JP2010254944A - Process for producing polyester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for producing a polyester at an increased reaction rate, in which generation of cyclic oligomers as a by-product is suppressed. <P>SOLUTION: The process for producing a polyester includes allowing a compound represented by general formula (1) (A) and an epoxy compound (B) to react with each other under the presence of a phosphine (C). In formula (1), R<SP>1</SP>to R<SP>6</SP>, which are identical or different, each represent a hydrogen atom, a 1-12C hydrocarbon group, a 1-12C halogenated hydrocarbon group or a 1-12C alkoxy group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing polyester.

  Conventionally, as a method for producing a polyester, a method is known in which a bicyclic bis (γ-butyrolactone) and an epoxide are alternately copolymerized using a nucleophile such as an organometallic compound such as a metal alkoxide (patent). Literature 1 and non-patent literature 1-5).

Japanese Patent Laid-Open No. 7-62065

T. Takata, A. Tadokoro, and T. Endo Macromolecules 1992, 25,2782. A. Tadokoro, T. Takata, and T. Endo Macromolecules 1993, 26,4400. T. Takata, A. Tadokoro, K. Chung, and T. Endo Macromolecules 1995, 28, 1340. K. Chung, T. Takata, and T. Endo Macromolecules 1995, 28, 3048. K. Chung, T. Takata, and T. Endo Macromolecules 1997, 30, 2532.

However, the conventional polyester production method has a problem that the reaction rate is low and a cyclic oligomer is produced as a by-product.
Accordingly, an object of the present invention is to provide a method for producing a polyester that does not use an organometallic compound as an initiator, has a high reaction rate, and suppresses the formation of a cyclic oligomer as a by-product.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that if bicyclic bis (γ-butyrolactone) s and epoxy compounds are reacted in the presence of phosphines, the reaction rate is large and cyclic The inventors have found that the production of oligomers can be suppressed and polyesters with high purity can be efficiently obtained, and the present invention has been completed.

  That is, the present invention provides a method for producing a polyester, characterized by reacting (A) a compound represented by the following general formula (1) with (B) an epoxy compound in the presence of (C) phosphines. Is to provide.

(In Formula (1), R < ¹ > -R < ⁶ > is the same or different, and is a hydrogen atom, a C1-C12 hydrocarbon group, a C1-C12 halogenated hydrocarbon group, or C1-C12. Represents an alkoxy group.)

  According to the method for producing a polyester of the present invention, it is possible to efficiently obtain a polyester having a high reaction rate and suppressing the formation of a cyclic oligomer as a by-product without using an organometallic compound.

1 is a diagram showing a ¹ H-NMR spectrum of a product obtained in Example 1. FIG. 1 is a diagram showing a ¹³ C-NMR spectrum of a product obtained in Example 1. FIG. 2 is a diagram showing an IR spectrum of the product obtained in Example 1. FIG. It is a figure which shows the MALDI-Tof-Mass spectrum of the product obtained in Example 1 and Comparative Example 1. It is a figure which shows the relationship between the monomer consumption rate in the polymerization reaction evaluated in Example 1 and Comparative Example 1, and polymerization reaction time. It is a figure which shows IR spectrum of the product obtained in Example 4.

  The polyester production method of the present invention is characterized in that (A) a compound represented by the following general formula (1) and (B) an epoxy compound are reacted in the presence of (C) phosphines.

(In Formula (1), R < ¹ > -R < ⁶ > is the same or different, and is a hydrogen atom, a C1-C12 hydrocarbon group, a C1-C12 halogenated hydrocarbon group, or C1-C12. Represents an alkoxy group.)

