ethyl-3-methylpentyloxy group, a 1-ethyl-4-methylpentyloxy group, a 2-ethyl-1-methylpentyloxy group, a 3-ethyl-1-methylpentyloxy group, a 4-ethyl-1-methylpentyloxy group, a 2-ethyl-3-methylpentyloxy group, a 2-ethyl-4-methylpentyloxy group, a 3-ethyl-2-methylpentyloxy group, a 4-ethyl-3-methylpentyloxy group, a 3-ethyl-4-methylpentyloxy group, a 4-ethyl-3-methylpentyloxy group, a 1-(2-methylpropyl)butyloxy group, a 1-(2-methylpropyl)-2- Examples of such alkyloxy groups include alkyloxy groups having 1 to 30 carbon atoms, such as a methylbutyloxy group, a 1,1-(2-methylpropyl)ethyloxy group, a 1,1-(2-methylpropyl)ethylpropyloxy group, a 1,1-diethylpropyloxy group, a 2,2-diethylpropyloxy group, a 1,1-ethylmethyl-2,2-dimethylpropyloxy group, a 2,2-ethylmethyl-1,1-dimethylpropyloxy group, a 2-ethyl-1,1-dimethylbutyloxy group, an n-nonyloxy group, an n-decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, and an icosyloxy group.

[0030] Furthermore, examples of the alkoxy group having 1 to 30 carbon atoms in R1 to R4 include, but are not limited to, a cyclopropoxy group, a cyclobutoxy group, a cyclopentoxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a 2-ethylcyclopentyloxy group, a 3-ethylcyclopentyloxy group, a 2,3-dimethylcyclopentyloxy group, a 2,4-dimethylcyclopentyloxy group, a 1-methylcyclohexyloxy group, a 2-methylcyclohexyloxy group, Examples of cycloalkyloxy groups include cycloalkyloxy groups having 3 to 30 carbon atoms, such as a cycloalkyloxy group, a 3-methylcyclohexyloxy group, a 4-methylcyclohexyloxy group, a 2,3-dimethylcyclohexyloxy group, a 2,3-dimethylcyclohexyloxy group, a 2,5-dimethylcyclohexyloxy group, a 2,6-dimethylcyclohexyloxy group, a 3,5-dimethylcyclohexyloxy group, a 2-ethylcyclohexyloxy group, a 3-ethylcyclohexyloxy group, and a 4-ethylcyclohexyloxy group.

[0031] Furthermore, examples of the alkoxy group having 1 to 30 carbon atoms in R1 to R4 include, but are not limited to, aryloxy groups having 6 to 30 carbon atoms, such as a phenoxy group, a benzyloxy group, a tolyloxy group, a xylyloxy group, a trimethylphenyloxy group, a cumenyloxy group, a biphenyloxy group, and a naphthyloxy group.

[0032] In the formula (2), examples of the ester group having 1 to 30 carbon atoms for R1 to R4 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, a heptyl ester group, an octyl ester group, a nonanyl ester group, a decyl ester group, a phenyl ester group, a benzyl ester group, a vinyl ester group, and an allyl ester group.

[0033] In the formula (2), examples of the acyl group having 1 to 30 carbon atoms for R1 to R4 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.

[0034] In the formula (2), examples of the unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms in R1 to R4 include, but are not limited to, a methyl group as a C1 alkyl group, an ethyl group as a C2 alkyl group, and an n-propyl group and a 2-propyl group as a C3 alkyl group; an n-butyl group, an isobutyl group, and a t-butyl group as a C4 alkyl group; an n-pentyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, and a 1,1-dimethylpropyl group as a C5 alkyl group; an n-hexyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, and a 3,3-dimethylbutyl group as a C6 alkyl group. C7 alkyl groups include n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl. Examples of dimethylpentyl groups include a 4,4-dimethylpentyl group, a 1,2-dimethylpentyl group, a 1,3-dimethylpentyl group, a 1,4-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3,4-dimethylpentyl group, a 2-methyl-3,3-dimethylbutyl group, a 1-methyl-3,3-dimethylbutyl group, a 1,2,3-trimethylbutyl group, a 1,3-dimethyl-2-pentyl group, and a 2-isopropylbutyl group.

