JP5069855B2 - Method for producing alicyclic olefin polyvalent carbonate compound and mixture of alicyclic olefin polyvalent carbonate compound - Google Patents

Description

  The present invention relates to a method for producing an alicyclic olefin polyvalent carbonate compound and an alicyclic olefin polyvalent carbonate. More specifically, a method for producing an alicyclic olefin polyvalent carbonate compound having 1 to 6 carbonate bonds, an alicyclic olefin polyvalent carbonate compound having 1 to 6 carbonate bonds and a low chlorine content, and carbonate The present invention relates to an alicyclic olefin polyvalent carbonate compound containing an oligomer having 3 to 6 bonds.

A carbonic acid ester compound of 3-cyclohexene-1-methanol and a synthesis method thereof are described in US Pat. No. 3,275,661. However, the production method described in this specification is based on a reaction between Δ ³ -tetrahydrobenzyl alcohol (3-cyclohexene-1-methanol) and phosgene. Since phosgene is highly toxic, a safer manufacturing method is required. Further, the carbonate ester compound described in the US patent specification is a monomer compound having a small molecular weight having one or two carbonate ester groups in the molecule, and an oligomer compound having a carbonate ester group in the molecule and having a molecular weight distribution. An oligomeric compound (mixture thereof) having a cyclohexene ring derived from 3-cyclohexene-1-methanol at the molecular end is not known. Moreover, since the carbonate compound obtained by using the phosgene described in the above-mentioned US patent specification has a high content of free chlorine, it has, for example, a carbonate bond obtained by epoxidizing it. Epoxy compounds and cured products thereof are corrosive, and their use is greatly limited.

US Pat. No. 3,275,661

  An object of the present invention is to provide a safe method for producing an alicyclic olefin polyvalent carbonate compound, and an oligomeric compound having 1 to 6 carbonic acid ester groups in the molecule and having a molecular weight distribution, wherein 3- An object of the present invention is to provide an alicyclic olefin polyvalent carbonate compound having a low free chlorine content and having a cyclohexene ring derived from cyclohexene-1-methanol. Another object of the present invention is an oligomer compound having an oligomer containing 3 to 6 carbonic acid ester groups in the molecule and having a molecular weight distribution, wherein a cyclohexene ring derived from 3-cyclohexene-1-methanol is attached to the molecular end. It is to provide an alicyclic olefin polyvalent carbonate compound.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by subjecting a carbonate compound, 3-cyclohexene-1-methanol, and a diol to a transesterification reaction, and has completed the present invention.

［式中、Ｒ¹およびＲ²は、同一又は異なって、炭素数１〜１２のアルキル基を示す］
で表されるアルコールの炭酸エステル化合物と、下記式（II）

で表される３−シクロヘキセン−１−メタノールと、ジオール化合物：ＨＯ−Ｒ−ＯＨ （III）とをエステル交換反応させて、下記式（IV）

［式中、Ｒはアルキレン基、シクロアルキレン基、シクロアルキリデン基若しくはアリーレン基、又はこれらが２以上直接又は酸素原子を介して結合した基を示す。ｎは０〜５の整数であり分布を有する］
で表される化合物を得ることを特徴とする脂環式オレフィン多価カーボネート化合物の製造方法を提供する。 That is, the present invention provides the following formula (I)

[Wherein, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 12 carbon atoms]
And a carbonate ester compound of alcohol represented by the following formula (II):

And a diol compound: HO—R—OH (III) is transesterified to give the following formula (IV):

[Wherein, R represents an alkylene group, a cycloalkylene group, a cycloalkylidene group or an arylene group, or a group in which two or more of these are bonded directly or via an oxygen atom . n is an integer of 0 to 5 and has a distribution]
The manufacturing method of the alicyclic olefin polyvalent carbonate compound characterized by obtaining the compound represented by these is provided.

  In the above production method, for example, dimethyl carbonate can be used as the carbonate compound of alcohol, and for example, alkanediol having 2 to 16 carbon atoms or alicyclic diol having 5 to 16 carbon atoms can be used as the diol compound.

  In a preferred embodiment of the above production method, a compound represented by the formula (IV) in which the content of the compound with n = 0 is 70% by weight or less with respect to the total amount of the compounds with n = 0 to 5 is obtained.

