JP2002256065A - New fumaric acid ester and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition and its cured material, excellent in curing property and surface hardness. SOLUTION: This new fumaric acid ester is composed of, as repeating units, fumaric acid and a structure of polyalcohol, having a alkenyloxy group (for example, a propenyl ether group) at a terminal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention is excellent in radical polymerizability, can give a polymer by light or heat, and can be used as a crosslinking agent for various polymers. Particularly, paints, coatings, adhesives, sealings, etc. The present invention relates to a novel fumaric acid ester which can be used in fields requiring curing under air, such as a material, a method for producing the ester, a polymerizable composition containing the ester, and a cured product thereof.

[0002]

2. Description of the Related Art Hitherto, polyfunctional compounds having a double bond have been used in many applications as raw materials for polymerizable compositions.

[0003] As a method for curing these polymerizable compositions, radical polymerization by light or heat is mainly used. Among them,
In recent years, particularly from the viewpoint of economy, high-speed photopolymerization using ultraviolet light (UV) has been performed. Those used as polymerizable compositions for high-speed photopolymerization generally include acrylic compounds,
Unsaturated carboxylic acid ester compounds are exemplified. However, these compounds have the following problems.

The crosslinking monomer of the acrylic compound is UV
Since it can be cured in a relatively short time in curing, it is applied to various UV curable materials such as paints and coatings. However, it has a relatively high skin irritancy and is easily susceptible to curing by oxygen, so it forms a thin film However, there is a disadvantage that stickiness is likely to occur during the operation.

On the other hand, as unsaturated carboxylic acid ester compounds, dialkyl esters of fumaric acid and maleic acid are known, but are poor in radical polymerizability alone.
Even in copolymerization with other resins, the strength of the obtained cured product may be insufficient due to insufficient crosslinking degree. Unsaturated polyesters alone have a large molecular weight and are inferior in homopolymerizability. Therefore, styrene monomers are generally used as a reactive diluent. However, alternatives are required for styrene monomers in terms of workability such as odor.

As means for solving these problems, vinyl ethers, which are a kind of alkenyl ether, have recently been receiving attention as non-acrylic compounds.

[0007] Such vinyl ethers are generally used as a cationically polymerizable curable material. It is said that radical polymerization of vinyl ether itself hardly proceeds. However, the progress of the copolymerization of maleic acid ester and vinyl ether is considered to be RadTec.
h North America, 167 (1992)
Reported in.

[0008] Several other examples of copolymerization systems are also known and are disclosed in US Pat. No. 5,334,455 and US Pat.
No. 334456 discloses a polymer obtained by polymerizing a polyfunctional vinyl ether and a reaction product of an epoxy and maleic anhydride, and a polymer obtained by polymerizing a polyfunctional vinyl ether and a maleic acid ester. Describe a composition of unsaturated polyester and vinyl ether.

Further, it is known that vinyl ether proceeds with acrylate while having low copolymerizability.

[0010] These vinyl ethers have low viscosity,
It has excellent diluting ability and high adhesion to the substrate during curing. However, as described above, vinyl ether has poor radical polymerizability alone, so in a system containing an unsaturated polyester or the like, the polymerization of the vinyl ether group is incomplete and the physical properties of the cured product are not sufficiently expressed, and The ratio between the other polymerizable group and the vinyl ether group had to be adjusted, and there was a problem that the amount used was limited.

As a method for solving these problems, Japanese Patent Publication No. 55-395533 discloses a method for producing a compound having a vinyl ether group at the terminal and a malate structure therein. A compound having an ether group and having a malate structure or a fumarate structure therein is described.

However, these polymerizable compounds have only two polymerizable groups at the terminal and one polymerizable group inside, and cannot be said to have a sufficient crosslinking point yet. Furthermore, these vinyl ethers and allyl ethers have an alkylene ether, and the refractive index of the cured product tends to be low, and problems such as electric characteristics and heat resistance may occur. There was no case.

[0013]

SUMMARY OF THE INVENTION The present invention can solve the disadvantages of the conventional radically polymerizable compounds, such as being inhibited by oxygen during curing and having a low surface hardness of the cured product. It is another object of the present invention to provide a novel fumaric acid ester having a sufficient crosslinking point, a method for producing the ester, a polymerizable composition containing the ester, and a cured product thereof.

[0014]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, as a radical polymerizable resin or as a crosslinking agent for the resin, it has an alkenyloxy group such as a vinyl ether group, a propenyl ether group and an allyl ether group and a fumarate group in the same molecule, and is further multifunctionalized having many double bonds. The present inventors have found a novel fumaric acid ester which has been subjected to the above, thereby solving the above-mentioned problems and completing the present invention.

That is, the present invention (I) is characterized in that it has a group represented by the general formula (1) as a terminal group and a group represented by the general formula (2) as a repeating unit. It is a fumaric acid ester.

General formula (1)

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General formula (2)

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(In the general formula (1), R ¹ each independently represents the general formula (3) or the general formula (4). In the general formula (1) or the general formula (2), X ¹ , X ^{And 2} independently represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms and having 2 to 6 hydroxyl groups, provided that X ¹ and X ² represent an ester bond, and (It can have a branched structure in which (1) is a terminal group and a group represented by formula (2) is a repeating unit.)

General formula (3)

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(In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

General formula (4)

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(In the general formula (4), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms.)

Also, the present invention (II) has a group represented by the general formula (1) as at least one terminal group, and a group represented by the general formula (2) and / or a group represented by the general formula (5) ) Is a fumaric acid ester having a repeating unit represented by the formula (1):

General formula (1)

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General formula (2)

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General formula (5)

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(In the general formula (1), R ¹ each independently represents the general formula (3) or the general formula (4). In the general formulas (1), (2) and (5), ,
X ¹ , X ² and X ³ each independently represent an organic residue derived from a polyhydric alcohol having 2 to 6 hydroxyl groups and having 2 to 30 carbon atoms. However, X ¹ , X ² , and X ^{3 each} have an ester bond and / or an ether bond, and further have the general formula (1) as a terminal group, and have a group represented by the general formula (2) and / or a general formula (5). It can have a branched structure in which the represented group is a repeating unit. )

General formula (3)

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(In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

General formula (4)

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(In the general formula (4), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms.)

The present invention (III) is the same as the present invention (I)
Or a method for producing a fumaric acid ester of the present invention (II).

The present invention (IV) further comprises the present invention (I)
Or a polymerizable composition comprising the fumaric acid ester of the present invention (II).

The present invention (V) is a cured product obtained by curing the polymerizable composition of the present invention (IV).

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below.
First, the present invention (I) will be described. The present invention (I)
Is a fumaric acid ester having a group represented by the general formula (1) as at least one terminal group and a group represented by the general formula (2) as a repeating unit.

General formula (1)

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General formula (2)

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(In the general formula (1), R ¹ each independently represents the general formula (3) or the general formula (4). In the general formula (1) or the general formula (2), X ¹ , X ^{And 2} independently represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms and having 2 to 6 hydroxyl groups, provided that X ¹ and X ² represent an ester bond, and (It can have a branched structure in which (1) is a terminal group and a group represented by formula (2) is a repeating unit.)

General formula (3)

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(In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

General formula (4)

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(In the general formula (4), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms.)

The present invention (I) has at least one group represented by the general formula (1) as a terminal group, and has a fumarate ester structure represented by the general formula (2) as one or more repeating units. And one of the typical examples is
Examples include the compound represented by the general formula (12).

General formula (12)

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(In the general formula (12), e represents an integer of 1 to 9.)

R ^{1 in the} general formula (1) according to the present invention represents either the general formula (3) or the general formula (4).

R of the general formula (3)^Two, R^ThreeAre independently
Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
You. In the general formula (3), preferred in view of radical polymerizability.
Kuha R ^Two, R^ThreeAt least one is a hydrogen atom or a methyl group
And the other is a hydrogen atom, a methyl group, an ethyl group, n-propyl
And at least one of an iso-propyl group. Yo
More preferably R^Two, R^ThreeAt least one is a hydrogen atom and the other
Is a hydrogen atom or a methyl group, most preferably
R^Two, R^ThreeAre hydrogen atoms. With 4 or more carbon atoms
Alkyl groups are not preferred because polymerizability may decrease.
No.

R ⁴ in the general formula (4) represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms. In the general formula (4), R ⁴ is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and i
It is at least one kind of a so-propyl group. More preferably, R ⁴ is a hydrogen atom or a methyl group. An alkyl group having 4 or more carbon atoms is not preferable because the polymerizability may decrease.

X ¹ and X ² are each independently 2 to 6
It represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms having two hydroxyl groups.

Specific examples of the polyhydric alcohol include ethylene glycol, neopentyl glycol, 1,2-
Alkylene diols such as propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and nonanediol, and substituted alkylene glycols include 1-phenylethylene Glycol, 1,2
-Diphenylethylene glycol, also these polyalkylene diols, 1,1-cyclohexanediol,
1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,
Alicyclic diols such as 1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, bisphenol A, bisphenol F, bisphenol S And aromatic diols such as benzene dimethanol, and ethylene oxide adducts, propylene oxide adducts, cyclohexene oxide adducts, and styrene oxide adducts of these polyhydric alcohols.

Further, trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerin; tetrahydric alcohols such as pentaerythritol, diglycerin and ditrimethylolpropane; hexahydric alcohols such as dipentaerythritol and sorbitol; Ethylene oxide adducts, propylene oxide adducts, cyclohexene oxide adducts, styrene oxide adducts, and the like of these polyhydric alcohols can also be added to such an extent that they do not gel.

Further, depending on the kind of the polyhydric alcohol, there may be a stereoisomer and a geometric isomer. For example, in the general formula (12), when e = 2 and X ² is an organic residue derived from 1,2-cyclohexanediol, the positional relationship between two ester bonds bonded to two cyclohexyl rings is cis- cis, cis-tran
s and trans-trans are considered, and the molecule as a whole may be an optical isomer. In such a case, it is possible to use a specific optical isomer with an increased abundance ratio in an optically active column or the like, or it may be used without such treatment.

In these, X ¹ is an ethylene group (-
(CH ₂ ) ₂ —), 1,3-propylene group (— (CH ₂ ) ₃
-), 1,2-propylene group (-CH ₂ -CH (CH ₃₎
-) And other alkylene groups having 2 to 4 carbon atoms, such as 1,1
-Cyclohexylene group, 1,2-cyclohexylene group,
1,3-cyclohexylene group, 1,4-cyclohexylene group,

[0054] Formula _{(-CH 2 -C 6 H 10 -CH} 2 -) organic residue derived from 1,1-cyclohexanedimethanol represented by the organic residue derived from 1,2-cyclohexane dimethanol Cured product after polymerization of a cycloalkylene having 6 to 8 carbon atoms such as a group, an organic residue derived from 1,3-cyclohexanedimethanol, or an organic residue derived from 1,4-cyclohexanedimethanol Excellent in terms of hardness.

Further, in order to improve the refractive index of the cured product, the cured product had a phenyl group or a phenylene group such as bisphenol A and an ethylene oxide adduct of bisphenol A, 1-phenyl-ethylene glycol and 1,2-diphenylene glycol. Alkylene diols are preferred.

The number of repeating units of the general formula (2) may be one or more, but is preferably 1 to 10 (e in the general formula (12) is an integer of 1 to 9). If the number of repeating units is 10 or more, the viscosity becomes extremely high, and gelation may occur during production, which is not preferable.

When X ¹ is a trihydric or higher polyhydric alcohol organic residue, it may have a branched structure represented by the following general formula (13).

General formula (13)

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(In the general formula (13), f represents an integer of 0 to 4.) When X ² is a trihydric or higher polyhydric alcohol organic residue, a branched structure represented by the following general formula (14) is obtained. It is also possible to take.

