WO2024166470A1 - Polyfunctional compound, method for producing same, polymerizable composition, and cured product - Google Patents

Abstract

The purpose of the present invention is to provide a polyfunctional compound that exhibits excellent solubility in organic solvents. The present invention is a polyfunctional compound represented by formula (I): CH₂=CH-(R¹)_l-R²-(R³)_m-O-CO-R⁴-CO-O-(R⁵)_n-R⁶-(R⁷)_o-CH=CH₂ (I) [In formula (I), R¹, R³, R⁵ and R⁷ are each independently a hydrocarbon group that may have a substituent group, R² is an aromatic group that may have a substituent group, R⁶ is an organic group, R⁴ is a hydrocarbon group which has 2-22 carbon atoms and may have a substituent group, and l to o are each independently 0 or 1].

Description

Polyfunctional compound, method for producing same, polymerizable composition, and cured product

The present invention relates to a polyfunctional compound, a method for producing the same, a polymerizable composition, and a cured product.

A crosslinking agent is a compound that crosslinks monomers together or reacts with a polymer to form a crosslinked structure between polymers when heated, etc., and such compounds usually have two or more functional groups.

Specific examples of crosslinking agents that can be used include polyfunctional compounds such as di(meth)acrylic acid esters having two vinyl groups, and such polyfunctional compounds can usually be used by adding them to a polymerizable composition containing a polymerizable monomer (for example, Patent Document 1).

JP 2022-22125 A

When using a polymerizable composition such as the one described above, the polymerizable composition is usually mixed with an organic solvent before the polymerization reaction is carried out. From the viewpoint of being usable for a wide range of applications, it is desirable that the polyfunctional compound contained in the polymerizable composition has excellent solubility in organic solvents.

Therefore, an object of the present invention is to provide a polyfunctional compound having excellent solubility in organic solvents, and a method for producing the same.
Another object of the present invention is to provide a polymerizable composition containing the above polyfunctional compound.
Another object of the present invention is to provide a cured product of the above polymerizable composition.

The present inventors have conducted extensive research with the aim of solving the above problems. The inventors have newly discovered that the above problems can be solved by a polyfunctional compound that contains at least two vinyl groups, at least two ester structures, a specific structure containing an aromatic ring group, and a specific hydrocarbon group, and have thus completed the present invention.

That is, an object of the present invention is to advantageously solve the above problems, and [1] the present invention provides a compound represented by the following formula (I):
CH ₂ =CH-(R ¹ ) _l -R ² -(R ³ ) _m -O-CO-R ⁴ -CO-O-(R ⁵ ) _n -R ⁶ -(R ⁷ ) _o -CH=CH ₂ (I)
[In formula (I), R ¹ , R ³ , R ⁵ and R ⁷ are each independently a hydrocarbon group which may have a substituent, R ² is an aromatic ring group which may have a substituent, R ⁶ is an organic group, R ⁴ is a hydrocarbon group having from 2 to 22 carbon atoms which may have a substituent, and l to o are each independently 0 or 1.]
The above-mentioned polyfunctional compounds have excellent solubility in organic solvents.

[2] In the polyfunctional compound of [1] above, it is preferable that R ¹ , R ³ , R ⁵ and R ⁷ in the formula (I) are each independently an unsubstituted hydrocarbon group or a hydrocarbon group having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group and a carboxyl group.
When R ¹ , R ³ , R ⁵ and R ⁷ in formula (I) are the above-mentioned hydrocarbon groups, the solubility of the polyfunctional compound in an organic solvent can be improved.

[3] In the polyfunctional compound of the above [1] or [2], it is preferable that l in the formula (I) is 0.
When l in formula (I) is 0, the vinyl group is directly bonded to the aromatic ring group of ^R2 , so that the polyfunctional compound can have a rigid structure.

[4] In any one of the polyfunctional compounds [1] to [3] above, m in the formula (I) is preferably 0.
When m in formula (I) is 0, the non-carbonyl oxygen atom is directly bonded to the aromatic ring group of ^R2 , so that the functional compound can have a rigid structure.

[5] In any of the polyfunctional compounds [1] to [4] above, it is preferable that R ⁶ in the formula (I) is an aromatic ring group which may have a substituent, and l to o in the formula (I) are 0.
When R ⁶ in formula (I) is an aromatic ring group which may have a substituent, and l to o in formula (I) are 0, the functional compound can have a more rigid structure. In addition, when R ⁶ in formula (I) is an aromatic ring group which may have a substituent, the reactivity of the polyfunctional compound can be increased.

[6] In any of the polyfunctional compounds [1] to [5] above, R ⁴ in the formula (I) is preferably an unsubstituted hydrocarbon group having 2 to 22 carbon atoms, or a hydrocarbon group having 2 to 22 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group, and a carboxyl group.
When R ⁴ in formula (I) is the above-mentioned hydrocarbon group, the solubility of the polyfunctional compound in an organic solvent can be improved.

[7] In the polyfunctional compound of [6] above, R ⁴ in the formula (I) is preferably a linear alkylene group having 2 to 22 carbon atoms.
When R ⁴ in formula (I) is a linear alkylene group having from 2 to 22 carbon atoms, the solubility of the polyfunctional compound in an organic solvent can be further improved.

[8] In any one of the polyfunctional compounds [1] to [7] above, the biomass ratio is preferably 50% or more.
When the biomass degree is equal to or higher than the above lower limit, the environmental load can be reduced, and the environmental load reduction properties of the polyfunctional compound can be improved.
In this specification, the "biomass degree" of a polyfunctional compound is calculated by the following calculation formula (1).
Biomass ratio = total molecular weight of carbon atoms of biomass-derived components / (total molecular weight of carbon atoms of biomass-derived components + total molecular weight of carbon atoms of fossil fuel-derived components) × 100 [%] (1)
For example, a refined product of a biomass-derived component or a reaction product between biomass-derived components (but excluding a catalyst) has a biomass content of 100%.
In addition, in this specification, "biomass" refers to any renewable natural raw material and its residue, whether derived from plants or animals, including fungi, yeasts, algae, and bacteria, and "fossil fuel" refers to petroleum, coal, natural gas, shale gas, etc., which are the remains of animals and plants that have been fossilized through deposition, pressure, etc. over hundreds of millions of years.

The present invention also aims to advantageously solve the above problems, and [9] the present invention provides a method for producing a polyfunctional compound according to any one of the above [1] to [8], comprising reacting a polyfunctional compound represented by the following formula (II):
HO-CO-R ⁴ -CO-OH (II)
[In formula (II), R ⁴ is the same as R ⁴ in formula (I)]
and a hydroxyl group-containing vinyl compound.
According to the above-mentioned production method, a polyfunctional compound having excellent solubility in organic solvents can be obtained.