［式中、Ｒはアルキレン基、シクロアルキレン基、シクロアルキリデン基若しくはアリーレン基、又はこれらが２以上直接又は酸素原子を介して結合した基を示す。ｎは０〜５の整数であり分布を有する］
で表され、ｎ＝２〜５の化合物の何れかを少なくとも含有している脂環式オレフィン多価カーボネート化合物の混合物を提供する。 The present invention further provides the following formula (IV):

[Wherein, R represents an alkylene group, a cycloalkylene group, a cycloalkylidene group or an arylene group, or a group in which two or more of these are bonded directly or via an oxygen atom . n is an integer of 0 to 5 and has a distribution]
And a mixture of alicyclic olefin polyvalent carbonate compounds containing at least any of the compounds of n = 2 to 5.

In the mixture of the above alicyclic olefin polyvalent carbonate compounds, the content of the compound of n = 0 may be 70% by weight or less based on the total amount of the compound of n = 0-5.

  The present invention enables safe production of an alicyclic olefin polyvalent carbonate compound, has a molecular weight distribution, and is a versatile alicyclic olefin polyvalent carbonate compound having a low free chlorine content, and An alicyclic olefin polyvalent carbonate compound containing an oligomer having a molecular weight distribution and having 3 to 6 carbonate bonds has been provided. By epoxidizing the double bond of the same cycloaliphatic olefin polyvalent carbonate compound with an epoxidizing agent such as organic peracid, the content of free chlorine is low, and the transparency is improved by curing. A useful alicyclic epoxy compound that gives a cured product having excellent physical properties and the like can be produced.

  The alicyclic olefin polyvalent carbonate compound in the present invention includes an alcohol carbonate compound represented by the formula (I) and 3-cyclohexene-1-methanol (1,2,5 represented by the formula (II). , 6-tetrahydrobenzyl alcohol) and a diol compound: HO—R—OH (III).

In formula (I), examples of the alkyl group having 1 to 12 carbon atoms in R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, octyl, decyl, dodecyl group and the like. And a linear or branched C _1-12 alkyl group. As the carbonate ester of the alcohol represented by the formula (I) that can be used, a carbonate ester of a lower alcohol having 4 or less carbon atoms is preferable, and among them, dimethyl carbonate, diethyl carbonate, and diisopropyl carbonate are particularly preferable.

  In the formula (III), R is a residue of a diol compound, for example, a substituted or unsubstituted alkylene group, cycloalkylene group, cycloalkylidene group, or arylene group, or a linking group such as two or more of these directly or an oxygen atom And a divalent organic group such as a group bonded via each other. Examples of the diol compound (III) that can be used include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentane Diol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-hexyl-1,3-propanediol, Low molecular weight diol compounds such as cyclohexanediol and cyclohexanedimethanol , And the like oligomers, such as alkylene oxide adduct of bisphenol A and the like. Among these, in particular, aliphatic diols such as linear or branched alkanediols having about 2 to 16 carbon atoms such as 1,6-hexanediol and 1,10-decanediol, and cycloalkanes such as cyclohexanedimethanol. An alicyclic diol having about 5 to 16 carbon atoms containing an alicyclic ring such as a ring (including a compound having only an alicyclic ring as a residue of the diol compound and a compound having an alkylene group together with the alicyclic ring) is preferable. These diol compounds can be used alone or in combination.

  In the formula (IV), R represents a residue of the diol compound. n is an integer of 0 to 5, and compounds having numerical values of n are generated with distribution. Therefore, the product produced by the production method of the present invention contains a compound containing no R which is a residue of the diol compound (III) in the formula (IV) in a considerable content, and n is 1 to 5 Obtained as a mixture with each compound having a numerical value. Depending on the charge ratio of the raw material compounds, a small amount of a compound having n exceeding 5 is produced. However, according to the charge ratio described later, a mixture of compounds having n up to 5 is substantially obtained. In the alicyclic olefin polyvalent carbonate compound represented by the formula (IV), the content of the compound in which n is 0 is preferably 70% by weight or less (for example, 10%) based on the total amount of the compounds in which n is 0 to 5. -70 wt%), more preferably 60 wt% or less (for example, 20-60 wt%). Moreover, as an alicyclic olefin polyvalent carbonate compound represented by Formula (IV), it is preferable to contain at least any one of compounds having n of 2 to 5, and n is a total of compounds having 2 to 5 The content is, for example, 5% by weight or more (for example, about 5 to 30% by weight), preferably 10% by weight or more (for example, about 10 to 30% by weight), based on the total amount of compounds in which n is 0 to 5; It is preferably 15% by weight or more (for example, about 15 to 30% by weight).