First, each component used for the manufacturing method of polyester of this invention is demonstrated.
[(A) component]
The component (A) is a bicyclic bis (γ-butyrolactone), which is a compound represented by the above formula (1).
In formula (1), R ^{1 to} R ⁶ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a halogenated hydrocarbon group having 1 to 12 carbon atoms, or an alkoxy having 1 to 12 carbon atoms. Indicates a group. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, phenyl group, naphthyl group , Biphenyl and the like. The halogenated hydrocarbon group having 1 to 12 carbon atoms includes a halogenated alkyl group having 1 to 12 carbon atoms, a halogenated cycloalkyl group having 3 to 12 carbon atoms, and a halogenated aromatic carbon atom having 6 to 12 carbon atoms. Examples thereof include a hydrogen group, specifically, a trichloromethyl group, a trifluoromethyl group, a tribromomethyl group, a pentachloroethyl group, a pentafluoroethyl group, a pentabromoethyl group, a chlorophenyl group, a chloronaphthyl group, and the like. Can be mentioned. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, phenoxy group, allyloxy group, and benzyloxy group.

Among these, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, including a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. More preferably it is.
Among these, R ^{3 to} R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. It is more preferably a group, and particularly preferably a hydrogen atom.

Specific examples of the compound represented by the formula (1) include 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₃ , R ² ~R ⁶ = H), 2,8- dioxa-1-ethylbicyclo [3.3.0] octane-3,7-dione _{^{(R 1 = C 2 H 5}} , R 2 ~R 6 = H), 2 , 8-dioxa-1-propylbicyclo [3.3.0] octane-3,7-dione (R ¹ = C ₃ H ₇ , R ^{2 to} R ⁶ = H), 2,8-dioxa-1-isopropyl Bicyclo [3.3.0] octane-3,7-dione (R ¹ = i-Pr, R ^{2 to} R ⁶ = H), 2,8-dioxa-1-phenylbicyclo [3.3.0] octane 3,7-dione _{^{(R 1 = C 6 H 5}} , R 2 ~R 6 = H), 2,8- dioxa-1- (3,4,5-trimethoxyphenyl) bicyclo B [3.3.0] octane-3,7-dione _{^{(R 1 = C 6 H 2}} (OCH 3) 3, R 2 ~R 6 = H), 2,8- dioxa-1- (phenoxymethyl) And bicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₂ OC ₆ H ₅ , R ^{2 to} R ⁶ = H).

[Component (B)]
Component (B) is an epoxy compound having at least one epoxy group, and any of a compound having one epoxy group and a compound having two or more epoxy groups can be used. Or it is a compound which has two epoxy groups.
In addition, as an epoxy compound which has an at least 1 epoxy group, the polymer containing an epoxy group is also included. In this case, the epoxy group may be present at any part of the molecular structure. For example, it may be present at the end of the main chain or may be present at the end of the side chain. From the viewpoint of reaction efficiency, a compound having an epoxy group at the end of the side chain is usually preferred. Examples of the polymer containing an epoxy group include polyglycidyl methacrylate and polyglycidyl acrylate.

  As a compound having one epoxy group, the compound represented by the formula (3)

(In formula (3), R ¹⁰ and R ¹¹ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent (other than an epoxy group)). And the compounds represented. Here, examples of the substituent on the hydrocarbon group represented by R ¹⁰ and R ¹¹ include a halogen atom and an alkoxy group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, and an aromatic hydrocarbon group. The alkyl group has 1 to 12 carbon atoms, the cycloalkyl group has 3 to 12 carbon atoms, and the aromatic group has 6 to 12 carbon atoms. A hydrocarbon group is more preferred. Examples of such compounds having one epoxy group include ethylene oxide, propylene oxide, glycidol, epoxybutane, pentamethylene oxide, epoxypentane, epoxybutane, epoxycyclopentane, epoxycyclohexane, styrene oxide, phenyl glycidyl ether, dibromophenyl glycidyl. Examples include ether, epichlorohydrin, epibromohydrin and the like.

  As a compound having two epoxy groups, a compound represented by the formula (4)