[0035] Examples of C8 alkyl groups include n-octyl, 2-octyl, 3-octyl, 4-octyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethyl ...5,4-dimethylhexyl, 5,5-dimethylhexyl, 6-methylheptyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 5,5-dimethylhexyl, 5,6-dimethylhexyl, 5,7-dimethylhexyl, 5,8-dimethylhexyl, 6,9-dimethylhexyl, 7,10-dimethylhexyl, 7,11-dimethylhexyl, 7,12-dimethylhexyl, 7,13-dimethylhexyl, 7,14-dimethylhexyl, 7,15-dimethylhexyl, 7,16-dimethylhexyl, 7,17-dimethylhexyl, 7,1 Methylhexyl, 5,5-dimethylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethylmethylpentyl, 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2- Examples of the alkyl group include a methylpentyl group, a 1-ethyl-3-methylpentyl group, a 1-ethyl-4-methylpentyl group, a 2-ethyl-1-methylpentyl group, a 3-ethyl-1-methylpentyl group, a 4-ethyl-1-methylpentyl group, a 2-ethyl-3-methylpentyl group, a 2-ethyl-4-methylpentyl group, a 3-ethyl-2-methylpentyl group, a 4-ethyl-3-methylpentyl group, a 3-ethyl-4-methylpentyl group, a 4-ethyl-3-methylpentyl group, a 1-(2-methylpropyl)butyl group, a 1-(2-methylpropyl)-2-methylbutyl group, a 1,1-(2-methylpropyl)ethyl group, a 1,1-(2-methylpropyl)ethylpropyl group, a 1,1-diethylpropyl group, a 2,2-diethylpropyl group, a 1,1-ethylmethyl-2,2-dimethylpropyl group, a 2,2-ethylmethyl-1,1-dimethylpropyl group, and a 2-ethyl-1,1-dimethylbutyl group.

[0036] Furthermore, examples of the C9 alkyl group include nonyl and isononyl groups, examples of the C10 alkyl group include decyl and isodecyl groups, examples of the C11 alkyl group include undecyl groups, examples of the C12 alkyl group include dodecyl groups, examples of the C13 alkyl group include tridecyl groups, examples of the C14 alkyl group include tetradecyl groups, examples of the C15 alkyl group include pentadecyl groups, examples of the C16 alkyl group include hexadecyl groups, examples of the C17 alkyl group include heptadecyl groups, examples of the C18 alkyl group include octadecyl groups, examples of the C19 alkyl group include nonadecyl groups, and examples of the C20 alkyl group include icosyl groups.

[0037] In the formula (2), any two or more of R1 to R4 may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure. The alkylene group is -(CH2) n -, and the alkylenedioxy group is -O-(CH2) n It is represented by -O-, and the ester group is -OC(=O)-(CH2) m A carbonate group is represented by -OC(=O)-O-. In the alkylene group and alkylenedioxy group, n is 1 to 30, and in the ester group, m is 1 to 29. In the formula (2), R1 to R4 are preferably a hydrogen atom, a hydroxyl group, a phosphate group, or an alkoxy group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, and even more preferably a hydrogen atom.

[0038] In the formula (2), when R1 to R4 are all hydrogen atoms, the compound is trans-1,2-cyclohexene carbonate represented by the following formula (3), which is particularly preferable as a cyclic carbonate having an alicyclic skeleton used in the method for producing a polycarbonate of the present embodiment.

[0039] [ka]

[0040] (Method for synthesizing cyclic carbonates having alicyclic skeletons) The method for synthesizing the cyclic carbonate having an alicyclic skeleton represented by the formula (2) is not particularly limited, but it can be obtained by reacting a precursor cycloalkanediol with a halogenated formate ester, a carbonate ester, urea, phosgene, or the like. It can also be synthesized by the addition reaction of a precursor cycloalkylene oxide with carbon dioxide.