  A part of the diol compound to be used may be replaced with one or more diamines such as hexamethylene diamine, xylene diamine, isophorone diamine, monoethanol amine, or amino alcohol. The purpose of adding such an amine is to adjust the molecular weight.

  In the transesterification reaction in the production method of the present invention, in order to accelerate the reaction, it is preferable to use an esterification catalyst usually used in the esterification reaction. Examples of the esterification catalyst used in the present invention include titanium compounds such as tetrapropyl titanate, tetrabutyl titanate, and tetrastearyl titanate, stannous octylate, dibutyltin dilaurate, stannous chloride, Stannous, stannous iodide, dibutylene dichloride, butyltin trichloride, tin compounds such as dibutyltin oxide, alkylbenzenesulfonic acid metal salts such as sodium paratoluenesulfonate, alkylsulfonic acids such as methanesulfonic acid, Examples include cobalt hydroxide, manganese acetate, zinc oxide, and cobalt octylate. Preferred esterification catalysts in the present invention are titanium compounds and tin compounds.

  The amount of the esterification catalyst used is preferably 0.01 to 10,000 ppm by weight, more preferably 1 to 100 ppm by weight, based on the total weight of the three starting materials. If the amount of the esterification catalyst used is less than 0.1 ppm by weight, the reaction rate is slow. Conversely, if it exceeds 10000 ppm by weight, side reactions occur and the yield of the target compound decreases, or the target compound is colored. Neither is preferred.

  Next, the transesterification reaction step will be described. The first step is a carbonic esterification reaction step, and a known method used in a transesterification reaction can be applied. That is, usually, the raw materials are charged into the reactor, and then heated and stirred. Then, it is gradually heated to 150 to 280 ° C., preferably 200 to 240 ° C., more preferably about 220 ° C. at normal pressure. If the reaction temperature is less than 150 ° C., the reaction rate is slow, and conversely, if the reaction temperature exceeds 280 ° C., side reactions occur and the yield of the target compound decreases, so that neither is preferable. In this way, the carbonation esterification reaction is allowed to proceed until a predetermined reaction rate is reached.

  The second step is a step of removing alcohol such as methanol. In order to sufficiently advance the carbonic esterification reaction, a lower alcohol such as methanol desorbed from the carbonic ester compound is 0.1 to 600 torr (13.3 pa to 79.8 kPa), more preferably 10 to 200 torr ( 1.33 kPa to 26.6 kPa) while removing under reduced pressure.

The charging ratio of the carbonate ester compound (I) of alcohol and the diol compound (III) and 3-cyclohexene-1-methanol (II) at the time of charging was the number average of the target alicyclic olefin polyvalent carbonate compound (IV). Determined by molecular weight (molecular weight distribution). Usually, in a molar ratio, 3-cyclohexene-1-methanol (II) / diol compound (III) / carbonic acid ester compound of alcohol (I) = 2 / (1-10) / (1-9), preferably 2 / (1-5) / (1-7), more preferably 2 / (1-3) / (1-4).

  That is, in the production method of the present invention, the distribution of the number of n (molecular weight) in the alicyclic olefin polyvalent carbonate compound represented by the formula (IV) by varying the amount of the carbonate compound (I) charged with alcohol. Distribution) can be arbitrarily adjusted. Therefore, the value of n can be controlled to be substantially 5 or less.

  If the amount of the carbonate compound (I) of alcohol is relatively large, n in the formula (IV) exceeds 5, and the flowability and reactivity decrease with increasing molecular weight, and the carbonation of unreacted alcohol. If ester compound (I) will remain and the amount of 3-cyclohexene-1-methanol (II) or diol compound (III) charged is relatively large, 3-cyclohexene-1-methanol (II) or Since the diol compound (III) remains unreacted, neither is preferable. When the amount of the diol compound (III) is relatively small relative to the other two compounds, the content of the compound with n = 0 increases.