(In Formula (4), R < ¹² > and R <^13> are the same or different and show a hydrogen atom or a C1-C24 hydrocarbon group which may have a substituent (other than an epoxy group), R ¹⁴ represents a hydrocarbon group which may have a substituent having 2 to 24 carbon atoms, or a heterocyclic group which may have a substituent. Examples of the substituent on the hydrocarbon group and the heterocyclic group represented by R ^{12 to} R ¹⁴ include a halogen atom and an alkoxy group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, and a group in which these are bonded. The alkyl group having 1 to 12 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, and the carbon number. 6-12 aromatic hydrocarbon groups are more preferred. Examples of the heterocyclic group include heterocyclic groups having 1 to 4 selected from an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the compound having two epoxy groups include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol F diglycidyl ether, 1,3-bis- {4- [1-Methyl-1- (4-oxiranylmethoxyphenyl) -ethyl] -phenoxy} -propan-2-ol, 1,3-bis- {2,6-dibromo-4- [1- (3 5-Dibromo-4-oxiranylmethoxyphenyl) -1-methyl-ethyl] -phenoxy} -propan-2-ol, 1- (3- (2- (4-((oxiran-2-yl) methoxy) Phenyl) propan-2-yl) phenoxy) -3- (4- (2- (4-((oxiran-2-yl) methoxy) Eniru) propan-2-yl) phenoxy) propan-2-ol, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.

  Among the epoxy compounds described above, styrene oxide, phenyl glycidyl ether, dibromophenyl glycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol F diglycidyl ether, polyethylene glycol di Glycidyl ether and polypropylene glycol diglycidyl ether are preferably used. Styrene oxide, phenyl glycidyl ether, dibromophenyl glycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ether is better used It is.

[Component (C)]
(C) As a component, it is phosphines, A phosphine compound, a phosphite compound, etc. can be mentioned, Especially the compound represented by following formula (2) is used suitably.

In formula (2), R ^{7 to} R ⁹ are the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a halogenated hydrocarbon group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms. An alkoxy group is shown.

  Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group, vinyl group, allyl group, phenyl group, naphthyl group And biphenyl group. The halogenated hydrocarbon group having 1 to 12 carbon atoms includes a halogenated alkyl group having 1 to 12 carbon atoms, a halogenated cycloalkyl group having 3 to 12 carbon atoms, and a halogenated aromatic carbon atom having 6 to 12 carbon atoms. Examples thereof include a hydrogen group, specifically, a trichloromethyl group, a trifluoromethyl group, a tribromomethyl group, a pentachloroethyl group, a pentafluoroethyl group, a pentabromoethyl group, a chlorophenyl group, a fluorophenyl group, a chloro A naphthyl group etc. can be mentioned. Examples of the alkoxy group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, phenoxy group, allyloxy group, and cyclohexyloxy group.

Among these, R ^{7 to} R ⁹ are preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and the like. More preferably a group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group or a phenyl group, and particularly preferably a phenyl group.

  Examples of the solvent used in the method for producing a polyester of the present invention include alkanes such as pentane, hexane, heptane, and octane; cycloalkanes such as cyclohexane, cycloheptane, decalin, and norbornane; benzene, toluene, xylene, Aromatic hydrocarbons such as cumene; halogenated compounds such as chlorobutane, bromohexane, dichloromethane, dichloroethane, chloroform, chlorobenzene, dichlorobenzene, trifluoromethylbenzene; saturated carboxylic acid esters such as ethyl acetate; dibutyl ether, tetrahydrofuran, dimethoxyethane Ethers such as acetone; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, chlorobenzene, and 1,4-dioxane are preferable, and halogenated compounds are more preferable. Properly, specifically, tetrahydrofuran is particularly preferred.

  The reaction time for the above reaction is preferably 1 to 360 hours, more preferably 24 to 120 hours, and particularly preferably 48 to 72 hours. The reaction temperature of the above reaction is preferably from room temperature to 300 ° C, more preferably from 60 to 180 ° C, particularly preferably from 100 to 140 ° C. Moreover, it is preferable to perform the reaction pressure of the said reaction at about 1-2 atmospheres, and it is more preferable to carry out under atmospheric pressure.

  After completion of the reaction, the target polyester can be collected by known means such as solvent distillation, reprecipitation, centrifugation, or filtration. The obtained polyester is less contaminated with cyclic oligomers as a by-product, and a highly pure polyester can be obtained.

  (A) The compound represented by the above general formula (1) and the polyester obtained by reacting with the (B) epoxy compound used the compound represented by the above formula (3) as the (B) epoxy compound. In some cases, it has a repeating unit represented by the following formula (5).