[0041] Examples of the halogenated formate ester include, but are not limited to, methyl chloroformate, ethyl chloroformate, methyl bromoformate, ethyl bromoformate, methyl iodoformate, and ethyl iodoformate. Examples of the carbonate ester include, but are not limited to, dimethyl carbonate, diethyl carbonate, propyl carbonate, isopropyl carbonate, butyl carbonate, isobutyl carbonate, and diphenyl carbonate.

[0042] In the method for synthesizing a cyclic carbonate having an alicyclic skeleton using the halogenated formate ester, the reaction temperature is preferably −30 to 50° C., more preferably 0 to 10° C. The reaction pressure is preferably atmospheric pressure, and the reaction time is preferably 1 to 24 hours, more preferably 6 to 12 hours. The reaction is preferably carried out in an inert gas atmosphere such as an argon atmosphere or a nitrogen atmosphere. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, a continuous system, etc. After completion of the reaction, the cyclic carbonate can be separated and purified by means of concentration, distillation, extraction, crystallization, recrystallization, ion exchange, silica gel column, etc.

[0043] The synthesis method of cyclic carbonates consisting of alicyclic skeletons using carbonate esters preferably uses a catalyst.The catalyst is not limited to the following, but includes metal oxides such as beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, lanthanum oxide, zinc oxide, aluminum oxide, cerium oxide, iron oxide, cobalt oxide, nickel oxide, silicon oxide, copper oxide, and silver oxide; and organic bases such as triethylamine, tripropylamine, tributylamine, tripentylamine, 4-ethylmorpholine, picoline, pyridine, N,N-dimethyl-4-aminopyridine, diazabicycloundecene, dipropylamine, dibutylamine, propylamine, butylamine, morpholine, pyrimidine, imidazole, and aniline.Preferably, it is a metal oxide, more preferably, it is an alkaline earth metal oxide such as calcium oxide, magnesium oxide, and barium oxide, and even more preferably, it is calcium oxide.

[0044] The carbon dioxide used in the reaction with the cycloalkylene oxide may be in any state, such as gas, liquid, or solid. It may be pure carbon dioxide or a mixture with compounds inert to other reactions, such as inert gases such as nitrogen, argon, and helium, or with hydrocarbons, or may contain carbon monoxide or a small amount of oxygen or water.

[0045] A catalyst is used in the reaction of cycloalkylene oxide with carbon dioxide, and examples of the catalyst include porphyrin compounds such as chloro(5,10,15,20-tetra-p-tolylporphyrinato)chromium, amines such as N-methylimidazole, and alkali metal or alkaline earth metal halides, preferably alkali metal or alkaline earth metal halides.

[0046] Examples of the alkali metals and alkaline earth metals include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium. Examples of the halides of these metals include lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, radium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, francium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, radium chloride, lithium bromide, sodium bromide, rubidium bromide, and cesium bromide. compounds of a single metal and a single halogen, such as lithium iodide, francium bromide, beryllium bromide, magnesium bromide, strontium bromide, barium bromide, radium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, francium iodide, beryllium iodide, magnesium iodide, calcium iodide, strontium iodide, barium iodide, and radium iodide; double salts, such as sodium magnesium chloride, potassium magnesium chloride, calcium potassium chloride, and potassium magnesium bromide; and polyhalides, such as potassium bromine fluoride, potassium iodine chloride, rubidium iodine chloride, cesium iodine chloride, cesium bromine chloride, rubidium iodine chloride bromide, potassium iodine bromide, cesium iodine bromide, and rubidium iodine bromide. These alkali metal and alkaline earth metal halides may be used alone or in combination of two or more. Among these halides, those containing bromine or iodine are preferred, and iodides are particularly preferred. The amount of the alkali metal and alkaline earth metal halides is not particularly limited, but is usually preferably in the range of 0.001 to 1,000 times the amount of the cycloalkylene oxide used.

