JP2021176934A - Polymerization method for vinyl monomer and vinyl polymer - Google Patents

Abstract

To provide a novel production method for a vinyl polymer that can readily provide a plurality of vinyl polymers that (a) are free from thioester groups and (b) have main chains of different compositions.SOLUTION: A method for producing a vinyl polymer has a cationic polymerization step in which, in the presence of a compound having a specific structure, a polymerizable monomer is subjected to cationic polymerization.SELECTED DRAWING: None

Description

The present invention relates to a method for polymerizing a vinyl-based monomer and a vinyl-based polymer.

Reversible Addition Fragmentation chain Transfer Polymerization (also referred to as RAFT polymerization) is known as one of the typical living radical polymerization methods (for example, Patent Documents 1 and 2).

Recently, molecular weight control by the RAFT mechanism has been achieved even in cationic polymerization (for example, Patent Document 3 and Non-Patent Documents 1 and 2). The techniques described in Patent Document 1 and Non-Patent Document 1 are techniques using a compound containing a thioester as a chain transfer agent. The technique described in Non-Patent Document 2 is a technique using vinyl ether as a monomer and a phosphorus atom-containing chain transfer agent as a chain transfer agent.

Japanese Unexamined Patent Publication No. 7-2954 Japanese Unexamined Patent Publication No. 2010-31159 Japanese Unexamined Patent Publication No. 2016-176042

Angew. Chem. Int. Ed. 2015, 54, 1924-1928. Polym. Chem. 2016, 7, 1387-1396

However, in the prior art as described above, (a) a vinyl-based polymer containing no thioester group can be easily obtained, and (b) the diversity of the main chain of the vinyl-based polymer (type of monomer to be polymerized). From the perspective of diversity, there was still room for improvement.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is (a) a plurality of vinyl-based weights having no thioester group and (b) main chains having various compositions. It is an object of the present invention to provide a novel method for producing a vinyl-based polymer, which can easily provide a coalescence.

As a result of diligent studies to solve the above problems, the present inventors have independently found that the above problems can be solved by having a step of cationically polymerizing a polymerizable monomer in the presence of a compound having a specific structure. We have found and completed the present invention.

That is, one embodiment of the present invention includes the following configurations.
[1] A method for producing a vinyl-based polymer, which comprises a cationic polymerization step of cationically polymerizing a polymerizable monomer in the presence of a compound having a structure represented by the following formula (1):

(In the formula (1), R ¹ is an independently monovalent organic group, n represents an integer from 0 to ^{5. R 2 to} R 5 are independently hydrogen or monovalent organic groups, respectively. It is.).
[2] The production method according to [1], wherein the polymerizable monomer is one or more selected from the group consisting of an isoolefin, a conjugated diene-based monomer, an aromatic vinyl-based monomer, and a vinyl ether. ..
[3] The production method according to [1] or [2], wherein in the formula (1), R ¹ is independently a methyl group, a methoxy group, a dimethylamino group or a diethylamino group.
[4] The cationic polymerization step is any one of [1] to [3], which is a step of cationically polymerizing the polymerizable monomer in the presence of a Bronsted acid component and / or a Lewis acid component. The manufacturing method described in.
[5] The structure represented by the following formula (2) or (3) is added to at least one end of the main chain, and the total of the structures represented by the following formulas (2) and (3) is 0. A vinyl polymer having 10 or more, measured by size exclusion chromatography, and having a number average molecular weight of 1000 to 1,000,000 converted to standard polystyrene:

(In formulas (2) and (3), R ¹ is an independently monovalent organic group, n represents an integer from 0 to 5, and R ^{2 to} R ⁵ are independently hydrogen or 1 respectively. It is an organic group of valence.).
[6] The vinyl-based polymer according to [5], wherein in the formulas (2) and (3), R ¹ is independently a methyl group, a methoxy group, a dimethylamino group or a diethylamino group.
[7] The structure according to [5] or [6], wherein the main chain has a structure derived from one or more selected from the group consisting of divalent polyisoolefins, polyaromatic vinyl-based polymers and polyvinyl ethers. Vinyl-based polymer.
[8] The vinyl-based polymer according to any one of [5] to [7], wherein the vinyl-based polymer has Mw / Mn of 1.00 to 2.00.
Here, the Mw is the weight average molecular weight of the vinyl polymer measured by size exclusion chromatography and converted into standard polystyrene.
The Mn is the number average molecular weight of the vinyl polymer measured by size exclusion chromatography and converted into standard polystyrene.
The Mw / Mn is the ratio of Mw to Mn.
[9] A compound having a structure represented by the following formula (4).

(In the formula (4), R ¹ is an independently monovalent organic group, and m represents an integer from 0 to 3. R ^{2 to R 7} are independently hydrogen or monovalent organic groups, respectively. Is.)

According to one embodiment of the present invention, there is an effect that (a) a plurality of kinds of vinyl-based polymers having no thioester group and (b) having main chains having various compositions can be easily provided.

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by combining the technical means disclosed in different embodiments or examples. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification. Further, unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".

[Technical Idea of One Embodiment of the Present Invention]
The present inventors have independently found that the techniques described in Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 described above still have room for improvement from the viewpoints described below.

In radical polymerization such as the techniques described in Patent Documents 1 and 2, there are restrictions on the monomers that can be used, for example, isobutylene cannot be polymerized by radical polymerization.

In the techniques described in Patent Document 3 and Non-Patent Document 1, since a compound containing a thioester is used as the chain transfer agent, the obtained polymer contains a thioester group at the end of the polymer. Since the thioester group causes coloring and / or odor, the polymers obtained by the techniques described in Patent Document 3 and Non-Patent Document 1 have room for further improvement from a practical point of view.

The technique described in Non-Patent Document 2 is a technique in which a chain transfer agent having no thioester group is used, but vinyl ether is used as a monomer.

That is, conventionally, there is no technique for cationic polymerization that can easily provide a polymer that uses an aromatic vinyl-based monomer such as styrene and / or an isoolefin as a monomer and does not contain a thioester group. Development was desired.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is (a) a plurality of kinds of vinyl-based vinyls which do not contain a thioester group and (b) have a main chain having various compositions. It is to provide a novel method for producing a vinyl-based polymer, and such a novel vinyl-based polymer, which can easily provide a polymer.