General formula (14)

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(In the general formula (14), g represents an integer of 0 to 4.)

The terminal polymerizable group R ^{1 of the} general formula (1)
Is poor in radical polymerizability alone and cure proceeds by copolymerization with a fumarate group, so that those having a molar ratio of R ¹ group / fumarate group close to ¹ are generally excellent in physical properties of a cured product. Preferably, the molar ratio of R ¹ group / fumarate group is in the range of 0.2 to 2, more preferably 0.8 to 1.
5 range.

R ¹ each independently represents the general formula (3) or the general formula (4). Therefore, the structure of the general formula (3) and the structure of the general formula (4) can coexist in the fumarate ester molecule in the present invention. The terminal having the structure of general formula (4) can also be produced by isomerizing all or part of the structure of general formula (3). R ² and R ³ in the general formula (3) are preferably a hydrogen atom or a methyl group, and more preferably both are hydrogen atoms. Further, R ⁴ in the general formula (4) is preferably a methyl group (the general formula (4) as a whole is a propenyl group).

Next, the present invention (II) will be described. The present invention (II) has at least one group represented by the general formula (1) as a terminal group, and has the general formula (2)
And / or a group represented by the general formula (5) as a repeating unit.

Formula (1)

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General formula (2)

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Formula (5)

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(In the general formula (1), R ¹ each independently represents the general formula (3) or the general formula (4). Further, the general formulas (1), (2) and (5) In, X
¹ , X ² and X ³ each independently represent an organic residue derived from a polyhydric alcohol having 2 to 6 hydroxyl groups and having 2 to 30 carbon atoms. However, X ¹ , X ² , and X ^{3 each} have an ester bond and / or an ether bond, and have the general formula (1) as a terminal group, and a group represented by the general formula (2) and / or
Alternatively, the compound may have a branched structure in which a group represented by the general formula (5) is a repeating unit. )

General formula (3)

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(In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

Formula (4)

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(In the general formula (4), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms.)

The fumaric acid ester of the present invention (II) has at least one group represented by the general formula (1) as a terminal group, and has a repeating structure represented by the general formula (2). It contains an acid ester structure and / or an ether structure represented by the general formula (5).

The terminal group represented by the general formula (1) and the repeating structure represented by the general formula (2) in the present invention (II) are the same as those in the present invention (I).

Further, X contained in the general formula (5)^ThreeIs one
X in general formula (1)¹, X of the general formula (2) ^Two2 to 6 as in
C2-C30 polyvalent alcohol having two hydroxyl groups
Represents an organic residue derived from a polymer.

X ^{3 is the same} as X ^{1 in} the general formula (1) and X ^{2 in the} general formula (2) also in terms of a polyhydric alcohol which can be preferred and a branch structure.

One of the typical examples of the fumaric acid ester of the present invention (II) is a compound represented by the following general formula (15).

Formula (15)

Embedded image (In the general formula (15), h, i, and k are 0 to 5 integers, and j is 1 to
An integer of 5 and n represents an integer of 1 to 9. However, h + i +
k ≧ 1. )

If any one of h, i, j, and k exceeds 5, the concentration of the polymerizable double bond decreases, and the curability and the hardness of the cured product may decrease.

The fumaric acid esters of the present invention (I) and (II) necessarily have at least one group represented by the general formula (1) as a terminal group. The carboxyl group of (8) or a hydroxyl group derived from a polyhydric alcohol can be used as a terminal group.

Specific examples having a carboxyl group of the general formula (8) derived from fumaric acid as a terminal group include compounds represented by the general formula (9).

The fumaric acid ester represented by the general formula (9) is a polymerizable compound having an alkenyl ether group and a carboxyl group derived from fumaric acid as terminal groups and having a fumarate skeleton therein. Alkenyl ether groups and fumarate groups have high radical copolymerizability. Further, the terminal carboxyl group can form an ester bond with various hydroxyl groups, and polymerizable esters having various physical properties can be synthesized.

On the other hand, specific examples of the compound having a hydroxyl group as a terminal group include a compound represented by the general formula (10).

The general formula (10) has a general formula (3), more preferably an allyl ether group and a general formula (4), more preferably a propenyl ether group, as a terminal group. It is a fumaric acid ester having a hydroxyl group derived from a polyhydric alcohol as a terminal group. Z in the general formula (10) represents an organic residue of a trihydric to hexahydric polyhydric alcohol.

The polyhydric alcohol mentioned here includes, for example,
Trimethylolpropane, trimethylolethane, trihydric alcohols such as glycerin, pentaerythritol, ditrimethylolpropane, tetrahydric alcohols such as diglycerin, sorbitol, hexahydric alcohols such as dipentaerythritol, or trihydric alcohols thereof Hexahydric alcohols obtained by adding Ethiolen oxide or Propylene oxide to hydroxyl groups, and mixtures of two or more of these.

Among these, trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, in which all hydroxyl groups are primary alcohols, ethylene oxide adducts of these alcohols, and mixtures of two or more of these alcohols Is preferred because of high reactivity of the ester formation reaction.

Next, the present invention (III) will be described. The present invention (III) is the present invention (I) or the present invention (I
This is a method for producing a fumaric acid ester of I).

The process for producing the fumaric acid ester of the present invention (I) or (II) can be divided into the following two steps A) and B). A) a step of forming an ester which is a main skeleton of the fumaric acid ester and a step of forming a repeating unit of the ester; and B) converting a terminal polymerizable group represented by the general formula (4) to a group represented by the general formula (3) It is a two-step process of forming by isomerization.

These two steps are not essential for producing the fumaric acid ester of the present invention (I) or (II).
Alternatively, it is possible to produce the fumaric acid ester of the present invention (II).

First, the step A) in the method for producing a fumarate of the present invention (I) or (II) will be described.

The fumaric acid ester represented by the general formula (9) of the present invention (I) is subjected to an addition reaction between maleic anhydride and an alcohol represented by the general formula (16) to obtain a maleic acid monoester. Thereafter, it can be produced by a method of isomerizing malate to fumarate. At this time, the isomerization ratio to fumarate is not always 100%, but may be a mixture of malate and fumarate. From the viewpoint of polymerizability, fumarate is more preferable.

Formula (16)

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[0093] (In the general formula (16), X ⁴ is the general formula (16) in, d pieces cycloalkylene group each independently an alkylene group or a carbon number of 5-12 carbon atoms in the X ⁴ of the presence or the general formula (6 ) Represents an alkylene group, and d represents any one of integers of 1 to 5.
R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) General formula (6)

Embedded image R ⁵ and R ⁶ each represent a hydrogen atom or a general formula (7). General formula (7)

Embedded image (In the general formula (7), R ⁷ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 3 carbon atoms)

Further, R in the general formula (10) of the present invention (I)
^The fumaric acid ester in which ¹ is represented by the general formula (3) can be produced by an esterification reaction between the fumaric acid ester represented by the general formula (9) and a polyhydric alcohol.

The fumaric acid ester represented by the general formula (3) wherein R ¹ of the general formula (11) is represented by a fumaric acid ester represented by the general formula (9) and an alcohol represented by the general formula (16) And an esterification reaction between an alcohol represented by the general formula (16) and fumaric acid, or a transesterification reaction between a dialkyl fumarate and an alcohol represented by the general formula (16).

Further, the fumaric acid ester represented by the general formula (3) wherein R ^{1 in} the general formula (12) of the present invention (I) is a fumaric acid ester represented by the general formula (17) and a polyhydric alcohol Can be produced by a transesterification reaction.

Formula (17)

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(In the general formula (17), R ¹ each independently represents the general formula (3) or the general formula (4). X ¹ has 2 to 6 hydroxyl groups and 2 to 30 carbon atoms. Represents an organic residue derived from a polyhydric alcohol of the formula ( ¹ ). Further, the fumaric acid ester represented by the general formula (15) of the present invention (II) wherein R ¹ is represented by the general formula (3) is represented by the general formula (18) )
And a polyhydric alcohol represented by the general formula (19).

Formula (18)

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General formula (19)

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The fumaric acid ester represented by the general formula (20) is obtained by an esterification reaction between the fumaric ester represented by the general formula (9) and an alcohol represented by the general formula (16), or It can be produced by an esterification reaction between an alcohol represented by the general formula (16) and fumaric acid. General formula (20)

Embedded image (In the general formula (20), X ⁴ is
d represents X ⁴ independently represents an alkylene group, a cycloalkylene group having 5 to 12 carbon atoms, or an alkylene group represented by the general formula (6);
Represents any one of integers from 1 to 5. R ² and R ³ are
Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) General formula (6)

Embedded image R ⁵ and R ⁶ each represent a hydrogen atom or a general formula (7). General formula (7)

Embedded image (In the general formula (7), R ⁷ is a hydrogen atom or carbon atom 1
First, a method for producing a fumarate represented by the general formula (9) will be described in detail. As a specific example of the method for producing the fumaric acid ester represented by the general formula (9), maleic anhydride and an alcohol represented by the general formula (16) are subjected to an addition reaction to produce a maleic acid monoester, and thereafter, There is a method of isomerizing malate to fumarate.

The addition reaction between maleic anhydride and the alcohol represented by the general formula (16) can be carried out without a catalyst or with a catalyst. The catalyst is not particularly limited as long as it is a general esterification catalyst, but preferably includes a basic catalyst such as triethylamine and N, N-dimethylaminopyridine.

The reaction is carried out at a temperature of 20 ° C. to 150 ° C., preferably 40 ° C. to 120 ° C. If the reaction temperature is lower than 20 ° C,
The progress of the reaction may be slow and take longer than necessary.
On the other hand, if the reaction temperature exceeds 150 ° C., the yield of diester increases, and the yield may decrease, which is not preferable.

The ratio of the charged amounts of maleic anhydride and the alcohol represented by the general formula (16) is not particularly limited. Generally, the alcohol represented by the general formula (16) is used in an amount of 0.2 mol equivalent to 10 mol per mol of maleic anhydride.
It is in the range of molar equivalents, preferably in the range of 0.5 molar equivalents to 5 molar equivalents, more preferably in the range of 0.9 molar equivalents to 2 molar equivalents.

When the ratio of the charged amount of the alcohol represented by the general formula (16) exceeds 10 molar equivalents, excess alcohol increases, and when it is less than 0.2 molar equivalents, unreacted maleic anhydride increases, Not economically desirable.

It is also possible to add a solvent during this addition reaction. Such solvents include benzene,
Toluene, aromatic hydrocarbons such as xylene, diethyl ether, dimethoxyethane, methoxyethyl ether,
Examples thereof include ethers such as tetrahydrofuran and 1,4-dioxane.

R of the alcohol represented by the general formula (16)
² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, similarly to R ² and R ³ in the general formula (3) described above.

It is particularly desirable that both R ² and R ³ are hydrogen atoms from the viewpoint of polymerizability. Such a general formula (1)
Specific examples of the alcohol represented by 6) include ethylene glycol monoallyl ether, propylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, 1,4-butylene glycol monoallyl ether, and cyclohexanediol monoallyl. Allyl ether, cyclohexane dimethanol monoallyl ether,
Diethylene glycol monoallyl ether, dipropylene glycol monoallyl ether, 2-allyloxy-
Examples thereof include 2-phenylethanol, 2-allyloxy-1-phenylethanol, and 2-allyloxy-1,2-diphenylethanol.

The resulting maleic acid monoester can be converted to a fumaric acid monoester using a known acidic catalyst such as hydrochloric acid, a basic catalyst such as morpholine, piperidine, diethylamine, or the like, or a catalyst such as thiourea, chlorine, bromine, iodine, or acid chloride. Can be isomerized.