[0047] When the alkali metal halide or alkaline earth metal halide is used as a catalyst for the reaction of cycloalkylene oxide with carbon dioxide, it is preferable to use the above-mentioned alkali metal halide or alkaline earth metal halide dissolved in cycloalkylene carbonate. Carbon dioxide is usually used in an amount of 0.01 to 1,000 times by mol, preferably 0.1 to 100 times by mol, more preferably 0.5 to 20 times by mol, based on the amount of cycloalkylene oxide. The reaction is carried out at a temperature of 50 to 400° C., preferably 100 to 300° C., and usually under normal pressure or elevated pressure, for a reaction time of several minutes to several tens of hours.

[0048] (Copolymerization process of cyclocarbonate having an alicyclic skeleton and ethylene carbonate) The method for producing a polycarbonate according to the present embodiment includes a step of copolymerizing a cyclic carbonate having an alicyclic skeleton represented by the above formula (2) with ethylene carbonate. The method for producing a polycarbonate according to the present embodiment includes a step of ionic polymerization, and the ionic polymerization is preferably anionic polymerization.

[0049] <Monomer> In the method for producing a polycarbonate according to the present embodiment, ethylene carbonate and a cyclic carbonate having an alicyclic skeleton represented by the above formula (2) are used as monomers. The cyclic carbonate having an alicyclic skeleton of the formula (2) may be used alone or in combination of two or more kinds. Cyclic carbonates having an alicyclic skeleton of the above formula (2) are capable of ring-opening polymerization and are more easily copolymerized with ethylene carbonate than homopolymerized. By using such a trans-type 1,2-cyclic carbonate directly bonded to an alicyclic skeleton, it is possible to easily obtain a polycarbonate copolymer.

[0050] <Polymerization initiator or polymerization catalyst> In the method for producing a polycarbonate according to the present embodiment, a polymerization initiator or a polymerization catalyst is used. Examples of the polymerization initiator include, but are not limited to, an acid catalyst, a base catalyst, and an enzyme catalyst, and preferably a base catalyst. Examples of the base catalyst include, but are not limited to, alkyl metals, metal alkoxides, metal organic acid salts, metal amides, organic base compounds, and phosphazene bases. Of these, metal alkoxides, metal amides, and phosphazene bases are preferred, and metal amides are more preferred.

[0051] Examples of alkyl metals include, but are not limited to, organic lithium such as methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and phenyllithium, methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, phenylmagnesium halide, trimethylaluminum, and triethylaluminum. Among these, methyllithium, n-butyllithium, or sec-butyllithium is preferably used.

[0052] Examples of metal ions in metal alkoxides include, but are not limited to, alkali metal and alkaline earth metal ions, preferably alkali metal ions. Examples of alkoxide ions include, but are not limited to, methoxide, ethoxide, propoxide, butoxide, phenoxide, and benzyl oxide. Phenoxide and benzyl oxide may have a substituent on the aromatic ring.

[0053] Examples of organic acid ions in the metal organic acid salts include, but are not limited to, carboxylate ions having 1 to 10 carbon atoms. Examples of metals in the metal organic acid salts include, but are not limited to, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, and tin.

[0054] Examples of metal amides include, but are not limited to, sodium amide, lithium diisopropylamide (LDA), sodium bistrimethylsilylamide, and the like, with lithium diisopropylamide (LDA) being preferred.

[0055] The organic base compound includes, but is not limited to, cyclic amines such as cyclic monoamines and cyclic diamines (particularly, cyclic diamine compounds having an amidine skeleton); triamine compounds having a guanidine skeleton, and heterocyclic compounds containing nitrogen atoms. Specific examples include 1,4-diazabicyclo-[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), diphenylguanidine (DPG), N,N-dimethyl-4-aminopyridine (DMAP), imidazole, pyrimidine, and purine.