In addition, polymers having various reactive groups are desired because they can be widely and suitably used in applications such as sealants, pressure-sensitive adhesives, and adhesives. Conventionally, a polymer having a reactive group is produced through a complicated process such as forming a polymer skeleton by a living polymerization method and then introducing a reactive group into a specific portion of the polymer skeleton. Therefore, a method for producing a reactive group-containing polymer by a simple process has been still desired.

As described above, in the conventionally known RAFT polymerization, the thioester group remaining in the obtained polymer may become a problem. Therefore, a method of removing the thioester group from the obtained polymer after polymerization has been studied. For example, a method of treating a polymer obtained under basic conditions. However, this method has a problem that its use is limited depending on the chemical resistance of the polymer itself.

Against this background, the development of RAFT polymerization using a novel chain transfer agent that does not require treatment of residues derived from the chain transfer agent after polymerization has been desired. Further, as a monomer other than vinyl ether and (meth) acrylic acid ester, application to RAFT polymerization, particularly to isoolefins and aromatic vinyl-based monomers, still needs to be examined.

One embodiment of the present invention is preferably accomplished by (a) a novel cationic RAFT polymerization system in which functional groups derived from chain transfer agents do not impair the performance of the polymer, and (b) simple. An object of the present invention is to provide a novel functional group-containing polymer obtained by a production method.

[Method for producing vinyl polymer]
The method for producing a vinyl-based polymer according to an embodiment of the present invention includes a cationic polymerization step of cationically polymerizing a polymerizable monomer in the presence of a compound having a structure represented by the following formula (1):

(In the formula (1), R ¹ is an independently monovalent organic group, n represents an integer from 0 to ^{5. R 2 to} R 5 are independently hydrogen or monovalent organic groups, respectively. It is.).

The "method for producing a vinyl polymer according to an embodiment of the present invention" may be hereinafter referred to as "the present production method". The "step of cationically polymerizing a polymerizable monomer in the presence of a compound having the structure represented by the formula (1)" may be hereinafter referred to as a "cationic polymerization step". The "compound having the structure represented by the formula (1)" may be hereinafter referred to as "compound (1)".

Since this production method has the above-mentioned structure, it has an advantage that a plurality of kinds of vinyl polymers having (a) no thioester group and (b) main chains having various compositions can be easily provided. Specifically, this production method can be said to be a cationic polymerization method of a polymerizable monomer such as an isoolefin other than vinyl ether and / or an aromatic vinyl-based monomer. Further, in this production method, it is not necessary to use a compound having a functional group containing a hetero atom such as a thioester group and / or a phosphorus atom. The vinyl-based polymer obtained by this production method is a functional group derived from the compound (1) instead of the functional group containing a hetero atom such as a thioester group and / or a phosphorus atom possessed by the conventional vinyl-based polymer. Can have a group. The functional group derived from the compound (1) does not impair the performance of the obtained vinyl polymer. Therefore, the vinyl-based polymer obtained by this production method does not require a step of removing functional groups that may impair the performance of the vinyl-based polymer, such as functional groups containing thioester groups and / or heteroatoms. The functional group derived from compound (1) is a highly reactive reactive group. That is, this production method does not require complicated steps such as a step of removing functional groups that may impair the performance of the vinyl polymer, and can provide a vinyl polymer containing a reactive group by a simple process. .. The vinyl-based polymer obtained by this production method can be used not only as a macromonomer but also suitably used for applications such as pressure-sensitive adhesives, adhesives, sealants, resin modifiers, and molding materials.

(Polymerizable monomer)
The polymerizable monomer in one embodiment of the present invention is not particularly limited. Examples of the polymerizable monomer include one or more monomers selected from the group consisting of olefins having 2 to 20 carbon atoms, aromatic vinyl-based monomers, vinyl ethers, vinylsilanes, and allylsilanes. ..

Specific examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, butadiene (also known as 1,3-butadiene), 1-butene, 2-butene, isobutylene (also known as isobutene and 2-methylpropene), and isoprene (also known as isoprene). Alias; 2-methyl-1,3-butadiene), amylene (also known as 2-methyl-2-butene), 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1- Examples thereof include penten, hexene, vinylcyclohexene, α-pinene, β-pinene, limonene and the like. Isobutylene and isoprene are sometimes referred to as isoolefins. Butadiene and isoprene are also conjugated diene-based monomers.

Specific examples of aromatic vinyl-based monomers include styrene, inden, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, trimethylstyrene, chlorostyrene, dichlorostyrene, methoxystyrene, and dimethoxy. Examples thereof include styrene, hydroxystyrene, and acetoxystyrene.

Specific examples of the vinyl ether include (a) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, t-butyl vinyl ether, isobutyl vinyl ether, n-pentyl vinyl ether, and 1-methyl. Butyl vinyl ether, 2-methylbutyl vinyl ether, 3-methylbutyl vinyl ether, 1-ethylpropyl vinyl ether, 1,1-dimethylpropyl vinyl ether, 1,2-dimethylpropyl vinyl ether, 2,2-dimethylpropyl vinyl ether, n-hexyl vinyl ether, 1-Methylpentyl vinyl ether, 2-methylpentyl vinyl ether, 3-methylpentyl vinyl ether, 4-methylpentyl vinyl ether, 1-ethylbutyl vinyl ether, 2-ethylbutyl vinyl ether, 1,1-dimethylbutyl vinyl ether, 1,2-dimethylbutyl Vinyl ether, 1,3-dimethylbutyl vinyl ether, 2,2-dimethylbutyl vinyl ether, 2,3-dimethylbutyl vinyl ether, 3,3-dimethylbutyl vinyl ether, 1-methyl-1-ethylpropyl vinyl ether, 1-methyl-2- Alkyl vinyl ethers such as ethyl propyl vinyl ether, 2-methyl-1-ethyl propyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, n-undecyl vinyl ether, n-dodecyl vinyl ether; b) Fluoroalkyl vinyl ethers such as trifluoromethylvinyl ether, pentafluoroethyl vinyl ether, 2,2,2-trifluoroethyl vinyl ether; (c) 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-tetrahydrofuranyl vinyl ether, 2 -Alkoxyalkyl vinyl ethers such as tetrahydropyranyl vinyl ether; (d) cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether, cycloheptyl vinyl ether, cyclooctyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether; (e) phenylvinyl ether, 4 − Methylphenyl vinyl ether, 4-trifluoromethylphenyl vinyl ether, etc. Vinyl ethers; (f) aralkyl vinyl ethers such as benzyl vinyl ethers and 4-fluorobenzyl vinyl ethers; (b) alkylsilyl vinyl ethers such as trimethylsilyl vinyl ethers; and (h) isopropenyl ethers, and the like.