  The end point of the transesterification reaction is usually preferably confirmed by quantifying the remaining diol compound (III) or carbonate compound (I) by gas chromatography or the like.

  After completion of the transesterification reaction, a lower alcohol such as methanol is distilled off under reduced pressure conditions of about 10 to 200 torr (1.33 kPa to 26.6 kPa) to obtain the alicyclic olefin polyvalent carbonate compound as the target compound. be able to.

  By the reaction as described above, the alicyclic olefin polyvalent carbonate compound represented by the formula (IV) [where n is stochastically distributed between 0 to 5 in the formula (IV)] does not use toxic phosgene. Manufactured in a safe way. Therefore, the obtained alicyclic olefin polyvalent carbonate compound has a free chlorine content of 100 ppm by weight or less, preferably 50 ppm by weight or less. Moreover, the alicyclic olefin polyvalent carbonate compound which has the molecular weight distribution and contains the oligomer which has 3-6 carbonate bonds by the said method is obtained. The alicyclic epoxy compound obtained by epoxidizing the alicyclic olefin polyvalent carbonate compound thus obtained is free from corrosiveness because it has a low free chlorine content, and also has a carbonate skeleton and a cross-linked alicyclic epoxy group. Since a compound having a long distance between points is included, a cured product having excellent transparency and mechanical properties is obtained by a curing reaction. Accordingly, it is extremely useful particularly in the field of electronic materials.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measurement conditions of GPC (gel permeation chromatography; standard polystyrene standard) are as follows.
Measuring device: High speed GPC device “HLC-8220GPC” manufactured by Tosoh Corporation
Mobile phase flow rate: 0.350 ml / min Mobile phase: tetrahydrofuran Column temperature: 40 ° C
Sample injection volume: 20 μl
Sample concentration: 1%

Example 1
A 2 liter round bottom flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a packed tower corresponding to three theoretical plates was charged with 275.2 g (3.06 mol) of dimethyl carbonate, 3-cyclohexene-1-methanol (1, 2,5,6-tetrahydrobenzyl alcohol) 342.7 g (3.06 mol), 1,6-hexanediol 180.5 g (1.53 mol), tetrabutyl titanate 32 mg as a catalyst, and stirring and heating under normal pressure did. The temperature of the reactor was gradually increased and reacted at 220 ° C. for 8 hours after reaching 220 ° C. Sampling was performed during the reaction, and the remaining diol component (here, 1,6-hexanediol) was quantified by gas chromatography, and it was confirmed that the transesterification reaction was completed, and the reaction was terminated.
After completion of the transesterification, the carbonate oligomer obtained by reducing the pressure to 100 Torr (13.3 kPa) and distilling the produced methanol had a viscosity of 97 mPa · s / 25 ° C., an acid value of 0.5 KOH mg / g, and moisture. 0.01 wt%, APHA 70, double bond equivalent was 158. Yield was 596 g.
In the analysis of the obtained carbonate oligomer by ¹ H-NMR (FIG. 1), a signal due to ¹ H on the hydrocarbon chain in the vicinity of δ1-2.5 ppm, a carbon atom adjacent to the oxygen atom constituting the ester bond in the vicinity of δ4 ppm signal by ¹ H above, is observed signals by ¹ H on the carbon-carbon double bond in the vicinity Deruta5.5Ppm, it is an alicyclic olefin polyhydric carbonate compounds represented by formula (IV), by GPC analysis From the result of analyzing the obtained chart (FIG. 2), in formula (IV), n = 0 is 59.8% by weight, 1 is 24.3% by weight, and 2 or more (2-5) Was found to be 15.8% by weight. The content of free chlorine analyzed by the atomic absorption method was 31 ppm by weight.