[0056] Examples of the phosphazene base include, but are not limited to, t-butylimino-tris(dimethylamino)phosphorane (hereinafter also referred to as "P1-t-Bu"), t-butylimino-tris(pyrrolidino)phosphorane (hereinafter also referred to as "P1-t-Bu-tris(tetramethylene")), 1-t-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (hereinafter also referred to as "P2-t-Bu"), 1-ethyl ... Examples of such phosphazene include bis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (hereinafter also referred to as "P2-Et"), 1-t-butyl-4,4,4-tris(dimethylamino)-2,2-bis-[tris(dimethylamino)phosphoranylideneamino]-2λ5,4λ5-catenadi(phosphazene) (hereinafter also referred to as "P4-t-Bu"), and 2-t-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (hereinafter also referred to as "BEMP").

[0057] The amount of polymerization initiator or polymerization catalyst used in the polymerization step of the polycarbonate production method of this embodiment may be appropriately adjusted depending on the target molecular weight of the polycarbonate, but is preferably 0.0001 mol% or more and 10 mol% or less, and more preferably 0.0002 mol% or more and 5 mol% or less, in terms of the amount of substance relative to the cyclic carbonate, which is the ring-opening polymerizable monomer. The above-mentioned polymerization initiators or polymerization catalysts may be used alone or in combination of two or more kinds.

[0058] <Co-catalyst> In the method for producing a polycarbonate according to the present embodiment, in addition to the above-mentioned base catalyst, ureas may be used as co-catalysts. Examples of the ureas include urea, thiourea, and guanidine.

[0059] Examples of urea include, but are not limited to, unsubstituted urea, mono-substituted urea, and di-substituted urea. Examples of the mono-substituted urea include, but are not limited to, methylurea, ethylurea, propylurea, butylurea, cyclohexylurea, [(tetrahydrofuran-2-yl)methyl]urea, 3-chlorophenylurea, N-benzoylurea, (4-bromophenyl)urea, and the like. Examples of the 2-substituted urea include, but are not limited to, 1,3-dimethylurea, 1,3-diethylurea, 1,3-diisopropylurea, 1,3-dicyclohexylurea, 1,3-diphenylurea, 1,3-bis[3,5-bis(trifluoromethyl)phenyl]urea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[2-(dimethylamino)cyclohexyl]urea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[3-(trifluoromethyl)phenyl]urea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[phenyl]urea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[cyclohexyl]urea, 1-[3-(trifluoromethyl)phenyl]-3-[phenyl]urea, 1-[cyclohexyl]-3-[phenyl]urea, and the like.

[0060] Examples of thiourea include, but are not limited to, unsubstituted thiourea, methylthiourea, ethylthiourea, propylthiourea, butylthiourea, cyclohexylthiourea, [(tetrahydrofuran-2-yl)methyl]thiourea, 3-chlorophenylthiourea, N-benzoylthiourea, and mono-substituted thiourea such as (4-bromophenyl)thiourea, 1,3-dimethylthiourea, 1,3-diethylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1,3-diphenylthiourea, and 1,3-bis[3,5-bis(trifluoromethyl)phenyl]thiourea. 1-[3,5-bis(trifluoromethyl)phenyl]-3-[2-(dimethylamino)cyclohexyl]thiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[3-(trifluoromethyl)phenyl]thiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[phenyl]thiourea, 1-[3,5-bis(trifluoromethyl)phenyl]-3-[cyclohexyl]thiourea, 1-[3-(trifluoromethyl)phenyl]-3-[phenyl]thiourea, 1-[cyclohexyl]-3-[phenyl]thiourea, and other 2-substituted thioureas. Among these, disubstituted thioureas are preferred.

[0061] The ureas may be used alone or in combination with other polymerization initiators, but are preferably used in combination with other polymerization initiators, and more preferably used in combination with thiourea and other polymerization initiators.

[0062] <Additives> In the method for producing a polycarbonate of the present embodiment, from the viewpoint of controlling the molecular weight of the target polycarbonate and from the viewpoint of expressing various properties by controlling the terminal structure, an additive may be used in addition to the above-mentioned polymerization initiator or polymerization catalyst. Examples of additives include, but are not limited to, monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, dodecanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, 5-norbornene-2-methanol, 1-adamantanol, 2-adamantanol, trimethylsilylmethanol, phenol, benzyl alcohol, and p-methylbenzyl alcohol; dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, nonanediol, tetramethylene glycol, and polyethylene glycol; polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, erythritol, and triethanolamine; and methyl lactate and ethyl lactate. The above additives may be used alone or in combination of two or more.