There is no particular limitation on the reaction temperature of the isomerization reaction. Generally in the range of 30 ° C to 200 ° C, preferably 5 ° C.
The range is from 0 ° C to 150 ° C, more preferably from 70 ° C to 120 ° C. When the reaction temperature exceeds 200 ° C., the risk of polymerization or decomposition reaction increases, which is not preferable.

In this isomerization reaction, a known hindered phenol-based polymerization inhibitor or solvent may be used. Here, as the solvent used, for example,
Aromatic hydrocarbons such as benzene, toluene and xylene,
Examples include ethers such as diethyl ether, dimethoxyethane, methoxyethyl ether, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; and ketones such as acetone and methyl ethyl ketone.

The fumaric acid ester represented by the general formula (9) thus obtained can be purified by a treatment such as distillation, liquid separation, and recrystallization.

Next, a method for producing a fumarate in which R ¹ in the general formula (10) is represented by the general formula (3) will be described.

The fumaric acid ester in which R ^{1 in the} general formula (10) is represented by the general formula (3) can be produced by an esterification reaction between the fumaric ester represented by the general formula (9) and a polyhydric alcohol. . Specific examples of the esterification reaction include

A method for esterifying a fumarate represented by the general formula (9) and a polyhydric alcohol in the presence of an acid catalyst, after derivatizing the fumarate represented by the general formula (9) to an acid halide. Method of esterifying by reacting with polyhydric alcohol There are three methods of esterifying by reacting a fumaric acid ester represented by the general formula (9) with a polyhydric alcohol using a condensing agent.

The first method will be described. Examples of the esterification catalyst that can be used in the method include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and known catalysts.
Examples include an ion exchange resin, a mixed catalyst of boric acid and sulfuric acid, polyphosphoric acid, and a Lewis acid such as boron trifluoride etherate.

The reaction can be carried out under normal pressure, under pressure or under reduced pressure, for example, at an absolute pressure of 15 Pa to 1 MPa. Reaction temperature 20 ° C to 200 ° C, preferably 40 ° C
The reaction proceeds at ~ 150 ° C. while distilling off by-produced water.
If the temperature is lower than 20 ° C., the reaction is slow.

At the time of the reaction, a solvent can also be used.
The solvent is not particularly limited, but specific examples include benzene, hexane, cyclohexane, toluene, and xylene.

There is no particular limitation on the ratio of fumaric acid represented by the general formula (9) to the polyhydric alcohol. Preferably, the hydroxyl group (—OH) of the polyhydric alcohol is in the range of 0.2 to 5 molar equivalents, more preferably the carboxyl group (—COOH) of the fumaric acid ester represented by the general formula (9). Ranges from 0.5 molar equivalents to 1.5 molar equivalents. If the charging ratio is less than 0.2 molar equivalent, the residual amount of the fumaric acid ester represented by the general formula (9) becomes too large, and if it exceeds 5 molar equivalent, unreacted hydroxyl groups remain, which is not preferable.

At this time, depending on the reaction conditions, for example, part of the alcohol corresponding to R ^1- (OX ⁵ ) a-OH is eliminated from the ester site of the fumarate represented by the general formula (10). Further, the alcohol may cause an esterification reaction with the carboxyl group of the fumaric acid ester represented by the general formula (9) to produce a diester monomer of fumaric acid, which may be contained in the product. Can be used as a polymerizable composition without removing it.

After the completion of the esterification reaction, purification can be performed to remove impurities and unreacted substances. As a purification method, for example, a fumarate ester is dissolved in an organic solvent such as benzene, toluene, cyclohexane, diethyl ether, methyl acetate, and ethyl acetate, and washed with water and an alkali to obtain an unreacted general formula (9) Can be removed as a salt.

Further, the product is decanted or reprecipitated with an organic solvent such as an aliphatic hydrocarbon such as hexane or octane, a method of column purification using silica gel or the like, or a purification by thin layer chromatography or the like. This can increase the purity.

Next, the method (1) will be described. Is a method in which the fumaric acid ester represented by the general formula (9) is derivatized to an acid halide and then reacted with a polyhydric alcohol to esterify the acid halide.

The method for derivatizing the fumaric acid ester represented by the general formula (9) into an acid halide is not particularly limited, and thionyl chloride, phosphoryl chloride, phosphorus pentachloride, phosphorus trichloride, phosgene and the like are used. It is possible by a known method.

In particular, when thionyl chloride is used, zinc chloride, pyridine, iodine, triethylamine and the like may be used in combination as a catalyst. It is also known that a mixture of thionyl chloride and dimethylformamide and a mixture of thionyl chloride and hexamethylphosphoric triamide are good reagents for synthesizing an acid halide.

The derivatized general formula (9)
By reacting the acid halide of the fumarate represented by the formula with a polyhydric alcohol by a known method, the fumarate represented by the general formula (5) of the present invention can be produced.

The last method will be described. Is a method in which the fumaric acid ester represented by the general formula (9) is reacted with a polyhydric alcohol using a condensing agent to perform esterification.

Specific examples of the condensing agent used in the above method include dicyclohexylcarbodiimide, trifluoroacetic anhydride, and sulfonyl chloride, but are not limited thereto. Any known condensing agent can be used without particular limitation.

In particular, a method using sulfonyl chloride is preferred in view of ease of handling. When a sulfonyl chloride is used as a condensing agent, as an example, a reaction is carried out by adding a base to a fumaric ester represented by the general formula (9) in the presence of a solvent, then adding the sulfonyl chloride, and finally adding A method in which a reaction is performed by adding a dihydric alcohol can be used.

The sulfonyl chloride used here includes p-toluenesulfonyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride and the like.

The amounts of the fumaric acid ester represented by the general formula (9) and the sulfonyl chloride are not particularly limited, but generally an equivalent or more of the sulfonyl chloride is used.
Preferably, the sulfonyl chloride is in the range of 1 molar equivalent to 2 molar equivalents with respect to the fumaric acid ester represented by the general formula (9).

There is no particular limitation on the charging ratio of the fumaric acid ester represented by the general formula (9) and the polyhydric alcohol. Preferably, the hydroxyl group (-OH) of the polyhydric alcohol is 0.2 molar equivalent to 2 to 2 relative to the carboxyl group (-COOH) of the fumaric acid ester represented by the general formula (9).
The range of molar equivalents, more preferably 0.4 molar equivalents to 1.
It is in the range of 2 molar equivalents.

The solvent used at this time is not particularly limited as long as it does not inhibit the reaction. Specific examples include ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene, and xylene; halides such as chloroform, dichloromethane, and dichloroethane; dimethylformamide, and dimethylsulfoxide.

Examples of the base include alkali metals such as sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.

The amount of the base depends on the kind thereof, but is preferably in the range of 1 molar equivalent to 5 molar equivalents with respect to the fumarate represented by the general formula (9).

The reaction temperature is from -20 ° C to 100 ° C, preferably from 0 ° C to 50 ° C. If the temperature exceeds 100 ° C., side reactions increase, and if it is lower than −20 ° C., the reaction may be delayed, which is not preferable.

The product obtained can be purified to remove impurities. As a purification method, for example,
Dissolve the product in an organic solvent such as benzene, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, diethyl ether, dichloroethane, chloroform,
Washing with water, alkali, acid, hexane,
Examples of the method include a method of decanting and reprecipitating a product with an organic solvent such as an aliphatic hydrocarbon such as octane. Further, the purity can be increased by performing column purification using silica gel or the like, or performing purification by thin layer chromatography or the like.

Next, a method for producing a fumarate in which R ^{1 in} the general formula (11) of the present invention (I) is represented by the general formula (3) will be described. The fumaric acid ester represented by the general formula (3) in which R ¹ of the general formula (11) is obtained by esterifying the fumaric ester represented by the general formula (9) with an alcohol represented by the general formula (16) It can be produced by a reaction or an esterification reaction between fumaric acid and an alcohol represented by the general formula (16). Specific examples of the esterification reaction are the same as the above-described method for producing a fumaric acid ester in which R ¹ in the general formula (10) is represented by the general formula (3). As another method, there is a transesterification reaction of dialkyl fumarate with the general formula (16). That is, the general formula (11)
Fumaric acid ester R ¹ is represented by the general formula (3) of the
The dialkyl fumarate and the alcohol represented by the general formula (16) can be produced by a method in which a reaction is carried out in the presence of a known transesterification catalyst while removing alcohol by-produced. As the dialkyl fumarate, dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate,
Examples include disec-butyl fumarate and t-butyl fumarate. Dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate and diisopropyl fumarate are preferred from the standpoint of easy removal of by-product alcohol.

There is no particular limitation on the transesterification catalyst that can be used here. Specifically, for example, alkali metals, alkaline earth metals and oxides thereof, Zn, S
Examples include oxides and hydroxides of n and Ti, alcoholates, acetylacetonato complexes, and the like.

The reaction can be carried out at a reaction temperature of 80 ° C. to 200 ° C. under a normal pressure, an increased pressure or a reduced pressure, for example, at an absolute pressure of 15 Pa to 1 MPa.

The fumaric acid ester represented by the general formula (11), in which the fumaric acid ester moiety is a maleic acid ester, is once synthesized and isomerized to give a compound represented by the general formula (11). Can be obtained.

The maleic acid ester used in this isomerization reaction is prepared by adding maleic acid or maleic anhydride to the compound represented by the general formula (1) in the same manner as in the production method of the fumaric acid ester represented by the general formula (11).
It can be produced by an esterification reaction with an alcohol represented by 6). Specific examples of the esterification reaction are the same as the above-described method for producing a fumaric acid ester in which R ¹ in the general formula (10) is represented by the general formula (3). Alternatively, a transesterification reaction of dialkyl maleate with the general formula (16) can be mentioned. As a specific example of the transesterification reaction, as described above, as in the transesterification reaction in which R ^{1 in the} general formula (11) is a method for producing a fumarate ester represented by the general formula (3), a dialkyl maleate and a general formula ( The alcohol represented by 16) can be produced by a method in which a reaction is carried out in the presence of a known transesterification catalyst while removing by-product alcohol.

As the catalyst for the isomerization reaction from malate to fumarate, it is preferable to use a complex of an element such as palladium, rhodium, ruthenium, or a supported catalyst in which these elements are supported on a carrier. In particular, when purifying the fumaric acid ester, it is preferable to use these supported catalysts from the viewpoint of removing the catalyst.

The carrier used for such a supported catalyst is not particularly limited, and may be any porous substance generally used as a carrier. Specific examples include silica, alumina, silica-alumina, zeolite, activated carbon, titania, magnesia, and other inorganic compounds.

The amount of the element supported on the carrier is preferably 0.05% by mass to 20% by mass relative to the total amount of the catalyst.
It is more preferably from 10% by mass to 10% by mass. Loading amount is 0.05
When the amount is less than 20% by mass, the reaction time is delayed, and
Exceeding the mass% is not preferable because elements that do not participate in the isomerization reaction increase.

The amount of the supported catalyst thus obtained may be from 0.01% by weight to 5% by weight based on the maleic acid ester.
0 mass% is preferable, and 1 mass%-30 mass% is more preferable. If the amount used is less than 0.01% by mass, the reaction time will be delayed, and if it exceeds 50% by mass, the amount of catalyst which does not participate in the isomerization reaction increases, which is not preferable. Further, as the isomerization catalyst, a single catalyst or two or more catalysts can be used.

The temperature for the isomerization reaction is not particularly limited. Generally, it is 30 ° C to 200 ° C, preferably 60 ° C to 1 ° C.
80 ° C, more preferably in the range of 80 ° C to 160 ° C. If the reaction temperature is lower than 30 ° C., the reaction is slow, and if it exceeds 200 ° C., polymerization may occur during isomerization, which is not preferable.