[10] In the method for producing a polyfunctional compound according to the above [9], at least one of the dicarboxylic acid and the hydroxyl group-containing vinyl compound is preferably derived from biomass.
When at least one of the dicarboxylic acid and the hydroxyl group-containing vinyl compound is derived from biomass, the environmental load of the polyfunctional compound can be reduced.

Another object of the present invention is to advantageously solve the above problems. [11] The present invention is a polymerizable composition comprising the polyfunctional compound according to any one of [1] to [8] above, a radical polymerizable monomer, and a radical initiator.
The polymerizable composition as described above can be used in a wide range of applications.

Another object of the present invention is to advantageously solve the above problems, and the present invention [12] relates to a cured product of the polymerizable composition according to the above [11].
The above-mentioned cured product has excellent productivity.

According to the present invention, it is possible to provide a polyfunctional compound having excellent solubility in organic solvents and a method for producing the same.
Furthermore, according to the present invention, there is provided a polymerizable composition containing the above polyfunctional compound.
Furthermore, according to the present invention, a cured product of the above polymerizable composition can be provided.

The present invention will be described in detail below.
In this specification, "may have a substituent" means "unsubstituted or substituted". Here, when a hydrocarbon group or the like contained in a chemical formula has a substituent, the number of carbon atoms of the hydrocarbon group having the substituent does not include the number of carbon atoms of the substituent. For example, when a hydrocarbon ring group having 2 to 22 carbon atoms has a substituent, the number of carbon atoms of the hydrocarbon ring group having 2 to 22 carbon atoms does not include the number of carbon atoms of such a substituent.
In addition, in this specification, the term "aromatic ring" refers to a cyclic structure having aromaticity in a broad sense according to Huckel's rule, i.e., a cyclic conjugated structure having (4n+2) n electrons, and a cyclic structure in which a lone electron pair of a heteroatom such as sulfur, oxygen, or nitrogen participates in an n-electron system and exhibits aromaticity, as typified by thiophene, furan, benzothiazole, etc.
In this specification, R ¹ to R ⁷ included in formula (I) and the like described later are all divalent groups.

(Polyfunctional Compound)
The polyfunctional compound of the present invention is a compound represented by the following formula (I).
CH ₂ =CH-(R ¹ ) _l -R ² -(R ³ ) _m -O-CO-R ⁴ -CO-O-(R ⁵ ) _n -R ⁶ -(R ⁷ ) _o -CH=CH ₂ (I)
The above-mentioned polyfunctional compounds have excellent solubility in organic solvents.

The polyfunctional compound of the present invention is not particularly limited, and can be used, for example, as a crosslinking agent that crosslinks monomers together or reacts with a polymer to form a crosslinked structure between polymers.
The polyfunctional compound of the present invention can also be used as a monomer. For example, when preparing a polymer, it is possible to use only the polyfunctional compound of the present invention as a monomer.

Here, when polymerization is carried out using the polyfunctional compound of the present invention, the polymerizability of the monomer can be improved. In addition, when the polyfunctional compound of the present invention is used to prepare a polymer (cured product), the occurrence of tackiness in the resulting polymer (cured product) can be effectively suppressed. Furthermore, for example, when the polyfunctional compound is used to prepare a film as the polymer (cured product), a clean film can be formed. The reasons for these are unclear, but are thought to be due to the fact that the polyfunctional compound of the present invention has an aromatic ring group, which will be described later.

<Explanation of Formula (I)>
Here, ^R2 in formula (I) is an aromatic ring group which may have a substituent.

Examples of the aromatic ring group of ^R2 include aromatic hydrocarbon ring groups such as a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a pyrene ring group, and a fluorene ring group; a 1H-isoindole-1,3(2H)-dione ring group, a 1-benzofuran ring group, a 2-benzofuran ring group, an acridine ring group, an isoquinoline ring group, an imidazole ring group, an indole ring group, an oxadiazole ring group, an oxazole ring group, an oxazolopyrazine ring group, an oxazolopyridine ring group, an oxazolopyridazyl ring group, an oxazolopyrimidine ring group, a quinazoline ring group, a quinoxaline ring group, a quinoline ring group, a cinnoline ring group, a thiadiazole ring group, a thiazole ring group, a thiazolopyrazine ring group, a thiazolopyridine ring group, a thiazolopyridazine ring group, a thiazolo and aromatic heterocyclic groups such as a pyrimidine ring group, a thiophene ring group, a triazine ring group, a triazole ring group, a naphthyridine ring group, a pyrazine ring group, a pyrazole ring group, a pyran ring group, a pyridine ring group, a pyridazine ring group, a pyrimidine ring group, a pyrrole ring group, a phenanthridine ring group, a phthalazine ring group, a furan ring group, a benzo[b]thiophene ring group, a benzo[c]thiophene ring group, a benzisoxazole ring group, a benzisothiazole ring group, a benzimidazole ring group, a benzoxadiazole ring group, a benzoxazole ring group, a benzothiadiazole ring group, a benzothiazole ring group, a benzothiophene ring group, a benzotriazine ring group, a benzotriazole ring group, a benzopyrazole ring group, and a benzopyranone ring group.
Among these, the aromatic ring group is preferably an aromatic hydrocarbon ring group, and more preferably a benzene ring group.

The aromatic ring group of ^R2 may be an unsubstituted aromatic ring group or an aromatic ring group having a substituent, but from the viewpoint of improving the solubility of the polyfunctional compound in an organic solvent, it is preferable that it is an aromatic ring group having a substituent. Note that the "aromatic ring group having a substituent" means that the substituent is directly bonded to the aromatic ring of the aromatic ring group.
Here, examples of the substituent that the aromatic ring group of ^R2 may have include a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group, a carboxyl group, etc. Among these, an alkoxy group is preferable.

The alkoxy group is a group represented by "-O-R ^A ".
Examples of R ^A include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl groups, and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, and propylphenyl groups. Among these, alkyl groups are preferred, and methyl groups are particularly preferred.

The ester group is a group represented by "--R ^B -CO--OR ^C ".
Examples of R 3 ^B include alkylene groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a cyclohexylene group, and an octylene group; and arylene groups such as a phenylene group, a tolylene group, a dimethylphenylene group, a trimethylphenylene group, an ethylphenylene group, and a propylphenylene group.
Examples of R ^C include those similar to those listed for R ^A.

The ether group is a group represented by "-R ^D -O-R ^E ".
Examples of R ^D include those similar to those listed for R ^B.
Examples of ^RE include the same as those listed for ^RA .

^R6 in formula (I) is an organic group.