[0063] <Mixing> In the method for producing a polycarbonate according to the present embodiment, it is preferable to stir the reactants and / or products in the copolymerization step. Examples of the stirring method include, but are not limited to, stirring using a mechanical stirrer and agitating blades, and stirring using a magnetic stirrer and a rotor.

[0064] <Reaction temperature> In the method for producing the polycarbonate of this embodiment, the reaction temperature in the copolymerization step is not particularly limited as long as it is within a range in which the polycarbonate of this embodiment can be produced, but is preferably 0°C or higher and 150°C or lower, more preferably 0°C or higher and 130°C or lower, and even more preferably 0°C or higher and 120°C or lower.

[0065] <Response time> In the method for producing the polycarbonate of the present embodiment, the reaction time in the copolymerization step is not particularly limited as long as it is within a range in which the polycarbonate of the present embodiment can be produced, but is preferably 1 minute to 72 hours, more preferably 3 minutes to 48 hours, and even more preferably 5 minutes to 18 hours.

[0066] <Solvent> In the method for producing a polycarbonate according to the present embodiment, a solvent may or may not be used. Examples of the solvent include, but are not limited to, ether-based solvents such as diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, tert-butyl methyl ether, and propylene glycol monomethyl ether acetate; halogen-based solvents such as methylene chloride, chloroform, dichloromethane, dichloroethane, and trichloroethane; saturated hydrocarbon-based solvents such as hexane, heptane, octane, nonane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon-based solvents such as toluene, xylene, o-xylene, m-xylene, p-xylene, and cresol; and ketone-based solvents such as acetone, 2-butanone, 2-pentanone, 3-pentanone, cyclopentanone, cyclohexanone, and methyl isobutyl ketone.

[0067] <Polymerization terminator> In the method for producing a polycarbonate according to the present embodiment, a polymerization terminator may be used in addition to the above-mentioned polymerization initiator or polymerization catalyst, from the viewpoint of controlling the average molecular weight of the resulting polycarbonate. Examples of the polymerization terminator include, but are not limited to, inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, metaphosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, citric acid, ascorbic acid, gluconic acid, oxalic acid, tartaric acid, Meldrum's acid, and benzoic acid.

[0068] The polycarbonate of this embodiment can be quantified by techniques well known to those skilled in the art. For example, 1 H-NMR, 13 Examples of the method include C-NMR, high performance liquid chromatography, and gas chromatography. EXAMPLES

[0069] Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples, but the present invention is not limited in any way to the following examples and comparative examples. In the examples and comparative examples, various measurements were carried out as follows.

[0070] [Measurement of physical properties of polycarbonate] ( 1 H-NMR measurement) Using an NMR device (manufactured by JEOL Ltd., product name: ECZ400R) and a TFH probe, NMR measurements were performed as follows to determine the molecular structure of polycarbonate. 1 H-NMR spectra were obtained. The reference peaks of the heavy solvents were 7.26 ppm when chloroform-d was used, 2.50 ppm when dimethylsulfoxide-d6 was used, and 7.15 ppm when benzene-d6 was used, and the measurements were performed with eight accumulations. FIG. 1 shows the polycarbonate of Example 1. 1 The H-NMR spectrum is shown.

[0071] ( 13 C-NMR measurement) Using an NMR device (product name: ECZ400R, manufactured by JEOL Ltd.) and a TFH probe, NMR measurements were performed as follows to determine the molecular structure of polycarbonate. 13 C-NMR spectra were obtained. The reference peaks of the heavy solvents were 77.0 ppm when chloroform-d was used, 39.5 ppm when dimethylsulfoxide-d6 was used, and 128.0 ppm when benzene-d6 was used, and the measurements were performed with 256 accumulations. FIG. 2 shows the polycarbonate of Example 1. 13 The C-NMR spectrum is shown.