The isomerization reaction in the present invention can be carried out in a solvent. As the solvent to be used, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, dimethoxyethane, methoxyethyl ether, tetrahydrofuran, ethers such as 1,4-dioxane, ethyl acetate, esters such as butyl acetate, Examples include ketones such as acetone and methyl ethyl ketone, and alcohols such as methanol, ethanol and isopropanol. When these solvents are used, two or more kinds of solvents may be mixed.

This isomerization reaction is carried out under normal pressure or under pressure.
For example, it can be performed at 1 KPa to 1 MPa.

Further, during the transesterification reaction and the isomerization reaction, a polymerization inhibitor may be added to suppress the polymerization.

As the polymerization inhibitor, p-benzoquinone,
Quinones such as naphthoquinone and 2,5-diphenyl-p-benzoquinone; polyhydric phenols such as hydroquinone, pt-butylcatechol and 2,5-di-t-butylhydroquinone; hydroquinone monomethyl ether; di-t- Phenols such as butyl paracresol and α-naphthol are exemplified.

Next, a method for producing a fumaric ester in which R ^{1 in} the general formula (12) of the present invention (I) is represented by the general formula (3) will be described.

The fumaric acid ester of the present invention (I) wherein R ^{1 in} the general formula (12) is represented by the general formula (3) is represented by the general formula (1)
It can be produced by a transesterification reaction of a fumaric acid ester represented by 7) with a polyhydric alcohol. That is, the general formula (1)
The fumaric acid ester represented by the general formula (3) wherein R ^{1 in} 2) is a by-product of the fumaric ester represented by the general formula (17) and a polyhydric alcohol in the presence of a known transesterification catalyst. It can be produced by a method of performing a reaction while removing alcohol.

Specific examples of the transesterification reaction are the same as the above-mentioned transesterification reaction in which R ¹ in the general formula (11) is a method for producing a fumaric acid ester represented by the general formula (3).

In this reaction, the fumaric ester represented by the general formula (17) may remain in the product depending on the charging ratio with the polyhydric alcohol, but can be used without particular removal. .

The fumaric acid ester represented by the general formula (12) in which the fumaric acid ester moiety is a maleic acid ester is once synthesized and subjected to isomerization reaction to give a compound represented by the general formula (12). Can be obtained.

The maleic acid ester used in this isomerization reaction can be mixed with the maleic acid diester corresponding to the fumaric acid ester represented by the general formula (17) in the same manner as in the production method of the fumaric ester represented by the general formula (11). It can be synthesized by transesterification of a polyhydric alcohol.

The isomerization reaction from malate to fumarate is the same as the above-mentioned method for producing the fumarate of the general formula (11).

Next, a method for producing a fumarate in which R ¹ is represented by the general formula (3) in the general formula (15) of the present invention (II) will be described.

In the general formula (15), the fumaric acid ester represented by the general formula (3) wherein R ¹ is represented by the general formula (3) is the same as the fumaric ester represented by the general formula (18). It can be produced by transesterification of alcohol.

Specifically, the fumaric acid ester represented by the general formula (18) is prepared by ^first combining an ethylene glycol allyl ether or propylene glycol allyl ether corresponding to R ¹ —O—X ¹ —OH with an X ³ unit. The corresponding alcohol is synthesized by an addition reaction with an epoxy compound having, for example, ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, etc., followed by an esterification reaction with fumaric acid or a transesterification reaction with a dialkyl fumarate. Can be manufactured.

The polyhydric alcohol having an ether bond represented by the general formula (19) is, for example, ethylene glycol,
It can be produced by an addition reaction between an alcohol such as propylene glycol and an epoxy compound, for example, ethylene oxide, propylene oxide, cyclohexene oxide and styrene oxide.

The above is a description of A) the method of forming the ester, which is the main skeleton of the fumaric acid ester, and the method of forming the repeating unit of the ester.

Next, B) the step of forming a terminal polymerizable group by isomerization will be described.

The fumaric acid ester of the present invention (I) wherein R ^{1 in} the general formula (10) is represented by the general formula (4):
The fumaric acid ester in which R ^{1 in} the general formula (11) is represented by the general formula (4) is a fumaric acid ester in which R ¹ in the general formula (10) is represented by the general formula (3), (11)
The end groups of the fumaric acid ester R ¹ is represented by the general formula (3) can be prepared by the method of isomerization of.

Further, R ^{1 in} the general formula (12) of the present invention (II) is a fumaric ester represented by the general formula (4) and R ^{1 in} the general formula (15) of the present invention (I) is a general formula The fumaric acid ester represented by (4) can also be produced by a method of isomerizing a fumaric acid ester in which each corresponding R ¹ is represented by the general formula (3).

The isomerization reaction will be described below.
The isomerization reaction from the general formula (3) to the general formula (4) can be performed by using a known complex of elements such as palladium, rhodium, ruthenium, or a supported catalyst in which these elements are supported on a carrier. it can.

The carrier used for such a supported catalyst is not particularly limited, and may be any porous substance generally used as a carrier. Specific examples include silica, alumina, silica-alumina, zeolite, activated carbon, titania, magnesia, and other inorganic compounds.

The amount of the element supported on the carrier is preferably 0.05% by mass to 20% by mass, more preferably 2% by mass to 10% by mass, based on the total amount of the catalyst. If the supported amount is less than 0.05% by mass, the reaction time will be delayed, and if it exceeds 20% by mass, elements not involved in the isomerization reaction will increase, which is not preferable.

The amount of the supported catalyst thus obtained can be represented by the following general formulas (10), (11) and (1).
0.01% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on 2) and the fumaric acid ester represented by the general formula (3) of the general formula (15). When the amount of the catalyst is less than 0.01% by mass, the reaction time is delayed, and when the amount exceeds 50% by mass, the amount of the catalyst which does not participate in the isomerization reaction increases, which is not preferable. Further, as the isomerization catalyst, a single catalyst or two or more catalysts can be used.

The reaction temperature of the isomerization reaction is not particularly limited. Generally, it is 30 ° C to 200 ° C, preferably 60 ° C.
C. to 180C, more preferably 80C to 160C. If the reaction temperature is lower than 30 ° C., the reaction is slow,
If the temperature exceeds ℃, polymerization may occur during isomerization, which is not preferable.

The isomerization reaction in the present invention can be performed in a solvent. As the solvent to be used, benzene, toluene, aromatic hydrocarbons such as xylene, diethyl ether, dimethoxyethane, methoxyethyl ether, tetrahydrofuran, ethers such as 1,4-dioxane, ethyl acetate, esters such as butyl acetate, Examples include ketones such as acetone and methyl ethyl ketone, and alcohols such as methanol, ethanol and isopropanol. When these solvents are used, two or more kinds of solvents may be mixed.

The isomerization reaction can be carried out under normal pressure or under pressure, for example, at 1 KPa to 1 MPa.

In order to suppress polymerization during the isomerization reaction, a polymerization inhibitor may be added. Examples of the polymerization inhibitor include quinones such as p-benzoquinone, naphthoquinone and 2,5-diphenyl-p-benzoquinone; and polyhydric phenols such as hydroquinone, pt-butylcatechol and 2,5-di-t-butylhydroquinone. And phenols such as hydroquinone monomethyl ether, di-t-butylparacresol and α-naphthol.

Next, the present invention (IV) will be described. The present invention (IV) is the present invention (I) or the present invention (I
A polymerizable composition containing the fumaric acid ester of I).

The polymerizable composition of the present invention (IV) may contain, if necessary, a compound having a radical polymerizability or a radical polymerization initiator in addition to the fumaric acid ester of the present invention (I) or (II). Can be included.

Examples of the radical polymerizable compound include unsaturated polyesters, oligomers having a (meth) acrylate group, and radical polymerizable monomers.

The unsaturated polyester is obtained by a polycondensation reaction between an α, β-unsaturated polybasic acid or acid anhydride and a saturated polybasic acid or polyhydric alcohol.

Examples of the α, β-unsaturated polybasic acid include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like. Further, as the saturated polybasic acid used in combination as the acid component, succinic acid, adipic acid, saturated aliphatic dicarboxylic acids such as sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid,
Pyromellitic anhydride, aromatic polycarboxylic acids such as 2,6-naphthalenedicarboxylic acid, endic acid anhydride,
Alicyclic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, and 1,4-cyclohexanedicarboxylic acid are exemplified. Polyhydric alcohols include ethylene glycol, diethylene glycol, 1,
2-propanediol or 1,3-propanediol, dipropylene glycol, 1,3-butanediol or 1,4-butanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methyl-1 Aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, 1,6-nonanediol or 1,9-nonanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A Alicyclic diols, such as ethylene oxide of bisphenol A, aromatic diols such as propylene oxide adducts, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and trihydric or higher alcohols such as dipentaerythritol. .

Other unsaturated polyesters include those obtained by transesterification of the above-mentioned saturated polybasic acids and dialkyl esters of unsaturated polybasic acids with polyhydric alcohols. In this case, the alkyl group is usually a methyl group, an ethyl group, a propyl group, a butyl group or the like.

The (meth) acrylate compound used in the present invention is a compound having two or more (meth) acryloyl groups in the structure. Specifically, urethane (meth) acrylate, polyhydric alcohol And polybasic acid or its anhydride and (meth) acrylic acid.

Specifically, a polyester (meth) acrylate, a polyether (meth) acrylate obtained by reacting a polyhydric alcohol obtained by adding ethylene oxide or propylene oxide to a hydroxyl group-containing compound with (meth) acrylic acid, an epoxy compound, Epoxy (meth) acrylate obtained by reacting (meth) acrylic acid or (meth) acrylate having a carboxyl group, and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, glycerin di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Data pentaerythritol tetra (meth) acrylate, polyfunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, silicon having a siloxane group and a (meth) acryloyl group-containing (meth) acrylate.

Further, the urethane (meth) acrylate of the present invention is a known one, and can be obtained by reacting a polyhydric alcohol, a polyisocyanate, and hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate. The polyhydric alcohol is, for example, the same as that described in the polyhydric alcohol of the unsaturated polyester, and as the polyisocyanate, toluene diisocyanate, 4,4′-diphenylmethane isocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone And diisocyanates.

The polybasic acid and polyhydric alcohol used as a raw material of the polyester (meth) acrylate and polyether (meth) acrylate of the present invention are, for example, the same as those described for the unsaturated polyester. No.

The epoxy compound used as a raw material for the epoxy (meth) acrylate of the present invention includes epoxy resin-based glycidyl ethers such as bisphenol A-type, bisphenol S-type and bisphenol F-type bisphenols, and novolak-type glycidyl ethers. Compounds and the like are known.

The radical polymerizable monomer of the present invention has a polymerizable group having a double bond, and specifically includes methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate Monofunctional (meth) acrylates such as 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and isobornyl (meth) acrylate; styrene, α-styrene, methoxystyrene, divinylbenzene, and the like. Aromatic vinyl esters such as aromatic vinyl compounds, vinyl esters of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl stearate and vinyl caproate; vinyl esters of cyclohexane carboxylic acid; Acid vinyl ester, t-butyl benzoate Aromatic vinyl esters such as fragrance vinyl esters, hydroxyethyl vinyl esters, hydroxypropyl vinyl esters, hydroxyalkyl vinyl esters such as hydroxybutyl vinyl esters,
Diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl fumarate,
Diallyl itaconate, diallyl trimellitate, triallyl cyanurate, triallyl isocyanurate, diallyl carbonate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether,
Allyl compounds such as pentaerythritol triallyl ether, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-2-methylphenylmaleimide, N-2-chlorophenylmaleimide, N-2- Maleimides such as methoxyphenylmaleimide, N, N-4,4'-diphenylmethanebismaleimide, maleic acid, fumaric acid,
Unsaturated dibasic acids such as maleic anhydride, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconate, diethyl itaconate and the like, and also represented by formula (17) or (18) And a fumarate represented by the formula:

When the polymerizable composition of the present invention (IV) is used in combination with a fumaric acid ester represented by the general formula (17) or (18), it is hardly affected by oxygen inhibition at the time of curing, and Good properties are obtained. Further, these radically polymerizable monomers can be used alone or in combination of two or more.