Here, the organic group of ^R6 is not particularly limited, but examples thereof include an aliphatic hydrocarbon group which may have a substituent (e.g., an alkylene group, an alkenylene group, etc.), an aromatic ring group which may have a substituent, and the like.
The organic group of ^R6 is preferably an aromatic ring group which may have a substituent. Since aromatic rings are rigid, if the organic group of ^R6 is an aromatic ring group which may have a substituent, the polyfunctional compound can have a rigid structure. If the polyfunctional compound has a rigid structure, for example, when the polyfunctional compound is used as a crosslinking agent, the hardness of the resulting polymer can be improved. In addition, if the organic group of ^R6 is an aromatic ring group which may have a substituent, the reactivity of the polyfunctional compound can be increased.
The aromatic ring group and the substituent of ^R6 are the same as those of ^R2 .

R ⁴ in formula (I) is a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent.

Here, from the viewpoint of improving the solubility of the polyfunctional compound in an organic solvent, ^R4 in formula (I) is preferably an unsubstituted hydrocarbon group having 2 to 22 carbon atoms or a hydrocarbon group having 2 to 22 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group, and a carboxyl group, and more preferably an unsubstituted hydrocarbon group having 2 to 22 carbon atoms.
Examples of the alkoxy group, ester group and ether group that the hydrocarbon group having 2 to 22 carbon atoms may have include the same alkoxy group, ester group and ether group as described above for ^R2 .

Examples of the hydrocarbon group having 2 to 22 carbon atoms for R ⁴ (hereinafter, "2 to 22 carbon atoms" may be referred to as "C2-22") include C2-22 aliphatic hydrocarbon groups such as a C2-22 alkylene group and a C2-22 alkenylene group; and C2-22 aromatic hydrocarbon ring groups such as a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a pyrene ring group, and a fluorene ring group. Among these, a C2-22 aliphatic hydrocarbon group is preferred, and a C2-22 alkylene group is more preferred. Furthermore, as the C2-22 alkylene group, a C2-22 linear alkylene group is particularly preferred from the viewpoint of further improving the solubility of the polyfunctional compound in organic solvents.
In this specification, the term "straight-chain alkylene group" refers to an unbranched straight-chain alkylene group.

Here, from the viewpoint of improving the solubility of the polyfunctional compound in an organic solvent, ^R4 in formula (I) is preferably a hydrocarbon group having 2 carbon atoms which may have a substituent, or a hydrocarbon group having 6 to 22 carbon atoms which may have a substituent, and more preferably a linear alkylene group having 2 carbon atoms, or a linear alkylene group having 6 to 22 carbon atoms.

Examples of C2-22 linear alkylene groups include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene (-(CH ₂ ) ₁₀ -), eicosamethylene (-(CH ₂ ) ₂₀ -), docosamethylene (-(CH ₂ ) ₂₂ -), etc. Among these, from the viewpoint of further improving the solubility of the polyfunctional compound in organic solvents, ethylene, tetramethylene and octamethylene groups are preferred, ethylene and octamethylene groups are more preferred, and ethylene is even more preferred.

In formula (I), R ¹ , R ³ , R ⁵ and R ⁷ each independently represent a hydrocarbon group which may have a substituent.
In the following, "R ¹ , R ³ , R ⁵ and R ⁷ " may be referred to as "R ^1, etc.".

Here, from the viewpoint of improving the solubility of the polyfunctional compound in an organic solvent, it is preferable that ^R1 and the like in formula (I) are each independently an unsubstituted hydrocarbon group or a hydrocarbon group having at least one type of substituent selected from the group consisting of a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group, and a carboxyl group.
The alkoxy group, ester group and ether group which the above-mentioned hydrocarbon group may have include the same alkoxy group, ester group and ether group as explained above for ^R2 .

In formula (I), l to o are each independently 0 or 1.

In the polyfunctional compound of the present invention, it is preferable that l in formula (I) is 0. When l in formula (I) is 0, the vinyl group is directly bonded to the aromatic ring group of ^R2 , so that the polyfunctional compound can have a rigid structure. If the polyfunctional compound has a rigid structure, for example, when the polyfunctional compound is used as a crosslinking agent, the hardness of the obtained polymer can be improved.

In the polyfunctional compound of the present invention, m in formula (I) is preferably 0. When m in formula (I) is 0, the non-carbonyl oxygen atom is directly bonded to the aromatic ring group of ^R2 , so that the functional compound can have a rigid structure. If the polyfunctional compound has a rigid structure, for example, when the polyfunctional compound is used as a crosslinking agent, the hardness of the resulting polymer can be improved.

The polyfunctional compound of the present invention is more preferably one in which l and m in formula (I) are 0. When l and m in formula (I) are 0, the functional compound can have a more rigid structure. Furthermore, if the polyfunctional compound has a more rigid structure, for example, when the polyfunctional compound is used as a crosslinking agent, the hardness of the resulting polymer can be further improved.

Here, it is particularly preferable that the polyfunctional compound of the present invention has R ⁶ in formula (I) as an aromatic ring group which may have a substituent, and l to o in formula (I) as 0. If R ⁶ in formula (I) is an aromatic ring group which may have a substituent, and l to o in formula (I) as 0, the functional compound can have an even more rigid structure. If the polyfunctional compound has an even more rigid structure, for example, when the polyfunctional compound is used as a crosslinking agent, the hardness of the resulting polymer can be further improved. In addition, if R ⁶ in formula (I) is an aromatic ring group which may have a substituent, the reactivity of the polyfunctional compound can be increased.

The polyfunctional compound of the present invention preferably has the same structure on both sides of ^R4 in formula (I). That is, the polyfunctional compound of the present invention is represented by the following formula (IA):
CH ₂ =CH-(R ¹ ) _l -R ² -(R ³ ) _m -O-CO-R ⁴ -CO-O-(R ³ ) _m -R ² -(R ¹ ) _l -CH=CH ₂ (IA)
[In formula (IA), R ¹ to R ⁴ , l and m are the same as R ¹ to R ⁴ , l and m in formula (I), respectively.]
It is preferable that the compound is represented by the following formula:
If the polyfunctional compound is a compound represented by formula (IA), the number of raw materials used in the production of the polyfunctional compound can be reduced, making it possible to easily produce the polyfunctional compound. In addition, if the polyfunctional compound is a compound represented by formula (IA), the reactivity of the polyfunctional compound can be increased.
In addition, since the polyfunctional compound can be made to have a more rigid structure and can be more easily produced, it is particularly preferable that l and m in formula (IA) are 0. That is, the polyfunctional compound is represented by the following formula (Ia):
CH ₂ =CH-R ² -O-CO-R ⁴ -CO-O-R ² -CH=CH ₂ (Ia)
[In formula (Ia), ^R2 and ^R4 are the same as ^R2 and ^R4 in formula (I), respectively.]
It is particularly preferable that the compound is represented by the following formula:

Specific examples of the polyfunctional compound of the present invention include compounds represented by the following formulas (I-1) to (I-4). However, the polyfunctional compound of the present invention is not limited to the compounds represented by the following formulas (I-1) to (I-4). In the following formulas, "Me" means a methyl group.