Example 2
In a 2 liter round bottom flask equipped with a stirrer, thermometer, nitrogen inlet tube, packed tower corresponding to 3 theoretical plates, dimethyl carbonate 295.4 g (3.28 mol), 3-cyclohexene-1-methanol (1, 2,5,6-tetrahydrobenzyl alcohol) 245.2 g (2.19 mol), 1,6-hexanediol 258.4 g (2.19 mol), tetrabutyl titanate 32 mg as a catalyst, stirred under normal pressure, heated did. The temperature of the reactor was gradually increased and reacted at 220 ° C. for 8 hours after reaching 220 ° C. Sampling was performed during the reaction, and the remaining diol component (here, 1,6-hexanediol) was quantified by gas chromatography, and it was confirmed that the transesterification reaction was completed, and the reaction was terminated.
After the transesterification reaction is completed, the pressure is reduced to 100 Torr (13.3 kPa), and the properties of the carbonate oligomer obtained by distilling the produced methanol are viscosity 124 mPa · s / 25 ° C., acid value 0.03 KOH mg / g, moisture 0.02% by weight, APHA 80, double bond equivalent 180. Yield was 580 g.
In the analysis of the obtained carbonate oligomer by ¹ H-NMR (FIG. 3), a signal due to ¹ H on the hydrocarbon chain in the vicinity of δ1 to 2.5 ppm, a carbon atom adjacent to the oxygen atom constituting the ester bond in the vicinity of δ4 ppm. signal by ¹ H above, is observed signals by ¹ H on the carbon-carbon double bond in the vicinity Deruta5.5Ppm, it is an alicyclic olefin polyhydric carbonate compounds represented by formula (IV), by GPC analysis From the result of analyzing the obtained chart (FIG. 4), the formula (IV) in which n is 0 is 47.2% by weight, 1 is 34.2% by weight, and 2 or more (2 to 5) Was 18.6% by weight. The content of free chlorine analyzed by the atomic absorption method was 24 ppm by weight.

Example 3
In a 2 liter round bottom flask equipped with a stirrer, thermometer, nitrogen inlet tube, packed tower corresponding to 3 theoretical plates, dimethyl carbonate 262.2 g (2.91 mol), 3-cyclohexene-1-methanol (1, 2,5,6-tetrahydrobenzyl alcohol) 326.5 g (2.91 mol), 1,10-decanediol 209.9 g (1.46 mol), and 32 mg of tetrabutyl titanate as a catalyst were stirred and heated under normal pressure. did. The temperature of the reactor was gradually increased and reacted at 220 ° C. for 8 hours after reaching 220 ° C. Sampling was performed during the reaction, and the remaining diol component (here, 1,10-decanediol) was quantified by gas chromatography, and it was confirmed that the transesterification reaction was completed, and the reaction was terminated.
After the transesterification reaction is completed, the pressure is reduced to 100 Torr (13.3 kPa), and the properties of the carbonate oligomer obtained by distilling the produced methanol are viscosity 253 mPa · s / 25 ° C., acid value 0.03 KOH mg / g, moisture 0.01% by weight, APHA 50, double bond equivalent 162. The yield was 604g.
In the analysis of the obtained carbonate oligomer by ¹ H-NMR (FIG. 5), a signal due to ¹ H on the hydrocarbon chain in the vicinity of δ1 to 2.5 ppm, a carbon atom adjacent to the oxygen atom constituting the ester bond in the vicinity of δ4 ppm. signal by ¹ H above, is observed signals by ¹ H on the carbon-carbon double bond in the vicinity Deruta5.5Ppm, it is an alicyclic olefin polyhydric carbonate compounds represented by formula (IV), by GPC analysis From the result of analyzing the obtained chart (FIG. 6), in formula (IV), n = 0 is 51.1% by weight, 1 is 31.7% by weight, 2 or more (2-5) Of 17.2% by weight. The content of free chlorine analyzed by the atomic absorption method was 27 ppm by weight.