The amount of the fumaric acid ester of the present invention (I) or (II) used in the polymerizable composition of the present invention (IV) is 1% by mass to 99% by mass, preferably It is 5% by mass to 80% by mass. In particular, when the content is 5% by mass or more, the effect of oxygen inhibition during curing is small, and the surface is not sticky.

The radical polymerization initiator that can be used in the polymerizable composition of the present invention (IV) includes, for example, any radical polymerization initiator that generates radicals by heat, ultraviolet rays, electron beams or radiation. Use is also possible.

Examples of the radical polymerization initiator that can be used for the radical polymerization by heat include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobisisovaleronitrile, methyl ethyl ketone peroxide, methyl Ketone peroxides such as isobutyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as benzoyl peroxide, decanoyl peroxide and lauroyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t
Dialkyl peroxides such as -butyl peroxide,
1,1-bis (t-hexylperoxy) 3,3,5
Peroxyketals such as -trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane, t-butylperoxypivalate, t-butylperoxy -2-
Ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-
Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, t-butylperoxy 2-ethylhexanoate Alkyl peroxy esters such as t-hexyl peroxy 2-ethylhexanoate, and percarbonates such as diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate, and t-butyl peroxy isopropyl carbonate. No.

Further, in film formation such as coating by heat, it is also possible to carry out self-crosslinking without using a radical polymerization initiator.

Examples of the radical polymerization initiator which can be used for polymerization by ultraviolet rays and electron beams include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenyl ketone, and 2-methyl -1- [4-
(Methylthio) phenyl] -2-monforinopropanone-1,2-benzyl-2-dimethylamino-1- (4
Acetophenone derivatives such as -morpholinophenyl) -butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 4,4 ′
Benzophenone derivatives such as -bis (dimethylamino) benzophenone, 4-trimethylsilylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, benzoin, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether;
Benzoin derivatives such as benzoin isopropyl ether; methylphenylglyoxylate; benzoin dimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide;

The amount of these polymerization initiators used is from 0.01% by mass to 15% by mass, preferably from 0.1% by mass to 10% by mass, based on the weight of the polymerizable composition of the present invention (IV).
Range.

When polymerizing the polymerizable composition of the present invention, various components can be added depending on the purpose of use. For example, an ultraviolet absorber, an antioxidant, a coloring agent, a lubricant, an antistatic agent, an inorganic filler such as silica, alumina, and aluminum hydroxide may be used in combination.

The polymerizable composition of the present invention (IV) can be cured by a coating method such as a roll coater or a spin coater, a casting method, a stereolithography method or the like using ultraviolet rays, an electron beam or heat. Can be.

Further, the polymerizable composition of the present invention may use a solvent if it is necessary to lower the viscosity by a curing method. Examples of the solvent to be used include aromatic hydrocarbons such as toluene and xylene, acetates such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and tetrahydrofuran. And ethers such as dioxane, and alcohols such as ethyl alcohol, (iso) propyl alcohol, and butyl alcohol.

Finally, the present invention (V) will be described. The present invention (V) is a cured product obtained by curing the polymerizable composition of the present invention (IV).

The cured product of the present invention (V) is, for example, a coating material such as woodwork coating, film coating, metal coating, plastic coating, inorganic coating, hard coating, optical fiber coating, gel coating agent, paint such as paint or printing ink. It can be widely used in the field of curable resins, such as materials, optical molding materials, optical materials such as optical disks, eyeglass lenses, and prisms, adhesives, photoresists, sealants, and molding materials. In particular, it is useful for a thin film coating material which is easily affected by oxygen. The substrate to be coated is not particularly limited. Specifically, for example, metal, glass, plastic and the like can be mentioned.

Further, the resin obtained by curing the polymerizable composition of the present invention can obtain a cured product having a high crosslinking density and a high surface hardness. In particular, a cured resin of a fumarate ester having a skeleton of a trivalent to hexavalent polyhydric alcohol represented by the general formula (10) has a high surface hardness and a pencil hardness (JIS K-54).
00) is 4H to 8H, which is optimal for a field requiring abrasion resistance and scratch resistance.

[0200]

The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to the embodiments without departing from the gist of the present invention.

The following instruments were used for measurement of various data. (Equipment used) ¹ H-NMR use model: JEOL EX-400 (400 MHz) Dissolved in deuterated chloroform, measured using tetramethylsilane as an internal standard substance, and calculated chemical shift. FT-IR model used: PerkinElmer Spectrum
The measurement was performed by a liquid film method using a GX KBr plate.

GPC use model: Pump ShodexDS-4 UV detector Waters484RI detector ShodexRI
SE-61 Column used: Shodex KG + K-801 (K-802 was added in Example 1) Measurement conditions: eluent chloroform Flow rate 1 ml / min.
Column temperature 40 ° C detection UV254nm GC (monomer analysis) Model used: GC-14B (manufactured by Shimadzu Corporation) Column used: DB-23 0.25μ × 30m (J & W
Carrier gas: nitrogen 1 ml / min. Split ratio: 1:50 Septum purge: 10 ml / min. Detector: FID Injection temperature: 230 ° C Detector temperature: 230 ° C Temperature program 40 ° C (10 min.) → (10 ° C / m
. in) → 200 ℃ UV irradiation apparatus Apparatus used: Tosukyua 401 (manufactured by Toshiba Corporation) Light source: mercury lamp irradiation intensity: irradiation distance 100mm-70mW / cm ² Melting Point Apparatus used: MP-500D (manufactured by Yanaco Co.) Refractive rate Apparatus used: (manufactured by Atago Co.) Abbe refractometer 1T refractive index using the above model the (n _D) was measured. As the contact liquid, α-bromonaphthalene was used. Measurement temperature:
25 ° C

Example 1 A 1-liter flask equipped with a distillation apparatus was charged with 312 g of bis (2-allyloxyethyl) malate, 135 g of a 2-mol ethylene oxide adduct of bisphenol A, 0.4 g of dibutyltin oxide, and a polymerization inhibitor. Certain tetrakis [methylene-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] methane (trade name: IRGANOX1010, manufactured by Ciba Specialty Chemicals)
The reaction system was heated to 160 ° C. while gradually reducing the pressure in the reaction system to distill off by-produced ethylene glycol monoallyl ether. Finally, the pressure was reduced to about 400 Pa, and almost the theoretical amount of ethylene glycol monoallyl ether was distilled off.

After cooling the reaction solution to room temperature, 385 g of
I took things out. Of the resulting product ¹H-NMR and
Measure IR and determine bis (2-allyloxyethyl) male
And bisphenol A ethylene oxide 2 mol adduct
It was confirmed to be a condensate of

According to GC analysis, the product was bis (2-
Allyloxyethyl) malate was contained at 30.3%.

¹ H-NMR δ (ppm) 7.13 to 7.11 (m, Ph),
6.81~6.78 (m, Ph), 6.29 (s, -OCOC H = C H COO-), 5.95~
_{5.84 (m, CH 2 = C} H -CH 2 -), 5.31~5.25 (m, C H 2 = CH-CH
_{2 -), 5.21~5.17 (m,} C H 2 = CH-CH 2 -), 4.52~3.64 (m, -O
-CH ₂ -C H ₂ -COO-, CH ₂ = CH-C H _2- , -OC H ₂ -CH ₂ -COO-, Ph-O-
C H ₂ -C H ₂ -OCO-C = C-), 1.63 (s, Ph-C ( Me ) ₂ -Ph), 1.62 (Ph-
C ( Me ) ₂ -Ph). IRν (CO) ＝ 1733cm ^-1 , ν (allyl C = C, maleate C =
C) = 1647cm ^-1

62.4 g of the obtained mixture was mixed with toluene 6
0 ml, 60 ml of 1-propanol 6.2 g of Ru-C having a carrying amount of 5% by mass was charged and replaced with nitrogen.
The temperature rose. Then, the mixture was heated and stirred at the same temperature for 10 hours. After cooling, the catalyst was filtered off from the reaction solution, and the solvent was distilled off from the filtrate under reduced pressure to obtain 59.2 g of a yellow liquid having a high viscosity. When analyzed by NMR, the isomerization rate from the double bond of maleic acid residue (δ = 6.29 ppm) to the double bond of fumaric acid residue (δ = 6.93 to 6.86 ppm) was determined. 100%.

Table 1 shows the area percentage in the chart of the results of analysis by GPC of the obtained product as the degree of condensation n (the number of repeating units) of the product.

[0209]

[Table 1]

Example 2 A 3 L glass flask was charged with 500 g of maleic anhydride, 573 g of ethene glycol monoallyl ether, and 0.0 of hydroquinone monomethyl ether.
5 g was charged and heated and stirred at 50 ° C. for 24 hours under a nitrogen atmosphere. 1 kg of 1,4-dioxane, 10 g of concentrated hydrochloric acid, 0.1 g of hydroquinone monomethyl ether were added to the obtained reaction product.
Was added and heated and stirred at 100 ° C. for 1 hour. Then 1,4
-Dioxane was distilled off under reduced pressure, and
g and 1 kg of water were added and the mixture was separated. When toluene was distilled off from the organic layer under reduced pressure, 1020 g of a pale yellow liquid was obtained.
Analysis by NMR and FT-IR confirmed that the product was mono (2-allyloxyethyl) fumarate.

¹ H-NMR δ (ppm) 10.44 (br.s, 1H, -COO H ), 7.30 to 6.83 (m, 2
H, -OCOC H = C H COO-), 5.92 to 5.88 (m, 1H, CH ₂ = C H -CH
_2- ), 5.32 to 5.21 (m, 2H, C H ₂ = CH-CH _2- ), 4.37 (br.s, 2
H, -O-CH ₂ -C H ₂ -COO-), 4.07 (br.s, 2H, CH ₂ = CH-C H _2- ),
3.73 (br.s, 2H, -OC H ₂ -CH ₂ -COO-). IRν (OH) = 3300 ~ 2500cm ^-1 , ν (CO) = 1727cm ^-1 , ν
(allyl C = C) = 1647cm ^-1

Example 3 154 g of mono (2-allyloxyethyl fumarate) obtained in Example 2 and pentaerythritol 21 were placed in a 500 mL glass flask equipped with a stirrer, a thermometer, a condenser, and a water content receiver. .
8 g, 200 mL of benzene, and 0.25 g of p-toluenesulfonic acid were charged. The mixture was heated and stirred in an oil bath, the reaction temperature was raised to 80 ° C., and the reaction was continued while distilling off water produced as the reaction proceeded. When the amount of distilled water reached the theoretical amount, the reaction was completed and the system was cooled. The reaction solution was transferred to a separatory funnel, and 300 mL of benzene was added to add 10 mL of benzene.
% Aqueous sodium carbonate solution and water. Thereafter, the mixture was concentrated under reduced pressure to obtain 120 g of a product.