Specific examples of vinylsilanes and allylsilanes include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, and 1,3-divinyl. 1,1,3,3-Tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane , Diaryldimethylsilane and the like.

The polymerizable monomer is preferably one or more selected from the group consisting of isoolefins, conjugated diene-based monomers, aromatic vinyl-based monomers and vinyl ethers. According to this structure, the obtained vinyl polymer has an advantage of high industrial utility value. Further, the isoolefin, the conjugated diene-based monomer, the aromatic vinyl-based monomer and the vinyl ether also have an advantage that they are highly reactive and easily available.

Among these, polymerizable monomers include 1-butene, 2-butene, isobutylene, butadiene, isoprene, amylene, vinylcyclohexene, α-pinene, β-pinene, limonene, styrene, etc. One or more selected from the group consisting of α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, inden, methylvinyl ether, ethyl vinyl ether, isobutyl vinyl ether, adamantyl vinyl ether, vinyltrimethylsilane and allyltrimethylsilane. Is preferable.

Due to its high reactivity, the polymerizable monomers are isobutylene, butadiene, isoprene, α-pinene, β-pinene, limonene, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methyl. More preferably, it is one or more selected from the group consisting of styrene, inden, n-butyl vinyl ether, isobutyl vinyl ether, adamantyl vinyl ether, vinyl trimethyl silane and allyl trimethyl silane.

Since a vinyl-based polymer having high industrial availability can be obtained, the polymerizable monomers are isobutylene, butadiene, isoprene, α-pinene, β-pinene, limonene, styrene, α-methylstyrene, o-. More preferably, it is one or more selected from the group consisting of methylstyrene, m-methylstyrene, p-methylstyrene and inden.

Since the obtained vinyl-based polymer has high industrial utility value, the polymerizable monomers are isobutylene, butadiene, isoprene, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methyl. It is preferably one or more selected from the group consisting of styrene, inden, n-butyl vinyl ether, isobutyl vinyl ether and adamantyl vinyl ether.

One of these polymerizable monomers may be used alone, and two or more kinds of monomers may be mixed (combined) as long as the effect according to the embodiment of the present invention is not impaired. ) May be used. When two or more kinds of polymerizable monomers are mixed (combined) and used, the content of the main monomer capable of providing desired physical properties and / or performance is preferably 50% by weight or more. It is more preferably 80% by weight or more, and further preferably 90% by weight or more.

One or more singles selected from the group consisting of isoolefins, conjugated diene-based monomers, aromatic vinyl-based monomers and vinyl ethers in the total amount (100% by weight) of the polymerizable monomers used in this production method. The weight is preferably 50% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more.

In the total amount (100% by weight) of the polymerizable monomer used in this production method, isobutylene, butadiene, isoprene, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, inden, One or more monomers selected from the group consisting of n-butyl vinyl ether, isobutyl vinyl ether and adamantyl vinyl ether are preferably 50% by weight or more, more preferably 80% by weight or more, and 90% by weight or more. It is more preferable to have.

(Compound (1))
In this production method, compound (1) is used. Compound (1) can function as a chain transfer agent and impart living polymerization characteristics to the cationic polymerization system through a reversible addition-elimination chain transfer (RAFT) mechanism. Therefore, compound (1) can be said to be a RAFT agent. The "function of imparting the characteristics of living polymerization to the cationic polymerization system through the RAFT mechanism" in the compound (1) may be referred to as "function as a RAFT agent". In addition, a part of compound (1) may react during polymerization to act like a polymerizable monomer.

In the benzene ring described in the above formula (1), the carbon atom that is not bonded to ^{R 1 is bonded to the hydrogen atom.}

In the above formula (1), R ¹ is an independently monovalent organic group, and R ^{2 to} R ⁵ are independently hydrogen or a monovalent organic group, respectively. The term "independently" ^{intends that R 1} and R ^{2 to} R ⁵ may be the same or different, respectively. Further, when R ¹ is a plurality, the plurality of R ¹ may be the same, respectively, may be different.

A compound in which R ¹ is an independently monovalent organic group having 1 to 12 carbon atoms and R ^{2 to} R ⁵ are independently hydrogen or a monovalent organic group having 1 to 12 carbon atoms (1). ) Is easy to obtain. Therefore, in the above formula (1), R ¹ is an independently monovalent organic group having 1 to 12 carbon atoms, and R ^{2 to} R ⁵ are independently hydrogen or 1 to 12 carbon atoms, respectively. It is preferably a monovalent organic group. A compound in which R ¹ is an independently monovalent organic group having 1 to 4 carbon atoms and R ^{2 to} R ⁵ are independently hydrogen or a monovalent organic group having 1 to 4 carbon atoms (1). ) Is inexpensive to manufacture and / or obtain, and has excellent reactivity. Therefore, in the above formula (1), R ¹ is an independently monovalent organic group having 1 to 4 carbon atoms and R ^{2 to} R ^{5 because of its excellent balance between economy and reactivity.} Is more preferably hydrogen or a monovalent organic group having 1 to 4 carbon atoms, respectively.

Specific examples of the monovalent organic groups of R ^{1 to} R ⁵ include methyl group, ethyl group, propyl group, butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl. Examples thereof include a group, a phenyl group, a benzyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a benzyloxy group, a dimethylamino group, a diethylamino group, a methylthio group and an ethylthio group.

In the above formula (1), R ¹ is preferably a methyl group, a methoxy group, a dimethylamino group or a diethylamino group, respectively, and more preferably a methyl group, a methoxy group or a dimethylamino group. It is more preferably a methyl group or a methoxy group, and even more preferably a methyl group. The compound (1) having such a constitution has an advantage that the raw material of the compound (1) can be produced and / or obtained at low cost, and also has excellent reactivity as a RAFT agent.

In the above formula (1), n is preferably 0. The compound (1) having such a constitution has an advantage that not only the raw material of the compound (1) can be produced and / or obtained at a lower cost, but also the reactivity as a RAFT agent is superior.