<Properties of polyfunctional compounds>
The polyfunctional compound preferably has a biomass degree of 50% or more, more preferably 70% or more, even more preferably 90% or more, and particularly preferably 100%. That is, it is particularly preferable that the polyfunctional compound is composed only of biomass-derived components.
When the biomass degree is equal to or higher than the above lower limit, the environmental load can be reduced, and the environmental load reduction properties of the polyfunctional compound can be improved.

The polyfunctional compound preferably has a melting point of 50° C. or higher, more preferably 60° C. or higher, and even more preferably 70° C. or higher, and preferably has a melting point of 250° C. or lower, more preferably 200° C. or lower, even more preferably 140° C. or lower, and even more preferably 100° C. or lower.
If the melting point is equal to or higher than the above lower limit, for example, when a polyfunctional compound is used as a crosslinking agent, the hardness of the obtained polymer can be improved.
On the other hand, when the melting point is equal to or lower than the above upper limit, the solubility of the polyfunctional compound in an organic solvent can be improved.
In this specification, the melting point of the polyfunctional compound can be measured according to the method described in the Examples.

(Method for producing polyfunctional compounds)
The method for producing a polyfunctional compound of the present invention comprises reacting a compound represented by the following formula (II):
HO-CO-R ⁴ -CO-OH (II)
and a hydroxyl group-containing vinyl compound.
According to the above-mentioned production method, it is possible to obtain a polyfunctional compound having excellent solubility in organic solvents, that is, the polyfunctional compound of the present invention can be obtained.
In the method for producing a polyfunctional compound of the present invention, after reacting a dicarboxylic acid with a hydroxyl group-containing vinyl compound, the target polyfunctional compound may be optionally isolated by a separation/purification means such as slurry washing or recrystallization.
The purity of the polyfunctional compound is usually 90% by mass or more, preferably 95% by mass or more, and more preferably 98% by mass or more.
In this specification, the purity of the polyfunctional compound can be measured by high performance liquid chromatography (HPLC) according to the method described in the Examples.

Here, in the method for producing a polyfunctional compound of the present invention, it is preferable that at least one of the dicarboxylic acid represented by formula (II) (hereinafter, sometimes simply referred to as "dicarboxylic acid") and the hydroxyl group-containing vinyl compound is derived from biomass.
When at least one of the dicarboxylic acid and the hydroxyl group-containing vinyl compound is derived from biomass, the environmental load of the polyfunctional compound can be reduced.
From the viewpoint of further improving the environmental load reducing properties of the polyfunctional compound, it is more preferable that both the dicarboxylic acid and the hydroxyl group-containing vinyl compound are derived from biomass in the method for producing a polyfunctional compound of the present invention.

<Dicarboxylic acid>
The dicarboxylic acid to be reacted with the hydroxyl group-containing vinyl compound is represented by the following formula (II):
HO-CO-R ⁴ -CO-OH (II)
[In formula (II), R ⁴ is the same as R ⁴ in formula (I)]
It is a compound represented by the formula:
Specific examples of the dicarboxylic acid represented by formula (II) include succinic acid in which R ⁴ is an ethylene group, adipic acid in which R ⁴ is a tetramethylene group, sebacic acid in which R ⁴ is an octamethylene group, and docosanedioic acid in which R ⁴ is an eicosamethylene group (-(CH ₂ ) ₂₀ -).

From the viewpoint of improving the environmental load reduction of the polyfunctional compound, the dicarboxylic acid is preferably derived from biomass, that is, the biomass ratio of the dicarboxylic acid is preferably 100%.
Examples of the biomass-derived dicarboxylic acid that can be used include succinic acid manufactured by BASF, adipic acid manufactured by INVISTA, and sebacic acid manufactured by Ito Oil Mills.

<Hydroxyl Group-Containing Vinyl Compound>
The hydroxyl group-containing vinyl compound to be reacted with the dicarboxylic acid is not particularly limited as long as it can give the polyfunctional compound of the present invention, and any of the conventionally known hydroxyl group-containing vinyl compounds can be used.

Examples of the hydroxyl group-containing vinyl compound include those represented by the following formula (III):
CH ₂ =CH-(R ¹ ) _l -R ² -(R ³ ) _m -OH (III)
[In formula (III), R ¹ to R ³ , l and m are the same as R ¹ to R ³ , l and m in formula (I), respectively.]
and a hydroxyl group-containing vinyl compound represented by the formula:
The following formula (IV):
HO-(R ⁵ ) _n -R ⁶ -(R ⁷ ) _o -CH=CH ₂ (IV)
[In formula (IV), R ⁵ to R ⁷ , n and o are the same as R ⁵ to R ⁷ , n and o in formula (I), respectively.]
and a hydroxyl group-containing vinyl compound represented by the formula (I) can be used. By using these hydroxyl group-containing vinyl compounds, the polyfunctional compound of the present invention (the compound represented by the formula (I)) can be easily produced.

In addition, when the polyfunctional compound of the present invention has the same structure on the left and right sides of ^R4 in formula (I), that is, when it is a compound represented by the above formula (IA), only the hydroxyl group-containing vinyl compound represented by the above formula (III) can be used as the hydroxyl group-containing vinyl compound.

In addition, when the polyfunctional compound of the present invention is a compound represented by formula (Ia), the hydroxyl group-containing vinyl compound may be a compound represented by the following formula (IIIa):
CH ₂ =CH-R ² -OH (IIIa)
[In formula (IIIa), ^R2 is the same as ^R2 in formula (Ia)]
Specific examples of the hydroxyl group-containing vinyl compound represented by formula (IIIa) include 4-vinylguaiacol and 4-vinylphenol.

From the viewpoint of improving the environmental load reduction of the polyfunctional compound, the hydroxyl group-containing vinyl compound is preferably derived from biomass, that is, the biomass ratio of the hydroxyl group-containing vinyl compound is preferably 100%.
Hereinafter, a method for preparing a biomass-derived hydroxyl group-containing vinyl compound will be described using 4-vinylguaiacol and 4-vinylphenol as examples, but the biomass-derived hydroxyl group-containing vinyl compound is not limited to these.

Biomass-derived 4-vinylguaiacol can be prepared by reacting biomass-derived ferulic acid with triethylamine. The reaction may be carried out in a solvent such as N,N-dimethylformamide, or under reflux when a solvent is used. The product obtained after the reaction may be appropriately purified.
Biomass-derived 4-vinylphenol can be prepared by substituting biomass-derived p-coumaric acid for biomass-derived ferulic acid in the preparation of biomass-derived 4-vinylguaiacol described above.
Ferulic acid derived from biomass may be ferulic acid manufactured by Tsuno Foods Industry Co., Ltd., and p-coumaric acid derived from biomass may be p-coumaric acid manufactured by Merck & Co., Ltd.