The product was analyzed by ¹ H-NMR, FT-IR,
GC and GPC were measured, and a condensate of pentaerythritol and mono (2-allyloxyethyl) fumarate and a bis (2-allyloxyethyl) fumarate monomer 43 were obtained.
% (GC measurement). IRν (CO) = 1727cm ⁻¹ , ν (allyl C = C) = 1647cm ⁻¹

Example 4 152 g of mono (2-allyloxyethyl fumarate) obtained in Example 2 and trimethylolpropane were placed in a 500 mL glass flask equipped with a stirrer, a thermometer, a condenser, and a water content receiver. 2
1.5 g, 200 mL of benzene, and 0.25 g of p-toluenesulfonic acid were charged. The mixture was heated and stirred in an oil bath, the reaction temperature was raised to 80 ° C., and the reaction was continued while distilling off water produced as the reaction proceeded. When the amount of distilled water reached the theoretical amount, the reaction was completed and the system was cooled. The reaction solution was transferred to a separatory funnel, and 300 mL of benzene was added to add 10 mL of benzene.
% Aqueous sodium carbonate solution and water. Thereafter, the mixture was concentrated under reduced pressure to obtain 118 g of a product.

The product was analyzed by ¹ H-NMR, FT-IR,
GC and GPC were measured, and a condensate of trimethylolpropane and mono-2-allyloxyethyl fumarate and bis (2-allyloxyethyl) fumarate monomer 30
% (GC measurement). IRν (CO) = 1727cm ⁻¹ , ν (allyl C = C) = 1647cm ⁻¹

Example 5 A 3 L glass flask was charged with 500.7 g of mono (2-allyloxyethyl) fumarate obtained in Example 2 and 1.8 kg of THF, and the inside of the reaction system was replaced with nitrogen. 345.5 g were added. After the generation of heat was completed, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. On the other hand, p-toluenesulfonyl chloride 52
A THF solution prepared by dissolving 4.3 g in 200 g of THF is prepared. When the temperature of the reaction solution became 10 ° C. or less, the adjusted p-toluenesulfonyl chloride / THF solution was added, and the mixture was stirred for 30 minutes. Then pentaerythritol 7
0.9 g and potassium carbonate 691.1 g were added and stirred.
At the end of the heat generation, ice water was removed, and the reaction solution was returned to room temperature and further stirred for 2 hours.

Next, the reaction solution was concentrated, and the concentrated solution was transferred to a separatory funnel. Ethyl acetate (2 kg) was added, and the mixture was washed with a 10% aqueous sodium carbonate solution and water. Thereafter, the mixture was concentrated under reduced pressure to obtain 240 g of a product. ¹ H-N of this product
By measuring MR, FT-IR and GPC, the general formula (21)
Pentaerythritol and fumaric acid mono (2-
(Allyloxyethyl). IRν (CO) = 1727cm ⁻¹ , ν (allyl C = C) = 1647cm ⁻¹

General formula (21)

Embedded image

Table 2 shows the area percentage of the chart of the result of analysis of the obtained product by GPC as the value of s in the formula (21).

[0220]

[Table 2]

The above mixture was subjected to silica-supported thin layer chromatography (Pre Coated PLC Plates SILICA G, manufactured by MERCK).
Ethyl acetate / hexane = 1/2 using EL 60 F-254)
By using as a developing solvent, the value of s is 4 and 3
Was isolated, and the NMR was measured to confirm that it was the above mixture.

[0222] ^{s = 4 1 H-NMRδ (} ppm) 6.92 (d, 4H, J = 15.6Hz, -OCOC H
= C H COO-), 6.85 (d, 4H, J = 15.6Hz, -OCOC H = C H COO-),
5.96 to 5.86 (m, 4H, CH ₂ = C H -CH _2- ), 5.30 (dd, 4H, J =
17.3Hz, J = 1.47Hz, C H ₂ = CH-CH _2- ), 5.22 (dd, 4H, J =
10.5Hz, J = 1.47Hz, C H ₂ = CH-CH _2- ), 4.38 (t, 8H, J =
4.6Hz, -O-CH ₂ -C H ₂ -COO-), 4.34 (s, 8H, CC H _2- ), 4.
04 (d, 8H, J = 5.4Hz, CH ₂ = CH-C H _2- ), 3.70 (t, 8H, J
= 4.6Hz, -OC H ₂ -CH ₂ -COO-). IRν (CO) = 1727cm ^-1 , ν (allyl C = C) = 1647cm ^-1

S = 3 ¹ H-NMR δ (ppm) 6.92 (d, 3H, J = 13.9 Hz, -OCOC H
= C H COO-), 6.87 (d, 3H, J = 13.9Hz, -OCOC H = C H COO-),
5.96 to 5.86 (m, 3H, CH ₂ = C H -CH _2- ), 5.30 (d, 3H, J = 1
7.1Hz, C H ₂ = CH-CH _2- ), 5.22 (d, 3H, J = 10.3Hz, C H ₂ = C
H-CH _2- ), 4.38 (t, 6H, J = 4.6Hz, -O-CH ₂ -C H ₂ -COO-),
4.31 (s, 6H, CC H 2 -), 4.04 (d, 6H, J = 5.9Hz, CH 2 = C
HC H _2- ), 3.70 (t, 6H, J = 4.6Hz, -OC H ₂ -CH ₂ -COO-),
3.63 (s, 2H, CC H _2- ). IRν (CO) = 1727cm ^-1 , ν (allyl C = C) = 1647cm ^-1

Example 6 A 3 L glass flask was charged with 500.2 g of mono (2-allyloxyethyl) fumarate obtained in Example 2 and 1.8 kg of THF, and the inside of the reaction system was replaced with nitrogen. 345.1 g were added. After the generation of heat was completed, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. On the other hand, p-toluenesulfonyl chloride 52
A THF solution prepared by dissolving 4.3 g in 200 g of THF is prepared. When the temperature of the reaction solution became 10 ° C. or less, the adjusted p-toluenesulfonyl chloride / THF solution was added, and the mixture was stirred for 30 minutes. Thereafter, 93.2 g of trimethylolpropane and 691.0 g of potassium carbonate were added and stirred. At the end of the heat generation, ice water was removed, and the reaction solution was returned to room temperature and further stirred for 2 hours.

Next, the reaction solution was concentrated, and the concentrated solution was transferred to a separatory funnel. Ethyl acetate (2 kg) was added, and the mixture was washed with a 10% aqueous sodium carbonate solution and water. Thereafter, the mixture was concentrated under reduced pressure to obtain 267 g of a product. ¹ H-N of the product
By measuring MR, FT-IR and GPC, the general formula (22)
Trimethylolpropane and fumaric acid mono (2
-Allyloxyethyl).

IRν (CO) = 1727 cm ⁻¹ , ν (allyl C = C)
= 1647cm ^-1

Formula (22)

[Of 60]

Table 3 shows the area percentage of the chart of the result of analysis of the obtained product by GPC as the value of s in the general formula (22).

[0229]

[Table 3]

Example 7 In a 1 L round bottom flask equipped with a stirrer, a magnetic stirrer, a Dimroth condenser, and a nitrogen inlet tube, 118.19 g of cyclohexanediol monoallyl ether, 148.71 g of maleic anhydride, and hydroquinone monomethyl ether 268 mg, toluene 3
63 g was added, and the mixture was heated and stirred at 110 ° C. for 24 hours under a nitrogen atmosphere. 12.6 g of concentrated hydrochloric acid and 267 mg of hydroquinone monomethyl ether were added to the obtained reaction product, and the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After cooling, the precipitated white precipitate was separated by filtration through a 0.1 μm membrane filter, and the filtrate was separated with water (500 mL × 3 times). The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using an evaporator to obtain 162.49 g of a pale yellow viscous liquid. ¹ H-NMR and FT-IR analysis of this product confirmed that it was mono (2-allyloxycyclohexyl) fumarate. IRν (COOH) = 3300cm ^-1 ~ 2500cm ^-1 , ν (CO) = 1723cm
^-1 , ν (allyl C = C) = 1646cm ^-1

Example 8 161.53 g of mono (2-allyloxycyclohexyl) fumarate obtained in Example 7 and cyclohexane were placed in a 1 L glass flask equipped with a stirrer, a thermometer, a condenser, and a water content receiver. 103.37 g of diol monoallyl ether, toluene 2
62.37 g, p-toluenesulfonic acid 8.6 g, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane as a polymerization inhibitor (manufactured by Ciba Specialty Chemicals) 520 mg (trade name: IRGANOX1010).
The mixture was heated and refluxed in an oil bath, and the reaction was continued while distilling off water produced as the reaction progressed. When the amount of distilled water reached the theoretical amount, the reaction was completed and the system was cooled. The reaction solution was transferred to a separatory funnel, and 300 g of toluene was added thereto.
Liquid separation was performed using an aqueous sodium hydroxide solution and water. Thereafter, the product was dried over sodium sulfate and concentrated under reduced pressure to obtain product 23.
0.28 g was obtained. Column purification of the obtained crude product was performed. Silica gel (WAKO- manufactured by Wako Pure Chemical Industries, Ltd.)
(GEL C-200) 130 g was slurried with hexane and packed in a column chromatography tube having a diameter of 5 cm. 20.2 g of the crude product obtained above was placed on the upper part of the column chromatography tube, and the crude product was eluted with ethyl acetate / hexane = 1/10, and TLC (Pre-coated by MERCK) was used.
TLC Plates SILICA GEL 60
F-254), fractions having an Rf value of 0.52 were collected, and concentrated under reduced pressure by an evaporator to give 15.1 g of a pale yellow oil. Of this product
¹ H-NMR, FT-IR and GPC were measured to confirm that the product was bis (2-allyloxycyclohexyl) fumarate. IRν (CO) = 1721cm ⁻¹ , ν (allyl C = C) = 1647cm ⁻¹

(Example 9 ) 53.9 g of mono (2-allyloxycyclohexyl) fumarate obtained in Example 7 was placed in a 500 mL glass flask equipped with a stirrer, a thermometer, a condenser, and a water content receiver. 6.0 g of erythritol, 50 mL of toluene, 811.8 mg of p-toluenesulfonic acid, and 54.6 mg of hydroquinone monomethyl ether were charged. The mixture was heated and refluxed in an oil bath, and the reaction was continued while distilling off water produced as the reaction progressed. When the amount of distilled water reached the theoretical amount, the reaction was completed and the system was cooled. The reaction solution was transferred to a separatory funnel, 300 mL of ethyl acetate was added, and the mixture was separated with a 10% aqueous sodium carbonate solution and water. Then, it was dried over sodium sulfate and concentrated under reduced pressure to obtain 38.9 g of a product.

The product was analyzed by ¹ H-NMR, FT-IR,
A composition containing a condensate of pentaerythritol and mono (2-allyloxycyclohexyl) fumarate and 40% of bis (2-allyloxycyclohexyl) fumarate monomer (GC measurement) by measuring GC and GPC. It was confirmed.

IRν (CO) = 1723 cm ⁻¹ , ν (allyl C = C)
= 1645cm ^-1

(Example 10) In a 3 L glass flask equipped with a stirrer, the mono (2-fumarate) obtained in Example 7 was added.
60.8 g of allyloxycyclohexyl), THF20
After 0 mL was charged and the inside of the reaction system was replaced with nitrogen, 22 g of potassium carbonate was added. After the generation of heat was completed, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. When the temperature of the reaction solution became 10 ° C. or lower, p-toluenesulfonyl chloride 7.6 was used.
g was added and stirred for 30 minutes. Thereafter, 5.4 g of pentaerythritol was added and stirred. The reaction solution was returned to room temperature and stirred for 12 hours. Next, the reaction solution was concentrated, and the concentrated solution was transferred to a separating funnel. Ethyl acetate (500 mL) was added, and the solution was separated and washed with a 10% aqueous sodium carbonate solution and water. afterwards,
The mixture was concentrated under reduced pressure to obtain 30 g of a product. ¹ of the product H-
NMR, FT-IR and GPC were measured and the general formula (2
It was confirmed to be a condensate of pentaerythritol represented by 3) and mono (2-allyloxycyclohexyl) fumarate.