[0072] (Conversion rate of cyclic carbonate having an alicyclic skeleton) Conversion rate x of trans-1,2-cyclohexene carbonate (hereinafter sometimes referred to as T6C), a cyclic carbonate with an alicyclic skeleton t (%) is the amount of crude product after reaction 1 The integral value A of the peak (3.22-3.26 ppm) derived from the methine proton of the T6C monomer in the H-NMR spectrum mt and the integral value A of the peaks (4.7 ppm, 4.9 ppm) derived from the methine signal of the polymer pt It was calculated according to the following formula (4).

[0073]

number

[0074] (Ethylene carbonate conversion rate) Conversion rate of ethylene carbonate (hereinafter sometimes referred to as EC) x e (%) is the crude product 1 The integral A of the peak (3.31 ppm) derived from the methylene protons of the monomer in the H-NMR spectrum me and the integral value A of the peak (3.8 ppm to 4.3 ppm) derived from the methylene protons of the polymerpe It was calculated according to the following formula (5).

[0075]

number

[0076] (Polycarbonate yield) The yield (%) of the polycarbonate was calculated by dividing the mass of the purified polycarbonate by the total mass of the monomers used, as shown in the following formula (6).

[0077]

number

[0078] (Composition ratio of cyclic carbonate having an alicyclic skeleton and ethylene carbonate) The composition ratio of T6C and EC in polycarbonate was calculated by the integral value A of the peaks (4.7 ppm, 4.9 ppm) derived from the methine signal of the purified polycarbonate. pt , and the integral value A of the peak (3.8 ppm to 4.3 ppm) derived from methylene derived from ethylene carbonate (EC) of the purified polycarbonate pe It was calculated by the following formulas (7) and (8). In the following formulas (7) and (8), the unit of composition ratio "%" is "mol%".

[0079]

number

[0080] (Ethylene glycol content in polycarbonate) The ethylene glycol content (EGC) in polycarbonate was calculated by the integral value A of the peak (3.8 ppm to 4.3 ppm) derived from methylene derived from ethylene carbonate (EC) in the purified polycarbonate. pe and the integral value A of the peak (3.6 ppm) derived from the methylene of the ethylene glycol unit pgIt was calculated according to the following formula (9). When the content of ethylene glycol in the polycarbonate was less than 1%, it was evaluated that the polycarbonate had no ether bonds. The unit of "%" for the ethylene glycol content in the polycarbonate of the following formula (9) is "mol%".

[0081]

number

[0082] (Measurement of number average molecular weight (Mn) of polycarbonate) A solution in which tetrahydrofuran was added in a ratio of 2.0 g to 0.02 g of polycarbonate was used as a measurement sample, and the weight average molecular weight and number average molecular weight of the polycarbonate resin were measured using a high-speed GPC device (JASCO: JASCO Corporation, LC-2000Plus series). The columns used were two TSKgel MultiporeHX-M columns (manufactured by Tosoh Corporation) connected in series. The column temperature was set to 40° C., and the analysis was performed at a rate of 0.60 mL / min using tetrahydrofuran as the mobile phase. The detector used was an RI detector. A calibration curve was prepared using polystyrene standard samples (molecular weights: 2,520,000, 1,240,000, 552,000, 277,000, 130,000, 66,000, 34,800, 19,700, 8,680, 3,470, 1,306, and 370) manufactured by Polymer Standards Service as standard samples. Based on the calibration curve thus prepared, the weight average molecular weight and number average molecular weight of the polycarbonate were determined. Table 1 shows the number average molecular weight Mn of the polycarbonate.