In the above formula (1), R ^{2 to} R ⁵ are preferably hydrogen, methyl group, methoxy group, dimethylamino group or diethylamino group, respectively, and are hydrogen, methyl group, methoxy group or dimethylamino group. Is more preferable, hydrogen, a methyl group or a methoxy group is more preferable, and hydrogen or a methyl group is more preferable, and hydrogen is particularly preferable. The compound (1) having such a constitution has an advantage that the raw material of the compound (1) can be produced and / or obtained at low cost, and also has excellent reactivity as a RAFT agent.

The ^{compound (1) in which R 1} is an independent methyl group, a methoxy group or a dimethylamino group and R ^{2 to} R ⁵ are independently hydrogen, a methyl group, a methoxy group or a dimethylamino group can be produced. It's easy. Therefore, in the above formula (1), R ¹ is independently a methyl group, a methoxy group or a dimethylamino group, and R ^{2 to} R ⁵ are independently hydrogen, a methyl group, a methoxy group or a dimethyl amino group, respectively. It is preferably a group. Compound (1) in which R ¹ is an independent methyl group or a methoxy group and R ^{2 to} R ⁵ are independently hydrogen, a methyl group or a methoxy group is expensive to manufacture and / or obtain. cheap. Therefore, from the viewpoint of economy, in the above formula (1), R ¹ is an independent methyl group or a methoxy group, and R ^{2 to} R ⁵ are independently a hydrogen, a methyl group or a methoxy group, respectively. More preferably. Compound (1) in which R ¹ is a methyl group and R ^{2 to} R ⁵ are independently hydrogen or methyl groups can be inexpensively produced and / or obtained, and is handled from the viewpoint of compound stability. It has the advantage of being easy. Therefore, in the above formula (1), ^{it is more preferable that R 1} is a methyl group and R ^{2 to} R ⁵ are independently hydrogen or methyl groups, respectively.

The molecular weight of compound (1) is preferably 100 to 1,000, more preferably 200 to 700. According to this configuration, it is preferable from the viewpoint of cost effectiveness. That is, the compound (1) having the constitution is economical (cheap) to be produced, (b) is easy to handle, and (c) the concentration of the structure represented by the chemical formula (1) contained in the compound (1) is high. It is preferable because it is easy to obtain the effect according to one embodiment of the present invention because it is appropriate.

Compound (1) may have two or more structures represented by the above formula (1). The compound (1) is preferably a compound represented by the following formula (5) or (6):

(In the formula (5), X independently represents the formula (1), R ⁸ is an independent hydrogen or monovalent organic group, and o is an integer from 1 to 6. show.);

(In the formula (6), X independently represents the formula (1), o is an integer from 1 to 6, and R ⁹ and R ¹⁰ are independently hydrogen or monovalent. It is an organic group, and R ¹¹ is an o-valent organic group).

In the terms (5) and (6), the term "independently" means that when there are a plurality of ^{X and / or R 8 to} R ^{10 , the plurality of X and R 8 to} R ¹⁰ are the same. It is intended that it may or may not be different.

The "compound having the structure represented by the formula (5)" may be referred to as "compound (5)". The "compound having the structure represented by the formula (6)" may be referred to as "compound (6)". Compound (5) and compound (6) are included in compound (1).

Compound (5) has the advantage of being easy to manufacture and / or available at low cost. Since the compound (6) in which o is 2 to 6 is polyfunctional, a polybranched and / or polyfunctional vinyl-based polymer can be easily provided. Multi-branched and / or polyfunctional vinyl-based polymers have the advantage of high utility value in applications such as adhesives, pressure-sensitive adhesives, sealants, and elastomeric materials. Further, the compound (6) having an o of 2 to 3 is easier and cheaper to manufacture and / or obtain than the compound (6) having an o of 4 to 6. Therefore, from the viewpoint of the utility value and / or economy of the obtained vinyl polymer, o is preferably an integer of 2 to 6 in the above formula (6), and is an integer of 2 to 3 More preferably.

^{Regarding R 9 to} R ¹⁰ in the above formula (6), the ^{description regarding R 2 to} R ⁵ in the above formula (1) can be appropriately incorporated. That is, in the above formula (6), ^{the embodiments of R 9 to} R ¹⁰ include a preferable embodiment and a reason thereof, and are the same as the embodiments ^{of R 2 to} R ^{5 in the above formula (1).} Further, in the above formula (6), when R ⁹ and R ¹⁰ are independently monovalent organic groups, the carbon atom (C) to which ^{X and R 9 to} R ^{11 are bonded is quaternary.} It becomes. The compound (6) in which the carbon atom (C) to which X and R ^{9 to} R ¹¹ are bonded is quaternary is said to have high reactivity as a RAFT agent because the carbocation which is a reaction intermediate is easily stabilized. Has advantages. Therefore, in the above formula (6), ^{it is preferable that R 9 to} R ¹⁰ are independently monovalent organic groups.

In the above formula (5), R ⁸ is independently (a) hydrogen, methyl group, ethyl group, propyl group, butyl group, tert-butyl group, pentyl group, 2,2-dimethylpropyl group, hexyl. Group, heptyl group, octyl group, nonyl group, decyl group, 4-methylcyclohexyl group, 4-methyl-3-cyclohexenyl group, phenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4- (dimethylamino) ) Phenyl group, 4- (diethylamino) phenyl group, benzyl group, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, benzyloxy group, dimethylamino group, diethylamino group, methylthio group or ethylthio group Preferably, (b) hydrogen, methyl group, tert-butyl group, 2,2-dimethylpropyl group, 4-methylcyclohexyl group, 4-methyl-3-cyclohexenyl group, phenyl group, 4-methylphenyl group, 4- More preferably, it is a methoxyphenyl group, a 4- (dimethylamino) phenyl group, a 4- (diethylamino) phenyl group, a benzyl group, a methoxy group, a phenoxy group, a benzyloxy group, a dimethylamino group or a diethylamino group, (c). Hydrogen, methyl group, tert-butyl group, 2,2-dimethylpropyl group, 4-methylcyclohexyl group, 4-methyl-3-cyclohexenyl group, phenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4 It is particularly preferably a − (dimethylamino) phenyl group or a 4- (diethylamino) phenyl group. Compound (6) having this composition is excellent in reactivity as a RAFT agent. Therefore, when the compound (6) having the above-mentioned structure is used, there is an advantage that the polymerization is sufficiently controlled, and as a result, a vinyl-based polymer having a narrow molecular weight distribution can be obtained.