IRν (CO) = 1723 cm ⁻¹ , ν (allyl C = C)
= 1645cm ^-1

Formula (23)

Embedded image

Table 4 shows the area percentage of the chart of the result of analysis of the obtained product by GPC as the value of s in the general formula (23).

[0239]

[Table 4]

Example 11 In a 3 L glass flask equipped with a dropping funnel, 1400 g of allyl alcohol and alumina (manufactured by Alumina N Super I ICN) were added.
351.6 g, 500 g of styrene oxide in dropping funnel
And heated to 50 ° C. under a nitrogen atmosphere and added dropwise. After completion of the dropwise addition, the mixture was heated and stirred for 10 hours. After cooling, alumina was removed with a 0.1 μm membrane filter, and excess allyl alcohol was removed from the reaction solution by an evaporator under reduced pressure. The obtained concentrate was distilled under reduced pressure, and 592 g of a mixture of 2-allyloxy-1-phenylethanol and 2-allyloxy-2-phenylethanol was obtained.
(80% yield) was obtained. IR ν (OH) = 3443 cm ⁻¹ , ν (Ph, CH) = 3050 cm ^{−1 to} 3030 cm ⁻¹ ,
ν (allyl C = C) = 1647cm ^-1 bp = 136 ℃ (13Torr)

(Example 12) 322.9 g of 2-allyloxy-phenylethanol obtained in Example 11 and 354.9 g of maleic anhydride were placed in a 2 L round bottom flask equipped with an induction stirrer, a Dimroth condenser, and a nitrogen inlet. , Hydroquinone monomethyl ether, 1.36 g, toluene 677.
5 g was charged and heated and stirred for 5 hours at an oil bath temperature of 130 ° C. under a nitrogen atmosphere. After cooling, 80 g of concentrated hydrochloric acid was charged and heated and stirred at 130 ° C. in an oil bath temperature for 10 hours in a nitrogen atmosphere. After cooling, the precipitated fumaric acid was separated by filtration, the filtrate was separated with water, dried over anhydrous sodium sulfate, and toluene was removed under reduced pressure using an evaporator. The obtained reaction solution was poured into hexane, and the precipitated white solid was filtered off and dried under reduced pressure. As a white solid, 375.8 g of mono (2-allyloxy-phenyl-ethyl) fumarate was obtained (yield: 75.50 g). 1
%) Obtained. Here, it was used for the next step without further purification. IR ν (COOH) = 3400 cm ^{−1 to} 2560 cm ⁻¹ , ν (CO) = 1723 cm ⁻¹ ,
ν (allyl C = C) = 1645cm ^-1 mp 71.2-71.4 ℃

(Example 13) In a 500 mL glass flask equipped with a stirrer, a thermometer, a condenser, and a water content receiver, the mono (2-fumarate) obtained in Example 12 was added.
Allyloxy-phenylethyl) 138.14 g, 2-
89.125 g of allyloxy-phenylethanol, 150 mL of benzene, 2.76 of p-toluenesulfonic acid
g, 138 mg of hydroquinone monomethyl ether as a polymerization inhibitor was charged. The mixture was heated and refluxed in an oil bath, and the reaction was continued while distilling off water produced as the reaction progressed. When the amount of distilled water reached the theoretical amount, the reaction was completed and the system was cooled. The reaction solution was transferred to a separatory funnel, 300 mL of benzene was added, and a 1% aqueous sodium hydroxide solution was added.
Separation with water was performed. Then, it dried with sodium sulfate and concentrated under reduced pressure to obtain 200 g of a crude product. By recrystallizing the obtained crude product from hot hexane, a white solid was obtained. ¹ H-NMR, FT-IR,
And GPC was measured and it was confirmed that it was bis (2-allyloxy-phenylethyl) fumarate. IR ν (Ph, CH) = 3050 cm ^{-1 to} 3030 cm ^-1 , ν (C = O) = 1725 cm ^-1 ν (allyl C = C) = 1647 cm ^-1 mp = 68.3 to 68.5 ° C

(Example 14) The mono (2-allyloxy-fumarate) obtained in Example 12 was placed in a 1-L glass flask.
(Phenylethyl) 75.7 g and THF 355.6 g were charged, and the inside of the reaction system was replaced with nitrogen, and then 38 g of potassium carbonate was added. After the generation of heat was completed, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. On the other hand, p-toluenesulfonyl chloride 5
A THF solution prepared by dissolving 1.5 g in 89 g of THF is prepared. When the temperature of the reaction solution became 10 ° C. or less, the adjusted p-toluenesulfonyl chloride / THF solution was added, and the mixture was stirred for 30 minutes. Then pentaerythritol7.
5 g and potassium carbonate 82.2 g were added and stirred. At the end of the heat generation, ice water was removed, and the reaction solution was returned to room temperature and further stirred for 5 hours. Next, the reaction solution was concentrated, the concentrated solution was transferred to a separating funnel, 1 kg of ethyl acetate was added, and the solution was separated and washed with a 10% aqueous sodium carbonate solution and water. Thereafter, the organic layer was concentrated under reduced pressure to obtain 32.5 g of a product. Column purification of the obtained crude product was performed. Silica gel (WAKO-GEL C-20 manufactured by Wako Pure Chemical Industries, Ltd.)
0) 1 kg was slurried with hexane and 10 cm in diameter
Was packed in a column chromatography tube. The crude product obtained above is placed on the top of the column chromatography tube, and ethyl acetate / hexane =
The crude product was eluted while applying a gradient from 1/20 to 1/5, and TLC (Pre-co manufactured by MERCK) was eluted.
atted TLC Plates SILICAGEL
60F-254) and a fraction having an Rf value of 0.50 (developing solution: ethyl acetate / hexane = 1/2) was collected and concentrated under reduced pressure by an evaporator to obtain 10.1 g of a pale yellow oil. . ¹ of the product H-
NMR, FT-IR and GPC were measured, and it was confirmed that S = 4 in a condensate of pentaerythritol and mono (2-allyloxy-phenyl-ethyl) fumarate. IR ν (Ph, CH) = 3080 cm ^{-1 to} 3030 cm ^-1 , ν (C = O) = 1725 cm ^-1 ν (allyl C = C) = 1647 cm ^-1

General formula (25)

Embedded image (Example 45) In a 300 mL glass flask equipped with a cooling tube, 20.0 g of fumaric acid and cyclohexene oxide 3 were added.
7.22 g, 1,4-dioxane 60.8 g, alumina (ICN Pharmaceuticals Inc. Al
After charging 3.7 g of Umina N-SuperI) and replacing the inside of the reaction system with nitrogen, the mixture was heated and stirred at an internal temperature of 60 ° C. for 13.5 hours. The obtained reaction solution was filtered with a membrane filter, and the filtrate was distilled off under reduced pressure to obtain 40.7 g of a transparent oily liquid. Next, in a 100 mL glass flask equipped with a stirrer, a thermometer, a condenser, and a water content receiver, 10.3 g of the transparent oily liquid obtained above and the mono (2-allyloxycyclohexyl fumarate) obtained in Example 7 were added. ) 17. g, 26.7 g of toluene, 338.2 mg of p-toluenesulfonic acid, and 10 mg of hydroquinone monomethyl ether as a polymerization inhibitor. The mixture was heated under reflux in an oil bath, and the reaction was continued while distilling off water produced as the reaction progressed. When the amount of distilled water reached the theoretical amount, the reaction was completed and the system was cooled. From this reaction solution, toluene was distilled off under reduced pressure, and a small amount of ethyl acetate was added to the obtained yellow viscous liquid, and then the mixture was reprecipitated in hexane. The obtained white viscous solid was washed with water and further washed with hexane to obtain 15 g of a white solid. ¹ H-NMR, FT-IR, and GP of the obtained white solid
C was measured, and it was confirmed that it was a polycondensate of 1,2-cyclohexanediol, fumaric acid, and allyl alcohol. IR ν (C = O) = 1722 cm ⁻¹ , ν (allyl C = C) = 1647 cm ⁻¹ (Examples 15 to 20) The mixture 50 obtained in Example 3
g, toluene 50 g, hydroquinone monomethyl ether (MEHQ) 10 mg. After adding 15 g of 5% Pd-Al ₂ O _{3 and} purging the inside of the reaction system, the mixture was heated and stirred at 140 ° C. for 3 hours. The 5% Pd-Al ₂ O ₃ than After cooling, the reaction solution was removed by filtration and toluene was distilled off under reduced pressure from the filtrate, the light yellow viscous liquid was obtained 48 g. By measuring ¹ H-NMR and comparing peaks of an allyl group and a propenyl group, it was confirmed that 98% was isomerized to a propenyl group.

By performing the same operation, Example 4,
The mixtures obtained in Example 5, Example 6, Example 7, and Example 8 were also subjected to an isomerization reaction. Table 5 summarizes the results.

[0246]

[Table 5]

(Example 21) 34 g of the crude product obtained in Example 14, 90 g of toluene, 10 mg of hydroquinone monomethyl ether (MEHQ), carbonyl chlorohydrido tris (triphenylphosphine) ruthenium (I)
I) After adding 3.13 g and purging the reaction system with nitrogen, 14
The mixture was heated and stirred at 0 ° C. for 30 minutes. After cooling, toluene was distilled off under reduced pressure from the reaction solution to obtain 33 g of a pale yellow viscous liquid.
Obtained. By measuring ¹ H-NMR and comparing peaks of an allyl group and a propenyl group, it was confirmed that 98% was isomerized to a propenyl group.

(Examples 22 to 35) The fumaric acid ester of the present invention obtained in the above Examples was applied on a glass substrate and subjected to UV curing or thermal curing to examine the surface hardness of the cured film. In addition, the surface hardness conformed to the pencil scratch test of JISK5400.

The results are shown in Table 6.

[0250]

[Table 6]

(Comparative Example 1) A 1 L flask equipped with a distillation apparatus was charged with 144 g of dimethyl fumarate, 245 g of ethylene glycol monoallyl ether, and 0.2 g of dibutyltin oxide, and heated to 140 ° C under nitrogen.
Methanol by-produced was distilled off. When the amount of methanol reached 70% of the theoretical amount, the pressure inside the reaction system was gradually reduced,
The evaporation of methanol was accelerated, and finally the pressure was reduced to about 400 Pa to completely evaporate the theoretical amount of methanol and the remaining ethylene glycol monoallyl ether. After cooling the reaction solution to room temperature, 283 g of the product was taken out. By measuring ¹ H-NMR and FT-IR of the obtained product,
It was confirmed to be bis (2-allyloxyethyl) fumarate.

This was applied on a glass substrate and subjected to UV curing, and the surface hardness of the cured film was examined. The surface hardness is JI
It conformed to the SK5400 pencil scratch test. Table 6 shows the results
Shown in

(Comparative Example 2) A 1 L flask equipped with a distillation apparatus was charged with 144 g of dimethyl fumarate, 279 g of hydroxybutyl vinyl ether, 0.2 g of zinc acetate, and 0.3 g of IRGANOX1010 as a polymerization inhibitor.
The mixture was heated to 140 ° C., and methanol as a by-product was distilled off. When the amount of methanol reached 70% of the theoretical amount, the pressure inside the reaction system was gradually reduced to accelerate the distillation of methanol.
Finally, the pressure was reduced to about 400 Pa, and the theoretical amount of methanol and the remaining hydroxybutyl vinyl ether were completely distilled off. After cooling the reaction solution to room temperature, 297 g of bis (4-vinyloxybutyl) fumarate was obtained.

This was applied on a glass substrate and thermally cured, and the surface hardness of the cured film was examined. The surface hardness is JIS
It conformed to the pencil scratch test of K5400. Table 6 shows the results.