<Reaction conditions>
The reaction conditions for reacting a dicarboxylic acid with a hydroxyl group-containing vinyl compound are not particularly limited as long as the desired polyfunctional compound can be obtained. For example, the desired polyfunctional compound can be efficiently obtained by mixing a dicarboxylic acid, a hydroxyl group-containing vinyl compound, and a solvent such as N-methylpyrrolidone, and reacting the mixture at a temperature of 10° C. or higher and 30° C. or lower for 10 hours or longer and 30 hours or shorter.

Here, the total amount of the hydroxyl group-containing vinyl compounds used relative to the amount of the dicarboxylic acids used ("hydroxyl group-containing vinyl compounds"/"dicarboxylic acids") is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.8 or less, in molar ratio.
When the total amount of the hydroxyl group-containing vinyl compound to be used relative to the amount of the dicarboxylic acid is equal to or less than the upper limit in terms of molar ratio, the yield of the obtained polyfunctional compound can be improved, and the polyfunctional compound can be easily purified.
On the other hand, the total amount of the hydroxyl group-containing vinyl compounds used relative to the amount of the dicarboxylic acid used is, for example, 1.0 or more, or may be 1.2 or more, or may be 1.5 or more, in terms of molar ratio.
When two kinds of hydroxyl group-containing vinyl compounds are used, the ratio of the amounts of the two kinds of hydroxyl group-containing vinyl compounds to be used is preferably equal in molar terms.

In the reaction between the dicarboxylic acid and the hydroxyl group-containing vinyl compound, a coupling agent, a co-catalyst, etc. may be added in addition to the dicarboxylic acid and the hydroxyl group-containing vinyl compound.
As the coupling agent, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC), N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide, or the like can be used.
As the co-catalyst, for example, dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), etc. can be used.

(Polymerizable composition)
The polymerizable composition of the present invention contains the above-mentioned polyfunctional compound of the present invention, a radical polymerizable monomer, and a radical initiator. Since the polymerizable composition of the present invention contains the polyfunctional compound of the present invention, it can be used for a wide range of applications.
Here, the polymerizable composition of the present invention usually contains an organic solvent, but when the polyfunctional compound of the present invention is dissolved in the radical polymerizable monomer, that is, when the radical polymerizable monomer also functions as an organic solvent, the polymerizable composition of the present invention may not contain an organic solvent. However, from the viewpoint of further expanding the use applications of the polymerizable composition of the present invention, it is preferable that the polymerizable composition of the present invention contains an organic solvent. That is, it is preferable that the polymerizable composition of the present invention contains the above-mentioned polyfunctional compound of the present invention, a radical polymerizable monomer, a radical initiator, and an organic solvent.
The polymerizable composition of the present invention may further contain any additive.

<Polyfunctional Compound>
The polyfunctional compound used is the polyfunctional compound of the present invention described above. In the polymerizable composition of the present invention, the polyfunctional compound has at least two vinyl groups, and therefore can function as a crosslinking agent that crosslinks radical polymerizable monomers contained in the polymerizable composition during a polymerization reaction.

<Radical polymerizable monomer>
The radical polymerizable monomer is a monomer having a radical polymerizable functional group. Examples of the radical polymerizable functional group include a group having a carbon-carbon double bond. Specific examples of the group having a carbon-carbon double bond include a (meth)acryloyl group and a vinyl group.
In this specification, (meth)acryloyl means acryloyl and/or methacryloyl.

Specific examples of monomers having a radically polymerizable functional group include monofunctional (meth)acrylic acid derivatives such as alkyl(meth)acrylates, and monofunctional aromatic vinyl monomers such as styrene. Among these, from the viewpoint of reactivity in radical polymerization such as photopolymerization, monofunctional (meth)acrylic acid derivatives are preferred, and alkyl(meth)acrylates are more preferred.
In this specification, (meth)acrylate means acrylate and/or methacrylate, and (meth)acrylic means acrylic and/or methacrylic.

<Radical initiator>
The radical initiator is a compound that generates an active species capable of initiating polymerization of a radical polymerizable monomer by light (ultraviolet light, etc.), heating, etc. Examples of the radical initiator that can be used include organic peroxides such as benzoyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxycarbonate, and t-butylperoxyisopropyl monocarbonate; azo compounds such as 2,2'-azobisisobutyronitrile (AIBN); and oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime). These may be used alone or in combination of two or more.

<Organic Solvent>
The organic solvent is not particularly limited as long as it can dissolve a predetermined amount of the polyfunctional compound, the radical polymerizable monomer, and the radical initiator, and for example, ethyl methyl ketone (MEK), ethyl acetate, toluene, propylene glycol monomethyl ether, methanol, tetrahydrofuran (THF), cyclopentyl methyl ether, xylene, cyclopentanone, 1,3 dioxolane, butyl acetate, etc. can be used. These may be used alone or in combination of two or more. Among these, it is particularly preferable to use tetrahydrofuran, since it is particularly suitable for dissolving the polyfunctional compound of the present invention.

<Optional Additives>
As optional additives that can be contained in the polymerizable composition of the present invention, various additives can be used depending on the application of the polymerizable composition. Specifically, the optional additives include, for example, light stabilizers, ultraviolet absorbers, catalysts, leveling agents, defoamers, polymerization accelerators, antioxidants, flame retardants, infrared absorbers, antistatic agents, slip agents, etc. These may be used alone or in combination of two or more. Among these, it is preferable that the polymerizable composition contains an antioxidant as an optional additive.

Examples of the antioxidant include 2,6-di-t-butyl-4-cresol (ANTAGE BHT, manufactured by Kawaguchi Chemical Industry Co., Ltd.), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (Sandant 2246, manufactured by Sanshin Chemical Industry Co., Ltd.), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide (Sandant 103, manufactured by Sanshin Chemical Industry Co., Ltd.), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, manufactured by BASF Japan), octadecyl ether, and the like. Examples of such methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate include isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076, manufactured by BASF Japan), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1135, manufactured by BASF Japan), hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259, manufactured by BASF Japan), and 4,6-bis(octylthiomethyl)-o-cresol (Irganox 1520L, manufactured by BASF Japan).
The content of the antioxidant in the polymerizable composition is preferably 50 ppm or more, more preferably 100 ppm or more, and is preferably 3000 ppm or less, more preferably 1000 ppm or less.

<Method for preparing polymerizable composition>
The polymerizable composition of the present invention can usually be prepared by dissolving the polyfunctional compound of the present invention, the radical polymerizable monomer, the radical initiator, and any additives in a predetermined amount in an organic solvent, etc. In addition, when the polyfunctional compound is soluble in the radical polymerizable monomer, the polymerizable composition of the present invention can be prepared without using an organic solvent.

(Cured product)
The present invention relates to a cured product of the above-mentioned polymerizable composition of the present invention. In other words, the cured product of the present invention is obtained by radical polymerization of the polymerizable composition of the present invention.
The above-mentioned cured product is obtained by curing the polymerizable composition of the present invention, which can be used in a wide range of applications, and therefore has excellent productivity.