In the above formula (6), R ¹¹ is preferably an organic group having 1 to 15 carbon atoms, and more preferably has an aromatic ring. In the above formula (6), R ¹¹ preferably has a structure (organic group) represented by any one of the following formulas (7) to (14), and is preferably the formula (7), the formula (8) or the formula (8). The structure represented by the formulas (10) to (14) is more preferable, and the structure represented by the formulas (7), (10) to (12), or the formula (14) is particularly preferable. .. Compound (6) having this composition is excellent in reactivity as a RAFT agent. Therefore, when the compound (6) having the above-mentioned structure is used, there is an advantage that the polymerization is sufficiently controlled, and as a result, a vinyl-based polymer having a narrow molecular weight distribution can be obtained.

(In the above formulas (7) to (14), "*" represents a place where the structure (group) represented by the following formula (15) is bonded. In the above formula (11), "tBu" is tert. -Represents a butyl group.).

(In formula (15), X represents formula (1), and R ⁹ and R ¹⁰ are independently hydrogen or monovalent organic groups, respectively).

The compound (1) is preferably a compound represented by the following formula (4):

(In the formula (4), R ¹ is an independently monovalent organic group, and m represents an integer from 0 to 3. R ^{2 to R 7} are independently hydrogen or monovalent organic groups, respectively. Is.)
In the benzene rings according to the equation (4), the carbon atom which is not bonded to R ¹ or a methoxy group is bonded to a hydrogen atom.

The term "independently" in equation (4) ^{is intended that R 1} and R ^{2 to} R ⁷ may be the same or different, respectively. Further, when R ¹ is a plurality, the plurality of R ¹ may be the same, respectively, may be different.

The "compound having the structure represented by the formula (4)" may be referred to as "compound (4)". Compound (4) is included in compound (1).

Compound (4) has an advantage of being excellent in reactivity as a RAFT agent.

^R 1 to R ⁵ embodiment in the above formula (4), including the preferred embodiments and the reasons thereof are the same as embodiment of ^R 1 to R ⁵ in the above-mentioned equation (1). ^{Regarding R 6 to} R ⁷ in the above formula (4), the ^{description regarding R 2 to} R ⁵ in the above formula (1) can be appropriately incorporated. That is, in the above formula (4), ^{the embodiments of R 6 to} R ⁷ include preferable embodiments and their reasons, and are the same as the embodiments ^{of R 2 to} R ^{5 in the above formula (1).}

The compound (1) is preferably a compound represented by the following formula (16):

(In formula (16), R ¹ is an independently monovalent organic group, and n represents an integer from 0 to 5.)
In the benzene ring described in the above formula (16), the carbon atom that is not bonded to ^{R 1 is bonded to the hydrogen atom.}

The "compound having the structure represented by the formula (16)" may be referred to as "compound (16)". Compound (16) is included in compound (1). A part of the compound (16) is also a compound (4), and a part of the compound (4) is also a compound (16).

Compound (16) has an advantage of being excellent in reactivity as a RAFT agent.

Examples of the compound (1) that can be particularly preferably used in this production method include compounds having structures represented by the following formulas (17) to (33).

In the above formula (26), "tBu" represents a tert-butyl group.

The "compounds having the structures represented by the formulas (17) to (33)" may be referred to as compounds (17) to (24), respectively. Compound (17) to compound (22), compound (27), compound (30) and compound (31) are included in both compound (5) and compound (6). Compounds (17) to (22) are also included in compound (16). Compound (20) is included in both compound (4) and compound (16). Compound (23) to compound (26), compound (28) and compound (29) are included in compound (6). Compound (32) and compound (33) are included in compound (5). Compound (17) is also referred to as α-methylstyrene dimer.

Compounds (17) to (33) are readily available to manufacture and / or obtain. When the compounds (17) to (33) are used, the polymerization can be easily controlled, and a vinyl-based polymer having a narrow molecular weight distribution can be easily obtained. Therefore, it is more preferable that the compound (1) is one or more selected from the group consisting of the compound (17) to the compound (33) because the balance between economy and effect is excellent.

Compound (17), compound (19) and compound (20) are more readily available to manufacture and / or obtain. When the compound (17), the compound (19) and the compound (20) are used, the polymerization can be controlled more easily, and a vinyl-based polymer having a narrow molecular weight distribution can be more easily obtained. Furthermore, compound (17), compound (19) and compound (20) are applicable to the production of vinyl-based polymers using various monomers. Therefore, from the viewpoint of better balance between economy and effect, it is more preferable that the compound (1) is one or more selected from the group consisting of the compound (17), the compound (19) and the compound (20). .. Compound (17) is more easily produced and / or obtained, and has sufficient reactivity as a RAFT agent. Therefore, from the viewpoint of further excellent balance between the economy and the effect, the compound (1) is, n is 0, and the compound R ² to R ⁵ is hydrogen (17), that is α- methylstyrene dimer Is even more preferable.

The amount of the compound (1) used in the present production method is not particularly limited and can be appropriately set according to the molecular weight required for the obtained vinyl polymer. In this production method, the molar ratio of the total molar amount of the polymerizable monomer used to the total molar amount of the compound (1) used (the molar amount of the polymerizable monomer / the molar amount of the compound (1)) is , (5/1) to (20,000/1), more preferably (30/1) to (10,000/1), and (50/1) to (50/1) to It is more preferably in the range of (5,000/1). According to this configuration, there is an advantage that the effect on the control of the polymerization reaction and the economic efficiency are excellently balanced.

In the cationic polymerization step, the time at which the compound (1) is added to the system is not particularly limited as long as the compound (1) is added to the system at least before the completion of the cationic polymerization. In the cationic polymerization step, the compound (1) may be added to the system before the start of the cationic polymerization, or the compound (1) may be added to the system during the cationic polymerization.

In the cationic polymerization step, a case where the compound (1) is added to the system during the cationic polymerization will be described. In this case, there is no particular limitation on when (at what timing) the compound (1) is added to the system during cationic polymerization. When the compound (1) is added to the system during the cationic polymerization, the polymerizable monomer is present in the system in an amount of 10% by weight or more based on 100% by weight of the total amount of the polymerizable monomers used in the cationic polymerization. It is preferable that the time is 30% by weight or more, and more preferably 50% by weight or more. Since the operation of cationic polymerization is simple, it is particularly preferable to add (charge) compound (1) into the system before the start of cationic polymerization.