Example 4
To a 2 liter round bottom flask equipped with a stirrer, thermometer, nitrogen inlet tube, packed tower corresponding to 3 theoretical plates, 241 g (2.67 mol) of dimethyl carbonate, 3-cyclohexene-1-methanol (1, 2, 5,6-tetrahydrobenzyl alcohol) 299.8 g (2.67 mol), 1,4-cyclohexanedimethanol 259.4 g (1.34 mol), and tetrabutyl titanate 32 mg as a catalyst were stirred and heated under normal pressure. . The temperature of the reactor was gradually increased and reacted at 220 ° C. for 8 hours after reaching 220 ° C. Sampling was performed during the reaction, and the remaining diol component (here, 1,4-cyclohexanedimethanol) was quantified by gas chromatography to confirm that the transesterification reaction was completed, and the reaction was terminated.
After completion of the transesterification, the carbonate oligomer obtained by reducing the pressure to 100 Torr (13.3 kPa) and distilling the produced methanol has a viscosity of 110 mPa · s / 25 ° C., an acid value of 0.02 KOH mg / g, and moisture. 0.01% by weight, APHA 50, double bond equivalent 178. The yield was 615g.
In the analysis of the obtained carbonate oligomer by ¹ H-NMR (FIG. 7), a signal due to ¹ H on the hydrocarbon chain in the vicinity of δ1 to 2.5 ppm and a carbon atom adjacent to the oxygen atom constituting the ester bond in the vicinity of δ4 ppm signal by ¹ H above, is observed signals by ¹ H on the carbon-carbon double bond in the vicinity Deruta5.5Ppm, it is an alicyclic olefin polyhydric carbonate compounds represented by formula (IV), by GPC analysis From the result of analyzing the obtained chart (FIG. 8), in formula (IV), n = 0 is 59.7% by weight, 1 is 24.3% by weight, and 2 or more (2-5) Was 16.0% by weight. The content of free chlorine analyzed by the atomic absorption method was 19 ppm by weight.

  From the above results, the present invention enabled safe production of alicyclic olefin polyvalent carbonate oligomers having a low chlorine content.

1 is a chart of ¹ H-NMR spectrum analysis of a carbonate oligomer obtained in Example 1. 2 is a GPC analysis chart of the carbonate oligomer obtained in Example 1. FIG. 2 is a chart of ¹ H-NMR spectrum analysis of a carbonate oligomer obtained in Example 2. FIG. 3 is a GPC analysis chart of the carbonate oligomer obtained in Example 2. FIG. 2 is a chart of ¹ H-NMR spectrum analysis of a carbonate oligomer obtained in Example 3. FIG. 4 is a GPC analysis chart of the carbonate oligomer obtained in Example 3. 2 is a chart of ¹ H-NMR spectrum analysis of a carbonate oligomer obtained in Example 4. FIG. 6 is a GPC analysis chart of the carbonate oligomer obtained in Example 4.

Claims (6)

Formula (I)

[Wherein, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 12 carbon atoms]
And a carbonate ester compound of alcohol represented by the following formula (II):

And a diol compound: HO—R—OH (III) is transesterified to give the following formula (IV):

[Wherein, R represents an alkylene group, a cycloalkylene group, a cycloalkylidene group or an arylene group, or a group in which two or more of these are bonded directly or via an oxygen atom . n is an integer of 0 to 5 and has a distribution]
The manufacturing method of the alicyclic olefin polyvalent carbonate compound characterized by obtaining the compound represented by these.   The method for producing an alicyclic olefin polyvalent carbonate compound according to claim 1, wherein the alcohol carbonate compound is dimethyl carbonate.   The method for producing an alicyclic olefin polyvalent carbonate compound according to claim 1, wherein the diol compound is an alkanediol having 2 to 16 carbon atoms or an alicyclic diol having 5 to 16 carbon atoms.   The compound represented by Formula (IV) whose content of the compound of n = 0 is 70 weight% or less with respect to the total amount of the compound of n = 0-5 is described in any one of Claims 1-3 obtained. A method for producing an alicyclic olefin polyvalent carbonate compound. Formula (IV) below

[Wherein, R represents an alkylene group, a cycloalkylene group, a cycloalkylidene group or an arylene group, or a group in which two or more of these are bonded directly or via an oxygen atom . n is an integer of 0 to 5 and has a distribution]
And a mixture of alicyclic olefin polyvalent carbonate compounds containing at least any of compounds of n = 2 to 5. The mixture of alicyclic olefin polyvalent carbonate compounds according to claim 5 , wherein the content of the compound of n = 0 is 70% by weight or less based on the total amount of the compounds of n = 0-5.

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