The form of the cured product of the present invention can be, for example, a film, a thread, a three-dimensional molded object, etc.

Applications of the cured product of the present invention include, for example, pressure sensitive adhesives, adhesives, resists, etc.

The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. Various measurements and evaluations in the examples were performed according to the following methods.

<NMR Measurement>
The polyfunctional compounds obtained in the examples and comparative examples were measured using a nuclear magnetic resonance apparatus "500 MHz NMR" manufactured by BRUKER.

<Purity measurement>
The purity of the polyfunctional compounds obtained in the Examples and Comparative Examples was measured by high performance liquid chromatography (HPLC). Here, the high performance liquid chromatograph used was a Thermo-scientific Dionex UltiMate 3000 system, and the software used was Chromeleon 7. The pump system used was a DGP-3600RS, the autosampler etc. used was a WPS-3000TRS, the detector used was a DAD (Diode Array Detector) 3000, and the column used was a 4.6 x 100-mm (1.8 um) ZORBAX Eclipse XDB-C18 column.
Specifically, using methanol as mobile phase A and ultrapure water (+0.1 wt % TFA-Trifluoroacetic Acid) as mobile phase B, the sample was separated in a mixed solvent of 40 vol % mobile phase A and 60 vol % mobile phase B for 5 minutes, and then the concentration was changed by applying a gradient so that mobile phase A became 40 to 95 vol % over 2 minutes. Finally, the sample was separated in a mixed solvent of 95 vol % mobile phase A and 5 vol % mobile phase B for 8 minutes, and the purity of the polyfunctional compound was measured.
The flow rate was 1.0 mL/min, the sample injection amount was 1 μL, and the detection wavelength was 254 nm.

<Melting Point>
The melting points of the polyfunctional compounds obtained in the examples and comparative examples were measured using a Melting Point System MP70 (manufactured by Mettler Toledo).
Specifically, first, the polyfunctional compound was heated from 50°C to 230°C at a heating rate of 10°C/min, and the approximate temperature (T _A ) at which the polyfunctional compound melted was determined visually. Next, the polyfunctional compound was heated from T _A -10°C to T _A +10°C at a heating rate of 1°C/min, and the temperature (T _B ) at which the polyfunctional compound started to melt and the temperature (T _C ) at which it completely melted were confirmed. The average value of T _B and T C ((T _B +T C)/2) was determined as the melting point of the polyfunctional compound.
The polyfunctional compound obtained in Example 2 below is exemplified as follows: First, the polyfunctional compound of Example 2 was heated from 50°C to 230°C at a heating rate of 10°C/min. Since the polyfunctional compound melted at approximately 70°C, 70°C was set as T _A. Next, the polyfunctional compound of Example 2 was heated from 60°C (T _A -10°C) to 80°C (T _A +10°C) at a heating rate of 1°C/min. As a result, the polyfunctional compound began to melt at 71.8°C (T _B ) and completely melted at 72.7°C (T _C ). The average value was calculated from these temperatures, and 72.25°C ((71.8°C +72.7°C)/2) was set as the melting point of the polyfunctional compound of Example 2.

<Solubility>
The solubility of the polyfunctional compounds obtained in the Examples and Comparative Examples was measured using methyl ethyl ketone (MEK), ethyl acetate, toluene, propylene glycol monomethyl ether, methanol and tetrahydrofuran (THF) as organic solvents.
Specifically, 0.1 g of the polyfunctional compound and 0.9 g of methyl ethyl ketone were added to a 10 ml eggplant flask, and the mixture was stirred at 20° C. for 0.5 hours, and the presence or absence of residual polyfunctional compound was visually confirmed. The same operation was performed for other organic solvents. If residual polyfunctional compound was present under the condition of 20° C., the temperature was raised to 50° C., and stirring was continued for another 0.5 hours, and the presence or absence of residual polyfunctional compound was visually confirmed. The solubility of the polyfunctional compound was evaluated according to the following criteria.
A: At 20° C., no polyfunctional compound remained undissolved.
B: At 20°C, there was residual polyfunctional compound, but at 50°C, there was no residual polyfunctional compound.
C: At both 20°C and 50°C, there was residual polyfunctional compound.

<Polymerizability>
2.5 g of butyl acrylate, 0.25 g of the polyfunctional compound obtained in Example 2 as a crosslinking agent, and 0.25 g of a photoinitiator as an oxime ester type photoradical generator (initiator) (NCI-730 (manufactured by ADEKA CORPORATION, ADEKA ARCLES)) were mixed to obtain a polymerizable composition as an evaluation sample. Next, 2 mL of the evaluation sample was placed in a 70 mmφ aluminum dish, and irradiated with UV light having a peak intensity of 0.345 W/ ^cm2 using a UV irradiation device (light source is a high-pressure mercury lamp) with a nitrogen concentration of 4% or less, while changing the light amount, to polymerize and harden the evaluation sample, thereby obtaining a cured film. The polymerizability of the obtained cured film was evaluated according to the following criteria. The smaller the light amount, the higher the polymerizability.
A: The evaluation sample was cured with a light amount of less than 3 J/cm ² .
B: The evaluation sample was cured with a light amount of 3 J/cm ² or more and less than 5 J/cm ² .
C: The evaluation sample was not cured even with a light amount of 5 J/cm ² or more.

<Tackiness>
The cured film prepared in the above-mentioned evaluation of polymerization property was placed on an electronic balance, and a load of about 2.5 kg was applied with the thumb of the hand, and the degree of adhesion and deformation of the cured film to the thumb were evaluated according to the following criteria: The less the cured film sticks to the thumb, the more the tackiness is suppressed.
A: The cured film does not stick to the thumb.
B: The cured film sticks to the thumb, but does not deform when peeled off.
C: The cured film stuck to the thumb, and stretched when peeled off.

<Appearance of the cured film>
The state of the cured film produced in the above evaluation of polymerizability was visually observed, and the appearance of the cured film was evaluated according to the following criteria.
A: A beautiful cured film was formed.
B: A part of the evaluation sample was precipitated on the surface of the cured film.
C: The evaluation sample was in a liquid state and hardly formed a film.

Example 1
<Synthesis of 4-vinylguaiacol>

A mixture was obtained by placing 100 g (1.0 mol) of biomass-derived ferulic acid (manufactured by Tsuno Foods Co., Ltd.), 156.35 g (1.0 mol) of triethylamine (Et ₃ N), and 200 ml of N,N-dimethylformamide (DMF) in a 1 L autoclave equipped with a stirrer. The mixture was then reacted under reflux for 4 hours and 50 minutes to obtain a crude product containing biomass-derived 4-vinylguaiacol.
The obtained crude product was extracted with ethyl acetate, and the obtained extract was purified by column chromatography using a mixed solvent of ethyl acetate and hexane to obtain biomass-derived 4-vinylguaiacol.