(Bronsted acid component and Lewis acid component)
In the cationic polymerization step, it is preferable to use the Bronsted acid component and / or the Lewis acid component together with the compound (1). In other words, the cationic polymerization step is preferably a step of cationically polymerizing the polymerizable monomer in the presence of a Bronsted acid component and / or a Lewis acid component. According to this configuration, a vinyl-based polymer having a narrow molecular weight distribution and a monomodal structure, that is, a small Mw / Mn can be easily obtained.

In the cationic polymerization step, the Bronsted acid component and the Lewis acid component can provide a cation that is a starting point for initiating the cationic polymerization. The Bronsted acid component and / or the Lewis acid component is not particularly limited as long as it has the ability to generate a cation, that is, to initiate cationic polymerization.

Specific examples of the blended acid component include hydrochloric acid, sulfuric acid, nitrate, phosphoric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, and fluoro. Examples thereof include sulfonic acid, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, perchloric acid and the like.

Specific examples of the Lewis acid component include (a) and (a-1) boron trifluoride, a complex of boron trifluoride (for example, a diethyl ether complex of boron trifluoride), boron trichloride, and boron trichloride. Complexes (eg, diethyl ether complex of boron trichloride), tin tetrachloride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, aluminum trichloride, aluminum halides such as aluminum tribromide, (a-2) TiCl Metal compounds having both halogen atoms and alkoxy groups on metals such as ₃ (OiPr), TiCl ₂ (OiPr) ₂ , TiCl (OiPr) _{3 , and (a-3) Et 2} AlCl, EtAlCl ₂ , Me ₂ Organic metal halides such as AlCl, MeAlCl ₂ , Et _1.5 AlCl _1.5 , Me _1.5 AlCl _1.5 , and (b) silver hexafluoroantimonate, silver hexafluorophosphate, silver trifluoromethanesulfonate. , Metal salts such as tetrakis (3,5-bis (trifluoromethyl) phenyl) sodium borate, and the like.

These Bronsted acid components and / or Lewis acid components may be used alone or in combination of two or more.

Among the above-mentioned blended acid components, (a) has a high ability to initiate cationic polymerization, is easily available, and is easy to handle. Therefore, hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, chlorosulfonic acid, and fluorosulfon. One or more selected from the group consisting of acid, perchloric acid and the like, and (b) one or more selected from the group consisting of hydrochloric acid, sulfuric acid and trifluoromethanesulfonic acid because they are more excellent in reactivity. Is more preferable.

Among the above-mentioned Lewis acid components, (a) a complex of boron trifluoride and boron trifluoride has a high ability to initiate cationic polymerization, is easily available, and is easy to handle. (For example, diethyl ether complex of boron trifluoride), boron trichloride, complex of boron trichloride (for example, diethyl ether complex of boron trichloride), tin tetrachloride, titanium tetrachloride, zinc dichloride, aluminum trichloride, etc. Metal halides of (a-2), metal compounds having both halogen atoms and alkoxy groups on metals such as _{TiCl 3} (OiPr), TiCl ₂ (OiPr) _{2 , and (a-3) Et 2} AlCl, It is preferably at least one selected from the group consisting of organic metal halides such as EtAlCl ₂ and Et _1.5 AlCl _{1.5, and preferably (b) tin tetrachloride because it is more excellent in reactivity.} , Titanium tetrachloride, aluminum trichloride, EtAlCl ₂ is more preferably one or more selected from the group.

The amount of the Bronsted acid component and / or the Lewis acid component used is not particularly limited. Since the ability to initiate cationic polymerization is excellent, the total amount of the Bronsted acid component and the Lewis acid component used is preferably in the range of 0.001 to 100 mol times with respect to 1 mol of the chain transfer agent, and is 0. It is more preferably in the range of .002 to 50 mol times, further preferably in the range of 0.005 to 10 mol times.

A case where a Lewis acid component is used in the cationic polymerization step will be described. In this case, a trace amount of water contained in each raw material in the cation polymerization step can react with the Lewis acid component to generate a cation. Further, in this case, in order to generate a cation, (a) intentionally water (water) is used in combination with the Lewis acid component, or (b) a protic compound such as an alcohol and / or a carboxylic acid, or , Compounds represented by the following formula (34) may be used in combination.

Z (Y) n (34)
(In formula (34), Z represents a monovalent or polyvalent aromatic hydrocarbon group or an aliphatic hydrocarbon group, and Y is selected from the group consisting of chlorine, bromine, iodine, methoxy group and acetoxy group. It represents one or more groups, where n represents a natural number.)
The "compound represented by the formula (34)" may be referred to as the compound (34). The compound (34) is not particularly limited. Specific examples of the compound (34) include milkyloride, (1-chloroethyl) benzene, p-methyl (1-chloroethyl) benzene, 4-methylmilkyloride, 4-tert-butyl-milkyloride, and m-dicumyl. Chloride, p-dikumilk lolide, 5-tert-butyl-1,3-dikumilk lolide, 5-methyl-1,3-dikumilk lolide, 1,3,5-trikumilk lolide, Cl- (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ C-Cl, Cl- (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ C-Cl, CH ₃ (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ C-Cl, cumylmethoxyde, (1-methoxyethyl) benzene, p-methyl (1-methoxyethyl) benzene, 4-methylcumylmethoxyd, 4-tert-butyl-cumylmethoxyd, m-dicumylmethoxyde, p. - dicumyl methoxide, 5-tert-butyl-1,3-dicumyl methoxide, 5-methyl-1,3-dicumyl methoxide, 1,3,5-tricumyl _methoxide, CH 3 O-( CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ C-OCH ₃ , CH _3- (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ C-OCH ₃ , CH ₃ O- (CH ₃₎ ) ₂ CCH ₂ (CH ₃ ) ₂ C-OCH ₃ , Cl-CH (CH ₃ ) -O-CH ₂ -CH (CH ₃ ) CH _{3 and} other compounds can be mentioned.

Among these, among these, cumylloride, m-dicumyllolide, p-dicumyllolide, 1,3,5-trikumilklolide, cumylmethoxydo, m-dicumylmethoxyde, p-dicumylmethoxyde, 1,3,5 -Tricumylmethoxydo, CH ₃ (CH ₃ ) ₂ CCH ₂ (CH ₃ ) ₂ C-Cl and Cl-CH (CH ₃ ) -O-CH ₂ -CH (CH ₃ ) CH ₃ are reactive and available It is particularly preferable in that respect.