[0083] [Preparation of polycarbonate] (Synthesis Example 1: Synthesis of trans-1,2-cyclohexene carbonate: T6C) Under a nitrogen stream, trans-1,2-cyclohexanediol (25.0 kg, 215.2 mol, BLD PHARMATECH) and THF (containing stabilizer) (250 L) were added to a 1000 L reaction vessel. While cooling the reaction vessel to -6 °C with stirring, a solution prepared by diluting ethyl chloroformate (70.0 kg, 645 mol) and triethylamine (87.4 kg, 863 mol) with dehydrated toluene (188 L) was added dropwise to the reaction solution in two portions over night with stirring, and then stirred for an additional 4 hours. The by-produced white solid was removed by filtration under reduced pressure, and the filtrate was concentrated under reduced pressure. THF / toluene (2 / 1) (60.0 L) was added to the residue to dissolve it, and then it was purified by silica gel column chromatography. The eluent was further concentrated, dissolved in 270 kg of chloroform, and then washed twice with 217 kg of ion-exchanged water. Thereafter, reprecipitation was carried out with 20 kg of chloroform and 100 L of heptane, and after concentration, the target trans-cyclohexene carbonate (22.81 kg, 160.5 mol, yield 75%) was obtained.

[0084] (Example 1) (Ring-opening copolymerization of T6C and ethylene carbonate) To a 25 mL mortar test tube, trans-1,2-cyclohexene carbonate: T6C (0.30 g, 2.11 mmol), ethylene carbonate (0.19 g, 2.11 mmol), and benzyl alcohol (4.35 μL, 0.422 mmol) were added, and the inside of the test tube was purged with nitrogen. The test tube was heated to 60 °C, and lithium diisopropylamide (LDA) 2M in THF / heptane / ethylbenzene (Sigma-Aldrich): 21.1 μL, 0.0422 mmol) was added, and stirred at 60 °C for 0.5 hour. After 0.5 hour, acetic acid (3.62 μL, 0.0633 mmol) was added to stop the reaction. After allowing the test tube to cool to room temperature, a small amount of chloroform was added to dissolve the contents. The resulting solution was added dropwise to 30 mL of methanol to precipitate the polymer. The precipitated polymer was recovered, added to chloroform to dissolve again, and then dropped again into 40 mL of methanol to cause reprecipitation. The polymer was collected by vacuum filtration and dried in vacuum at 40° C. to give 0.31 g of copolymer (62.1% yield). The ether content of the resulting polymer was less than 1%. The unit of ether content "%" is "mol%". FIG. 1 shows the polymer obtained in Example 1. 1 The H-NMR spectrum of the polymer obtained in Example 1 is shown in FIG. 13 The C-NMR spectrum is shown. These results reveal that a polycarbonate was obtained that contained no remaining monomer, contained the structural unit represented by the formula (1) above, and contained no ether bonds.

[0085] (Examples 2 to 10, Comparative Example 1) A polycarbonate was prepared in the same manner as in Example 1, except that the reaction temperature and / or the reaction time and / or the molar ratio of monomers charged were changed. The evaluation results are shown in Table 1 below.

[0086] [Table 1]

[0087] In all of Examples 1 to 10, the EGC was less than 1%, and polycarbonates containing the desired structural units without ether bonds could be prepared. [Industrial Applicability]

[0088] The polycarbonate of the present invention has industrial applicability in the fields of various optical materials such as solid electrolytes, polymer electrolytes, biocompatible materials, sacrificial agents, optical lens materials, optical devices, materials for optical components, and display materials.

Claims

1. A polycarbonate containing a structural unit represented by the following formula (1), which does not contain an ether bond: 【Chemistry 1】 (In formula (1), R 1 ~R 4 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. R 1 ~R 4 Any two or more of the above may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure. x and y are the numbers of repeating units, and the arrangement of the repeating units represented by x and y in the polymer is block or random.

2. The method includes a step of copolymerizing a cyclic carbonate having an alicyclic skeleton represented by the following formula (2) with ethylene carbonate: A method for producing polycarbonate. 【Chemistry 2】 (In formula (2), R 1 ~R 4 are each independently a hydrogen atom, a hydroxyl group, a phosphate group, an amino group, a vinyl group, an allyl group, an alkoxy group having 1 to 30 carbon atoms, an ester group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, or an unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. R 1 ~R 4 Any two or more of the above may be bonded to each other via at least one group selected from the group consisting of an alkylene group, an alkylenedioxy group, an ester group, and a carbonate group to form a cyclic structure.

Images