The obtained 4-vinylguaiacol was subjected to ¹ H-NMR measurement, and the results are shown below.
^1H -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 9.09 (s, 1H), 7.05-6.74 (m, 3H), 6.61 (dd, 1H, J = 11Hz, 17.5Hz), 5.64 (dd, 1H, J = 1Hz, 17.75H z), 5.07 (dd, 1H, J=1Hz, 11Hz), 4.01 (s, 3H)

<Synthesis of polyfunctional compound represented by formula (I-1)>

A mixture was obtained by adding 27.75 g (1.8 mol) of the biomass-derived 4-vinylguaiacol obtained above, 15.00 g (1.0 mol) of adipic acid derived from biomass (manufactured by INVISTA), 400 ml of N-methylpyrrolidone (NMP), 49 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) as a coupling agent, and 1.25 g of dimethylaminopyridine (DMAP) as a cocatalyst to a 1 L autoclave equipped with a stirrer. The mixture was then reacted at room temperature (23° C.) for 17 hours to obtain a crude product containing a polyfunctional compound represented by formula (I-1).
The resulting crude product was washed with ethanol to give a polyfunctional compound represented by formula (I-1).

The resulting polyfunctional compound represented by formula (I-1) was subjected to ¹ H-NMR measurement and ¹³ C-NMR measurement, and the results are shown below.
¹ H-NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 6.99-6.98 (m, 6H), 6.68 (dd, 2H, J = 10.5Hz, 17.75Hz), 5.69 (dd, 2H, J = 0.5Hz, 17.75Hz), 5.2 4 (dd, 2H, J=0.5Hz, 11Hz), 3.84 (s, 6H), 2.66-2.63 (m, 4H), 2.16-1.92 (m, 4H)
^13C -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 171.42, 151.09, 139.44, 136.61, 136.31, 122.75, 118.95, 114.09, 109.82, 55.79, 33.67, 24.37

The purity of the resulting polyfunctional compound represented by formula (I-1) was measured by HPLC. As a result, the purity was 98.6% by mass.

The resulting polyfunctional compound represented by formula (I-1) was subjected to melting point measurement and solubility evaluation. The results are shown in Table 1. Note that since the polyfunctional compound represented by formula (I-1) is a reaction product between biomass-derived components, the biomass content is 100%.

Example 2
<Synthesis of polyfunctional compound represented by formula (I-2)>

As a mixture to be used in the reaction, a mixture of 34.34 g (1.8 mol) of 4-vinylguaiacol derived from the biomass obtained above, 15.00 g (1.0 mol) of succinic acid derived from biomass (manufactured by BASF), 400 ml of N-methylpyrrolidone (NMP), 61 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) as a coupling agent, and 1.55 g of dimethylaminopyridine (DMAP) as a co-catalyst was used, and the same operation as in Example 1 was carried out to obtain a crude product containing a polyfunctional compound represented by formula (I-2).
The resulting crude product was washed with ethanol as a slurry, and further purified by recrystallization with ethyl acetate to obtain a polyfunctional compound represented by formula (I-2).

The resulting polyfunctional compound represented by formula (I-2) was subjected to ¹ H-NMR measurement and ¹³ C-NMR measurement, and the results are shown below.
^1H -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 7.01-6.98 (m, 6H), 6.68 (dd, 2H, J = 11Hz, 17.75Hz), 5.69 (dd, 2H, J = 0.5Hz, 17.5Hz), 5.25 (d d, 2H, J=5.75Hz, 10.5Hz), 3.83 (s, 6H), 3.04 (s, 4H)
^13C -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 170.23, 151.01, 139.31, 136.67, 136.24, 122.75, 118.90, 114.11, 109.83, 55.82, 29.06

The purity of the resulting polyfunctional compound represented by formula (I-2) was measured by HPLC. As a result, the purity was 99.8% by mass.

The resulting polyfunctional compound represented by formula (I-2) was subjected to melting point measurement and solubility evaluation. The results are shown in Table 1. Note that since the polyfunctional compound represented by formula (I-2) is a reaction product between biomass-derived components, the biomass content is 100%.

The obtained polyfunctional compound represented by formula (I-2) was used to evaluate the polymerizability, tackiness, and appearance of the cured film. The results are shown in Table 1.
In order to prevent polymerization of the resulting polyfunctional compounds with each other, the polyfunctional compounds were mixed with 2,6-di-t-butyl-4-cresol (Antage BHT, manufactured by Kawaguchi Chemical Industry Co., Ltd.) as an antioxidant so that the antioxidant concentration was 500 ppm.

Example 3
<Synthesis of polyfunctional compound represented by formula (I-3)>

Various operations were carried out in the same manner as in Example 2, except that a mixture of 20.05 g (1.8 mol) of 4-vinylguaiacol derived from the biomass obtained above, 15.00 g (1.0 mol) of sebacic acid derived from biomass (manufactured by Ito Oil Mills), 400 ml of N-methylpyrrolidone (NMP), 36 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) as a coupling agent, and 0.91 g of dimethylaminopyridine (DMAP) as a co-catalyst was used as the mixture used in the reaction, and a polyfunctional compound represented by formula (I-3) was obtained.

The resulting polyfunctional compound represented by formula (I-3) was subjected to ¹ H-NMR measurement and ¹³ C-NMR measurement, and the results are shown below.
^1H -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 6.99-6.97 (m, 6H), 6.68 (dd, 2H, J = 11Hz, 17.75Hz), 5.69 (dd, 2H, J = 1Hz, 17.5Hz), 5.24 (dd, 2H, J=0.5Hz, 11Hz), 3.84 (s, 6H), 2.59-2.56 (m, 4H), 1.79-1.74 (m, 4H), 1.46-1.38 (m, 8H)
^13C -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 171.88, 151.12, 139.51, 136.53, 136.33, 122.80, 118.96, 114.03, 109.85, 55.83, 34.04, 29.15, 29.0 1,25.02

The purity of the resulting polyfunctional compound represented by formula (I-3) was measured by HPLC. As a result, the purity was 99.7% by mass.

The resulting polyfunctional compound represented by formula (I-3) was subjected to melting point measurement and solubility evaluation. The results are shown in Table 1. Note that since the polyfunctional compound represented by formula (I-3) is a reaction product between biomass-derived components, the biomass content is 100%.

Example 4
<Synthesis of 4-vinylphenol>

A mixture was obtained by placing 100 g (1.0 mol) of biomass-derived p-coumaric acid (Merck), 184.9 g (1.0 mol) of triethylamine (Et ₃ N), and 500 ml of N,N-dimethylformamide (DMF) in a 1 L autoclave equipped with a stirrer. The mixture was then reacted under reflux for 6 hours to obtain a crude product containing biomass-derived 4-vinylphenol.
The resulting crude product was extracted with ethyl acetate, and the extract was purified by column chromatography using a mixed solvent of ethyl acetate and hexane to obtain biomass-derived 4-vinylphenol.