The protonic compound is not particularly limited. Suitable examples of protonic compounds include (a) the above-mentioned protonic acid (breasted acid), (b) methanol, ethanol, propanol, butanol, octanol, decanol, butanthiol, octanethiol, decanethiol, butanediol, Examples thereof include alcohols such as octanediol, decanediol, butanedithiol, octanedithiol and decandithiol, and (c) thiol and the like.

The amount of compound (34) used is preferably in the range of 0.001 to 100 mol times, more preferably 0.002 to 50 mol times, with respect to 1 mol of compound (1). It is more preferably in the range of 0.005 to 10 mol times.

In the cationic polymerization step of the present production method, only the Bronsted acid component may be used, only the Lewis acid component may be used, or the Bronsted acid component and the Lewis acid component may be used in combination.

The Bronsted acid component is easier to produce and cheaper to obtain than the Lewis acid component and / or compound (34). Further, when the Bronsted acid component is used, there is an advantage that the obtained vinyl-based polymer can be easily and inexpensively purified. Therefore, from the viewpoint of economy, it is preferable to use only the Bronsted acid component or to use more Bronsted acid component than the Lewis acid component in the cationic polymerization step.

When the compound (34) is not used in the cationic polymerization step and the Lewis acid component is used, there is an advantage that a vinyl-based polymer can be produced at low cost. In general, compound (34) is often expensive as an industrial raw material. Therefore, from the viewpoint of inexpensively producing a vinyl-based polymer, it is preferable not to use the compound (34) in the cationic polymerization step. In other words, the cationic polymerization step is preferably a step of cationically polymerizing the polymerizable monomer in the presence of the Lewis acid component. On the other hand, from the viewpoint of obtaining a vinyl-based polymer having a specific structure and / or increasing the polymerization reaction rate of the vinyl-based polymer and improving the productivity, the compound (34) is Lewis in the cationic polymerization step. It is preferably used in combination with an acid component.

A case where the Lewis acid component is used in combination with the compound (34) in the cationic polymerization step will be described. In this case, since the multi-branched structure derived from the polyfunctional structure derived from the compound (34) can be formed in the polymer, there is an advantage that the structure of the obtained polymer is diversified and (b). ) It also has an advantage that a vinyl-based polymer having a narrow molecular weight distribution and a single peak, that is, a small Mw / Mn can be easily obtained. Further, in this case, after consuming an arbitrary monomer A as the first-step polymerization reaction, a monomer B different from the monomer A is added to the system as the second-step polymerization reaction. There is an advantage that block copolymers, triblock copolymers and multi-block copolymers can be easily obtained. The triblock copolymer and the multiblock copolymer have an advantage that they can be suitably used as a thermoplastic elastomer. Therefore, when producing a polymer having a multi-branched structure, the cationic polymerization step further cation-polymerizes the polymerizable monomer in the presence of the Lewis acid component and the compound represented by the formula (34). It is preferable that it is a step of causing.

(solvent)
The cationic polymerization step is preferably a step of cationically polymerizing the polymerizable monomer in an organic solvent. The organic solvent used in the cationic polymerization step is not particularly limited as long as it is inert to the reaction (cationic polymerization) and can dissolve the obtained vinyl-based polymer. For example, it is generally used in cationic polymerization. Examples of the organic solvent used in the above. Preferable examples of the organic solvent used in the cationic polymerization step include halogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.

Specific examples of halogenated hydrocarbons include methyl chloride, methylene chloride, propyl chloride, butyl chloride, pentyl chloride, hexyl chloride and the like.

Specific examples of aliphatic hydrocarbons and / or aromatic hydrocarbons include pentane, hexane, heptane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, ethylbenzene, xylene (including ortho-form, meta-form, para-form) and the like. Can be mentioned.

Specific examples of the ether include dimethyl ether, diethyl ether, methyl-tert-butyl-ether, diisopropyl ether and the like.

The organic solvent is methyl chloride, methylene chloride, butyl butyl chloride, hexane, because (a) the obtained vinyl-based polymer is excellent in solubility, and (b) is easily available and / or inexpensive. It is particularly preferable that it is at least one selected from the group consisting of cyclohexane, methylcyclohexane, ethylcyclohexane and toluene.

One type of these organic solvents may be used alone, or two or more types may be mixed (combined) and used. When two or more kinds of organic solvents are mixed (combined) and used, two or more kinds of arbitrary organic solvents are mixed at an arbitrary ratio from the viewpoint of solubility and reactivity of the obtained vinyl polymer. Can be used.

The amount of the polymerization solvent used is the reaction of the vinyl polymer obtained with respect to the reaction mixture (100% by weight) in consideration of the viscosity of the reaction mixture (reaction solution) and / or the ease of heat removal of the reaction mixture. The concentration in the mixture is preferably set to 1 to 50% by weight, more preferably 3 to 35% by weight.

(Electron donor component)
In the cationic polymerization step, an electron donor component may be used as needed, as long as the effect is not impaired. In other words, the cationic polymerization step may be a step of cationically polymerizing the polymerizable monomer in the presence of an electron donor component. When an electron donor component is used in the cationic polymerization step, (a) side reactions derived from impurities contained in the system can be suppressed and / or (b) the acidity of the Lewis acid component is appropriately reduced. This has the advantage that a rapid reaction can be suppressed and a manufacturing method that is easy to carry out industrially can be obtained.

The electron donor component is not particularly limited, and pyridines, amines, amides, sulfoxides, esters, metal compounds having an oxygen atom bonded to a metal atom, and the like can be preferably exemplified.

As the electron donor component, those having a donor number of 15 to 60 defined as a parameter indicating the strength of various compounds as an electron donor (electron donor) can be more preferably used. Therefore, examples of the electron donor component include pyridine, 2-methylpyridine, 2,6-dimethylpyridine, triethylamine, tributylamine, N, N-dimethylaminopyridine, N, N-dimethylformamide, N, N. -Dimethylacetamide, ethyl acetate, butyl acetate, titanium (IV) tetramethoxyde, titanium (IV) tetraisopropoxide, titanium (IV) butoxide and the like can be more preferably used.

Of these, 2-methylpyridine, 2,6-dimethylpyridine, triethylamine, N, N-dimethylformamide, N, N-dimethylacetamide, and titanium (IV) tetraisopropoxide are particularly effective in terms of addition effect and availability. preferable.

The electron donor component is usually preferably used in an amount of 0.001 to 100 times the total amount of substance (molar) of the Bronsted acid component and the Lewis acid component, and is removed or waste in the purification step after polymerization. From the viewpoint of reduction, it is more preferably used in the range of 0.01 to 50 times the molar amount.