(In the formula (5), R ^{1 to} R ⁶ , R ¹⁰ and R ¹¹ are the same as above)

  Moreover, it is preferable that it is 1,000-100,000, and, as for the weight average molecular weight (Mw) of polyester obtained, it is more preferable that it is 3,000-50,000. The polyester obtained by the method of the present invention has a high purity and does not contain a metal as an initiator residue, so that it is particularly useful for an electric material, an electronic material, and the like.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to this at all.

Example 1
In a 10 mL volume ampoule under nitrogen atmosphere, 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₃ , R ^{2 to} R ⁶ = H) 250 mg ( 1.6 mmol), 239 mg (1.6 mmol) of glycidyl phenyl ether, 3.7 mg (12.8 μmol) of triphenylphosphine, and 0.8 mL of tetrahydrofuran, and after deaeration and sealing, the polymerization reaction was carried out at 120 ° C. for 72 hours. went. After the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain a product with a yield of 87%.
The obtained product was evaluated for structural analysis and weight average molecular weight by the following methods. The monomer consumption rate during the polymerization reaction was evaluated by the following method.

(1) Structural analysis It was performed by NMR (400 MHz, CDCl ₃ ), IR (KBr method).
(2) Weight average molecular weight For the weight average molecular weight, tetrahydrofuran was used as a solvent, and a molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.
(3) Monomer consumption rate After removing the solvent from the measurement sample collected from the reaction solution, the amount of 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione was determined by NMR. The monomer consumption rate was calculated from the following formula.
Monomer consumption rate = 1- (amount of 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione in the sample for measurement) / 2,8-dioxa-1-methylbicyclo [3.3.0] Charge of octane-3,7-dione)

The weight average molecular weight (Mw) of the obtained product was 8,600, and Mw / Mn was 1.32.
1 and 2 show the results of measuring ¹ H-NMR and ¹³ C-NMR (400 MHz, solvent CDCl ₃ ) of the obtained product, and FIG. 3 shows the results of measuring IR of the obtained product. .

(Comparative Example 1)
In a 10 mL capacity ampoule under nitrogen atmosphere, 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₃ , R ^{2 to} R ⁶ = H) 250 mg ( 1.6 mmol), 239 mg (1.6 mmol) of glycidyl phenyl ether, 5.6 mg (12.8 μmol) of t-butoxypotassium, and 0.8 mL of tetrahydrofuran were added, and after deaeration and sealing, a polymerization reaction was performed at 120 ° C. for 72 hours. Went. After the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain a product with a yield of 72%. The weight average molecular weight (Mw) of the obtained product was 8,100, and Mw / Mn was 1.22. Further, the monomer consumption rate during the polymerization reaction was evaluated in the same manner as in Example 1.

The results obtained by measuring the products obtained in Example 1 and Comparative Example 1 using MALDI-Tof-Mass are shown in FIG. In the product obtained in Example 1, the peak intensity of the cyclic oligomer (CY) is significantly reduced as compared with the case where conventional tertiary butoxy potassium is used as an initiator. That is, it can be seen that the formation of cyclic oligomers is suppressed when polymerization is performed in the presence of phosphines than when polymerization is performed in the presence of metal alkoxide.
As a result of measuring ¹ H-NMR, ¹³ C-NMR (400 MHz, solvent CDCl ₃ ) and FT-IR (Neat) of the obtained product, the same spectrum as that of the product obtained in Example 1 was shown. .

  FIG. 5 shows the relationship between the monomer consumption rate during the polymerization reaction evaluated in Example 1 and Comparative Example 1 and the polymerization reaction time. In Example 1, compared with the comparative example 1, it turns out that a monomer consumption rate is large and reaction rate is high. That is, it can be seen that the reaction rate is improved when polymerization is performed in the presence of phosphines than when polymerization is performed in the presence of metal alkoxide.