The obtained 4-vinylphenol was subjected to ¹ H-NMR measurement, the results of which are shown below.
^1H -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 9.09 (s, 1H), 7.05-6.74 (m, 3H), 6.61 (dd, 1H, J = 11Hz, 17.5Hz), 5.64 (dd, 1H, J = 1Hz, 17.75H z), 5.07 (dd, 1H, J=1Hz, 11Hz), 4.01 (s, 3H)

<Synthesis of polyfunctional compound represented by formula (I-4)>

The mixture used in the reaction was a mixture of 18.31 g (1.8 mol) of 4-vinylphenol derived from the biomass obtained above, 10.00 g (1.0 mol) of succinic acid derived from biomass (manufactured by BASF), 200 ml of N-methylpyrrolidone (NMP), 41 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) as a coupling agent, and 1.03 g of dimethylaminopyridine (DMAP) as a co-catalyst. Except for this, various operations were carried out in the same manner as in Example 2 to obtain a polyfunctional compound represented by formula (I-4).

The resulting polyfunctional compound represented by formula (I-4) was subjected to ¹ H-NMR measurement and ¹³ C-NMR measurement, and the results are shown below.
¹ H-NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 7.42-7.39 (m, 4H), 7.07-7.04 (m, 4H), 6.69 (dd, 2H, J = 10.5Hz, 17.5Hz), 5.70 (dd, 2H, J = 0.5Hz) , 17.5Hz), 5.24 (dd, 2H, J=0.5Hz, 11Hz), 2.99 (s, 4H)
^13C -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 170.73, 150.06, 135.82, 135.47, 127.19, 121.53, 114.10, 29.26

The purity of the resulting polyfunctional compound represented by formula (I-4) was measured by HPLC. As a result, the purity was 99.01% by mass.

The resulting polyfunctional compound represented by formula (I-4) was subjected to melting point measurement and solubility evaluation. The results are shown in Table 1. Note that since the polyfunctional compound represented by formula (I-4) is a reaction product between biomass-derived components, the biomass content is 100%.

(Comparative Example 1)
<Synthesis of polyfunctional compound represented by formula (I-5)>

The mixture used in the reaction was a mixture of 17.32 g (1.8 mol) of the biomass-derived 4-vinylguaiacol obtained above, 10.00 g (1.0 mol) of biomass-derived 2,5-furandicarboxylic acid (GS Biotech), 200 ml of N-methylpyrrolidone (NMP), 37 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) as a coupling agent, and 0.78 g of dimethylaminopyridine (DMAP) as a co-catalyst. Except for this, various operations were carried out in the same manner as in Example 1 to obtain a polyfunctional compound represented by formula (I-5).

The resulting polyfunctional compound represented by formula (I-5) was subjected to ¹ H-NMR measurement and ¹³ C-NMR measurement, and the results are shown below.
^1H -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 7.47 (s, 2H), 7.12-7.02 (m, 6H), 6.70 (dd, 2H, J = 11Hz, 17.75Hz), 5.73 (dd, 2H, J = 0.5Hz, 17.5H z), 5.28 (d, 2H, J=11Hz), 3.86 (s, 6H)
^13C -NMR (500MHz, CDCl ₃ , TMS) δ [ppm] = 178.88, 155.75, 151.07, 146.57, 138.55, 137.19, 136.20, 122.68, 119.95, 118.99, 114.47, 110.02 ,55.9,49.44,30.70,29.60,17.67

The purity of the resulting polyfunctional compound represented by formula (I-5) was measured by HPLC. As a result, the purity was 98.8% by mass.

The resulting polyfunctional compound represented by formula (I-5) was subjected to melting point measurement and solubility evaluation. The results are shown in Table 1. Note that since the polyfunctional compound represented by formula (I-5) is a reaction product between biomass-derived components, the biomass content is 100%.

As is clear from Table 1, the polyfunctional compounds of Examples 1 to 4 are soluble in at least one organic solvent, and therefore have excellent solubility in organic solvents.

According to the present invention, it is possible to provide a polyfunctional compound having excellent solubility in organic solvents and a method for producing the same.
Furthermore, according to the present invention, there is provided a polymerizable composition containing the above polyfunctional compound.
Furthermore, according to the present invention, a cured product of the above polymerizable composition can be provided.

Claims (12)

The following formula (I):
CH ₂ =CH-(R ¹ ) _l -R ² -(R ³ ) _m -O-CO-R ⁴ -CO-O-(R ⁵ ) _n -R ⁶ -(R ⁷ ) _o -CH=CH ₂ (I)
[In formula (I),
R ¹ , R ³ , R ⁵ and R ⁷ each independently represent a hydrocarbon group which may have a substituent;
^R2 is an aromatic ring group which may have a substituent;
^R6 is an organic group;
^R4 is a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent;
l to o each independently represent 0 or 1.
A polyfunctional compound represented by the formula: The polyfunctional compound according to claim 1, wherein R ¹ , R ³ , R ⁵ and R ⁷ in the formula (I) are each independently an unsubstituted hydrocarbon group or a hydrocarbon group having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group and a carboxyl group. The polyfunctional compound according to claim 1 or 2, wherein l in formula (I) is 0. The polyfunctional compound according to any one of claims 1 to 3, wherein m in formula (I) is 0. R ⁶ in the formula (I) is an aromatic ring group which may have a substituent,
The polyfunctional compound according to any one of claims 1 to 4, wherein l to o in the formula (I) are 0. The polyfunctional compound according to any one of claims 1 to 5, wherein R ⁴ in the formula (I) is an unsubstituted hydrocarbon group having 2 to 22 carbon atoms, or a hydrocarbon group having 2 to 22 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an amino group, an alkoxy group, an ester group, an ether group, and a carboxyl group. The polyfunctional compound according to claim 6 , wherein R ⁴ in the formula (I) is a linear alkylene group having 2 to 22 carbon atoms. The polyfunctional compound according to any one of claims 1 to 7, having a biomass ratio of 50% or more. A method for producing the polyfunctional compound according to any one of claims 1 to 8, comprising the steps of:
The following formula (II):
HO-CO-R ⁴ -CO-OH (II)
[In formula (II), R ⁴ is the same as R ⁴ in formula (I)]
and a dicarboxylic acid represented by the formula:
A method for producing a polyfunctional compound by reacting a hydroxyl group-containing vinyl compound with The method for producing a polyfunctional compound according to claim 9, wherein at least one of the dicarboxylic acid and the hydroxyl group-containing vinyl compound is derived from biomass. A polymerizable composition comprising the polyfunctional compound according to any one of claims 1 to 8, a radical polymerizable monomer, and a radical initiator. A cured product of the polymerizable composition according to claim 11.