(Examples 36 to 42 and 46) (Comparative Example 3,
4) The composition of the fumaric acid ester of the present invention was applied on a PET film or a glass substrate, and was subjected to UV curing or thermal curing, and the surface hardness of the cured film was examined. In addition, a tack-free product having no stickiness on the cured surface was evaluated as “good”, and a product having stickiness was evaluated as “x”.

Curing was performed under the following conditions. i) Thermal curing temperature 150 ° C.-1 hour ii) UV curing initiator: Irgacure 184 5% Irradiation amount: 300 mj / cm ^{2 The} results are shown in Table 7.

[0257]

[Table 7]

Example 43 The screw (2 ) described in Example 13
(Allyloxy-phenylethyl) fumarate at 80 ° C.
Then, 2% by mass of 1.1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane was added to bis (2-allyloxy-phenylethyl) fumarate as an initiator, C. (1 hour) and then 130 ° C. (1 hour). When the refractive index of the obtained cured product was measured, it was n ^D = 1.5573.

Example 44 To the condensate of pentaerythritol and mono (2-allyloxy-phenylethyl) fumarate described in Example 14, 1-tert-hexylperoxy-2-ethylhexanoate was used as an initiator. mass%
Compounded and cast cured at 80 ° C. (1 hour) and then at 120 ° C. (1 hour). When the refractive index of the obtained cured product was measured, it was n ^D = 1.5520.

(Comparative Example 5) The bis (2-allyloxyethyl) fumarate of Comparative Example 1 was used as an initiator in an amount of 1.1
-Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexyl was blended in an amount of 2% by mass and cast and cured.
When the refractive index of the obtained cured product was measured, n ^D = 1.
5132.

[0261]

As described above, since the fumaric acid ester of the present invention has a terminal alkenyloxy group having a higher copolymerizability with a fumarate group than the conventional one, the degree of cross-linking is increased. A cured product having excellent surface hardness can be provided. Also, a composition with another polymerizable compound can be used for the purpose of improving curability and surface hardness. Further, the fumaric acid ester containing an aromatic group has a high refractive index of 1.55 or more, and can be expected to be applied to applications requiring a high refractive index.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasushi Kadowaki Oita City, Oita City, Nakanoshima 2 Showa Denko Co., Ltd. Oita Production and Technology Management Department (72) Inventor Hiroshi Uchida Oita City, Oita City Oita City Nakanoshima 2 Showa F-term (reference) in Oita Production & Engineering Division, Denko Corporation 4J029 AA07 AB02 AE11 AE13 AE16 BA02 BA03 BA05 BA08 BA09 BA10 BB01 BC01 BD03A BD04A BD05A BD07A FC02 FC03 FC04 FC05 FC08 FC29 GA14 HA01 HA02 JF551 JF581

Claims (32)

[Claims] 1. A fumaric acid ester having a group represented by the general formula (1) as at least one terminal group and a group represented by the general formula (2) as a repeating unit. General formula (1) General formula (2) (In the general formula (1), R ¹ each independently represents the general formula (3) or the general formula (4). In the general formula (1) or the general formula (2), X ¹ and X ² each represent Independently 2
Represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms having 1 to 6 hydroxyl groups. Where X
¹ and X ² can further have a branched structure having a terminal group represented by the general formula (1) and a group represented by the general formula (2) by an ester bond. ) General formula (3) (In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) General formula (4) (In the general formula (4), R ⁴ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 11 carbon atoms. ) 2. A compound having a group represented by the general formula (1) as at least one terminal group, and a group represented by the general formula (2) and / or a group represented by the general formula (5) A fumaric acid ester having a repeating unit. General formula (1) General formula (2) General formula (5) (In the general formula (1), R ¹ each independently represents the general formula (3) or the general formula (4).
In the general formulas (2) and (5), X ¹ , X ² , X ³
Is independently 2 to 6 hydroxyl groups having 2 carbon atoms
Represents an organic residue derived from a polyhydric alcohol having 30 to 30 carbon atoms. However, X ¹ , X ² and X ³ are ester bonds and / or
Alternatively, a branched structure including a group represented by the general formula (2) and / or a group represented by the general formula (5) can be further provided by an ether bond having the general formula (1) as a terminal group. ) General formula (3) (In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) General formula (4) (In the general formula (4), R ⁴ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 11 carbon atoms. ) 3. The fumarate according to claim 1, wherein the number of repetitions of the repeating unit represented by the general formula (2) is in the range of 2 to 10. 4. The fumarate according to claim 2, wherein the number of repetitions of the repeating unit represented by the general formula (5) is in the range of 2 to 5. 5. The method according to claim ¹ , wherein 80% or more of R ^{1 in} the general formula (1) is the general formula (4).
A fumarate according to any one of the above. 6. R ⁴ in the general formula (4) is a hydrogen atom,
The fumaric acid ester according to any one of claims 1 to 5, which is at least one member selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. 7. General formula (1), general formula (2), general formula
X in (5)¹, X^Two, X ^ThreeBut each independently
Killened diols, alicyclic diols and aromatic diols
Alcohol selected from at least one of the group consisting of
2. The compound according to claim 1, which is a derived organic residue.
7. The fumaric acid ester according to claim 6. 8. The organic residue derived from the alkylene diol according to claim 7, represented by the general formula (6).
The fumaric acid ester represented by any one of the general formula (6): R ⁵ and R ⁶ are each independently a hydrogen atom or a general formula (7)
Represents General formula (7) (In the general formula (7), R ⁷ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 3 carbon atoms) 9. At least one of the terminal groups has a general formula (8)
The fumarate according to any one of claims 1 to 8, which is a group represented by the formula: General formula (8) 10. A fumaric acid ester represented by the general formula (9). General formula (9) (In the general formula (9), X ⁴ in the general formula (9) independently represents an alkylene group or a cycloalkylene group having 5 to 12 carbon atoms in d X ⁴ ,
d represents any one of the integers of 1 to 5. Also, R ² ,
R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) 11. The fumarate according to claim 10, wherein X ⁴ in the general formula (9) is an alkylene group represented by the general formula (6). General formula (6) R ⁵ and R ⁶ each represent a hydrogen atom or a general formula (7). General formula (7) (In the general formula (7), R ⁷ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 3 carbon atoms) 12. The fumaric acid ester according to claim 1, wherein at least one of the terminal groups is a hydroxyl group. 13. A fumaric acid ester represented by the general formula (10). General formula (10) (In the general formula (10), Z is an organic residue of a trihydric to hexavalent polyhydric alcohol, and R ¹ is each independently a general formula (3)
Or, in the general formula (4), X ⁵ represents a in the general formula (10)
Each independently represent an alkylene group or a cycloalkylene group having a carbon number of 5-12 carbon atoms in X ⁵ which number is present, a is an integer of 1 to 5, b is an integer from 1 to 6, c is 0
An integer of 5 and b + c is 3 to 6; ) General formula (3) (In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) General formula (4) (In the general formula (4), R ⁴ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 11 carbon atoms. ) 14. The fumarate according to claim 13, wherein X ⁵ in the general formula (10) is an alkylene group represented by the general formula (6). General formula (6) R ⁵ and R ⁶ each represent a hydrogen atom or a general formula (7). General formula (7) (In the general formula (7), R ⁷ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 3 carbon atoms) 15. A fumaric acid ester represented by the general formula (11). General formula (11) (In the general formula (11), R ¹ each independently represents the general formula (3) or the general formula (4), and l and m each independently represent an integer of 1 to 5.) General formula (3) Formula 22 (In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) General formula (4) (In the general formula (4), R ⁴ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 11 carbon atoms. (R ⁵ and R ⁶ each represent a hydrogen atom or a general formula (7).) (In the general formula (7), R ⁷ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 3 carbon atoms) 16. The method for producing a fumaric acid ester according to claim 1, wherein the terminal group has at least one general formula (8). And reacting a fumaric acid ester having the general formula (2) as a repeating unit with a polyhydric alcohol having 2 to 6 hydroxyl groups and having 2 to 30 carbon atoms in the presence of a catalyst. A method for producing a fumaric acid ester. 17. The method for producing a fumaric acid ester according to claim 13, wherein the method for producing the fumaric acid ester comprises the step of producing at least one fumaric acid ester having the general formula (8) in a terminal group and two to six hydroxyl groups. Having 2 to 30 carbon atoms
A method for producing a fumaric acid ester, the method comprising reacting a polyhydric alcohol with a polyhydric alcohol in the presence of a catalyst. 18. The method for producing a fumaric acid ester according to claim 1, wherein the terminal group has at least one of the general formula (8). A fumaric acid ester having a repeating unit of the general formula (2) and a polyhydric alcohol having 2 to 6 hydroxyl groups and having 2 to 30 carbon atoms in the presence of a condensing agent and a base A method for producing a fumaric acid ester, comprising: 19. The method for producing a fumaric acid ester according to claim 13, wherein the method for producing the fumaric acid ester comprises the step of producing at least one fumaric acid ester having the general formula (8) in a terminal group and two to six hydroxyl groups. Having 2 to 30 carbon atoms
Wherein the polyhydric alcohol is reacted with a condensing agent in the presence of a base. 20. The method according to claim 18, wherein the condensing agent is a sulfonyl chloride. 21. C2-C2 having 2 to 6 hydroxyl groups.
Polyhydric alcohols having 30 carbon atoms are trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane and dipentaerythritol,
The method for producing a fumarate according to any one of claims 16 to 20, wherein the at least one is selected from the group consisting of adducts of these with ethylene oxide and propylene oxide. 22. The terminal group of the fumaric acid ester having the general formula (3) as a terminal group is subjected to an isomerization reaction of the terminal group in the presence of a catalyst to convert the terminal group to the general formula (4). A method for producing a fumaric acid ester having a general formula (4) at a terminal group, characterized in that: 23. The method according to claim 22, wherein the fumaric acid ester having the general formula (3) as a terminal group is the fumaric acid ester according to any one of claims 1 to 15. A method for producing a fumaric acid ester having a general formula (4) at a terminal group. 24. The isomerization reaction, wherein 80% or more of the general formula (3) in the fumarate having the general formula (3) as a terminal group is converted into the general formula (4). A method for producing a fumaric acid ester having the general formula (4) as a terminal group according to Claim 22 or 23. 25. The catalyst according to claim 22, wherein the catalyst used in the isomerization reaction contains at least one of palladium, rhodium and ruthenium.
The method for producing a fumaric acid ester having a general formula (4) at a terminal group according to any one of the above. 26. A polymerizable composition comprising the fumaric acid ester according to claim 1. Description: 27. An oligomer having 1% to 99% by weight of fumaric acid ester according to any one of claims 1 to 15 and an unsaturated polyester, an oligomer having (meth) acrylate and a radical polymerizable monomer. At least one compound selected from the group consisting of: 1% by mass to 99%
27. The polymerizable composition according to claim 26, wherein the composition contains 0.1% by mass. 28. The polymerizable composition according to claim 26 or 27, wherein 100 parts by mass and a radical polymerization initiator
.. A polymerizable composition containing 0.01 to 15 parts by mass. A cured product obtained by curing the polymerizable composition according to any one of claims 26 to 28. 30. A fumaric acid ester having a group represented by the general formula (1) as at least one terminal group and a group represented by the general formula (2). 31. A compound having a group represented by the general formula (1) as at least one terminal group, and a group represented by the general formula (2) and / or a group represented by the general formula (5) A fumaric acid ester characterized by having: 32. A fumaric acid ester represented by the general formula (24). General formula (24) (In the general formula (24), R ¹ each independently represents the general formula (3) or the general formula (4), and p represents an integer of 1 to 9. The general formula (3) (In the general formula (3), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) General formula (4) (In the general formula (4), R ⁴ is a hydrogen atom or carbon atom 1
~ Represents an alkyl group having 11 carbon atoms. )