(Example 2)
In a 10 mL volume ampoule under nitrogen atmosphere, 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₃ , R ^{2 to} R ⁶ = H) 250 mg ( 1.6 mmol), glycidyl phenyl ether 239 mg (1.6 mmol), tri-normal butylphosphine 2.6 mg (12.8 μmol), tetrahydrofuran 0.8 mL, put a degassed sealed tube, and then polymerization reaction at 120 ° C. for 72 hours Went. After the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain a product with a yield of 90%.
The obtained product was evaluated for structural analysis and weight average molecular weight in the same manner as in Example 1. The weight average molecular weight (Mw) of the obtained product was 8,500, and Mw / Mn was 1.31. Further, when ¹ H-NMR, ¹³ C-NMR (400 MHz, solvent CDCl ₃ ) and IR of the obtained product were measured, the same spectrum as in Example 1 was obtained.

(Example 3)
In a 10 mL volume ampoule under nitrogen atmosphere, 2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₃ , R ^{2 to} R ⁶ = H) 250 mg ( 1.6 mmol), 239 mg (1.6 mmol) of glycidyl phenyl ether, 3.6 mg (12.8 μmol) of tricyclohexylphosphine and 0.8 mL of tetrahydrofuran, and after deaeration and sealing, the polymerization reaction was carried out at 120 ° C. for 72 hours. went. After the reaction, the reaction mixture was cooled, and then the reaction was stopped by adding a chloroform solution of acetic acid (1 vol%, 2 mL). This reaction solution was poured into methanol, and an oily product insoluble in methanol was collected and vacuum-dried to obtain a product with a yield of 64%.
The obtained product was evaluated for structural analysis and weight average molecular weight in the same manner as in Example 1. The weight average molecular weight (Mw) of the obtained product was 7,800, and Mw / Mn was 1.31. Further, when ¹ H-NMR, ¹³ C-NMR (400 MHz, solvent CDCl ₃ ) and IR of the obtained product were measured, the same spectrum as in Example 1 was obtained.

Example 4
2,8-dioxa-1-methylbicyclo [3.3.0] octane-3,7-dione (R ¹ = CH ₃ , R ^{2 to} R ⁶ = H) 160 mg (1.0 mmol), polyethylene glycol diglycidyl 269 mg (0.5 mmol) of ether and 5.4 mg (2.0 μmol) of triphenylphosphine were dissolved in 2 mL of THF, and the solution was put into a 2 mL volume mold, and then THF was distilled off at room temperature under reduced pressure (200 mmHg). . After the THF was distilled off, the mold was placed in an oven and reacted at 120 ° C. for 72 hours under a nitrogen atmosphere. After the reaction, the cured product taken out from the mold was washed with methanol and dried to obtain a cured product quantitatively.
About the obtained hardened | cured material, the structural analysis was performed by the following method.

(1) Structural analysis It was performed by IR spectrum measurement and TG and DSC measurement.

The result of measuring IR of the obtained product is shown in FIG. From the results of TG measurement, the 10% thermal decomposition temperature (T _d10 ) was 321 ° C., and from the results of DSC measurement, it was revealed that the glass transition point (T _g ) was −19 ° C.

Claims (3)

(A) A method for producing a polyester, comprising reacting a compound represented by the following general formula (1) with (B) an epoxy compound in the presence of (C) phosphines.

(In Formula (1), R < ¹ > -R < ⁶ > is the same or different, and is a hydrogen atom, a C1-C12 hydrocarbon group, a C1-C12 halogenated hydrocarbon group, or C1-C12. Represents an alkoxy group.) The method for producing a polyester according to claim 1, wherein the phosphine is a compound represented by the following general formula (2).

(In Formula (2), R < ⁷ > -R < ⁹ > is the same or different, and is a hydrogen atom, a C1-C12 hydrocarbon group, a C1-C12 halogenated hydrocarbon group, or C1-C12. Represents an alkoxy group.) (B) The manufacturing method of the polyester of Claim 1 or 2 whose epoxy compound is at least 1 sort (s) of the compound represented by following formula (3), and the following formula (4).

(In Formula (3), R ¹⁰ and R ¹¹ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent (other than an epoxy group)).

(In Formula (4), R < ¹² > and R <^13> are the same or different and show a hydrogen atom or a C1-C24 hydrocarbon group which may have a substituent (other than an epoxy group), R ¹⁴ represents a hydrocarbon group which may have a substituent having 2 to 24 carbon atoms, or a heterocyclic group which may have a substituent)

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