(Polymerization temperature)
The temperature at which this cationic polymerization step is carried out (polymerization temperature) is not particularly limited. The cationic polymerization step is preferably carried out at −120 ° C. or higher and lower than 120 ° C. For example, in the cationic polymerization step, at a temperature of −120 ° C. or higher and lower than 120 ° C., (a) compound (1), Bronsted acid component and / or Lewis acid component, organic solvent and polymerizable monomer, and if necessary, It is preferable to mix the electron donor components and (b) cationically polymerize the polymerizable monomer. The cationic polymerization step is more preferably carried out at −100 ° C. to 50 ° C., further preferably at −80 ° C. to 0 ° C., because of its excellent energy cost and excellent stability of the polymerization reaction. It is even more preferable to carry out at 80 ° C. to −30 ° C. When the cationic polymerization step is carried out at (a) −120 ° C. or higher, there is no risk of the obtained vinyl-based polymer being precipitated, and when (b) is carried out at a temperature lower than 120 ° C., the rate of side reactions is reduced. It has an advantage that a vinyl-based polymer can be efficiently obtained.

In the present production method, it is preferable that the amount of the compound having a functional group containing a hetero atom such as a thioester group and / or a phosphorus atom is small. In this production method, the amount of the compound having a functional group containing a hetero atom such as a thioester group and / or a phosphorus atom is 0. It is preferably 01 mol% or less, more preferably 0.001 mol% or less, further preferably 0.0001 mol% or less, and particularly preferably 0.00001 mol% or less. In the present production method, it is most preferable not to use a compound having a functional group containing a hetero atom such as a thioester group and / or a phosphorus atom.

(others)
Specific embodiments other than the above-mentioned points regarding the cationic polymerization step are not particularly limited, and known embodiments can be adopted. A preferred embodiment of the cationic polymerization step is (a) a polymerizable simpler in the presence of compound (1) and a Bronsted acid component and / or Lewis acid component, and (b) optionally other additives. This is an embodiment in which the weight is cationically polymerized. The order of addition of the compound (1), the blended acid component and / or the Lewis acid component and the polymerizable monomer is as follows: (a) Compound (1), the polymerizable monomer, an organic solvent and optionally other additives. The blended acid component and / or the Lewis acid component is added to the solution containing, or (b) contains the compound (1), the Bronsted acid component and / or the Lewis acid component, an organic solvent and optionally other additives. It is preferable to add the polymerizable monomer to the solution, and the former aspect (the aspect (a)) is more preferable from the viewpoint of ease of operation.

The cationic polymerization step is preferably carried out in a dry nitrogen atmosphere or an inert gas atmosphere such as an argon atmosphere.

In the cationic polymerization step, for example, a small amount of sample is sampled from the reaction mixture being polymerized, and the polymerization conversion rate of the monomer that can be confirmed by measuring the sample by GC (gas chromatography) is used as a guide for cationic polymerization. The reaction can be stopped at any time.

In the cationic polymerization step, the cationic polymerization reaction is stopped after the polymerization conversion rate of the polymerizable monomer reaches preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 99 mol% or more.

The time (reaction time) of the cationic polymerization step is preferably 0.000001 hours to 100 hours, more preferably 0.00001 hours to 24 hours. The cationic polymerization step can be suitably carried out not only in a batch reactor but also in a continuous polymerization apparatus which has been studied in recent years. When the cationic polymerization step is carried out in a continuous polymerization apparatus having excellent heat dissipation of reaction heat, the cationic polymerization step can be completed within an extremely short time (for example, 0.00001 hours to 24 hours).

In the cationic polymerization step, when the polymerization reaction is completed, the polymerization is stopped with pure water and a protonic substance such as alcohol, and if necessary, the reaction mixture is washed with pure water and purified to obtain high purity. A vinyl-based polymer can be obtained.

The protonic substance may contain a basic compound such as ammonia and triethylamine.

The amount of the protonic substance used is preferably 1 mol or more with respect to 1 mol of the total of the Bronsted acid component and the Lewis acid component, and from the viewpoint of efficiently terminating the polymerization reaction, the Bronsted acid component and the Lewis acid component. More preferably, it is 10 mol or more with respect to 1 mol of the total components.

When a Bronsted acid component and / or a Lewis acid component is used in the cationic polymerization step, this production method decomposes (inactivates) the Bronsted acid component and the Lewis acid component after the cationic polymerization step. May further have. In the acid component decomposition step, water, alcohol, amine and the like are added to the reaction mixture after the end of the cationic polymerization step (after the completion of the polymerization reaction). Thereby, the Bronsted acid component and the Lewis acid component in the reaction mixture can be decomposed (inactivated). The higher the temperature of water, alcohol, amine, etc. added to the reaction mixture, the higher the effect of decomposing (inactivating) the Bronsted acid component and the Lewis acid component. Therefore, from the viewpoint of productivity, the acid component decomposition step is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher with respect to the reaction mixture after the end of the cationic polymerization step. A step of adding one or more selected from the group consisting of water, alcohol and amine at ° C. and above.

The method for isolating the vinyl polymer obtained by this production method is not particularly limited, and a method for distilling off a solvent from the reaction mixture after termination of polymerization and a method for adding the reaction mixture to a poor solvent are added. Examples thereof include a method of reprecipitating a vinyl-based polymer.

[Vinyl polymer]
The vinyl polymer according to the embodiment of the present invention has a structure represented by the following formula (2) or (3) at at least one end of the main chain, which is represented by the following formulas (2) and (3). The total number of structures is 0.10 or more in one molecule, and the number average molecular weight measured by size exclusion chromatography and converted into standard polystyrene is 1000 to 1,000,000.

(In formulas (2) and (3), R ¹ is an independently monovalent organic group, n represents an integer from 0 to 5, and R ^{2 to} R ⁵ are independently hydrogen or 1 respectively. It is an organic group of valence.).

In the benzene rings described in the above formulas (2) and (3), the ^{carbon atom not bonded to R 1} is bonded to a hydrogen atom.

The "vinyl-based polymer according to one embodiment of the present invention" may be hereinafter referred to as "the present vinyl-based polymer".

The structures (functional groups) represented by the formulas (2) and (3) are highly reactive. Therefore, this vinyl-based polymer has an advantage that it can be used as a macromonomer.

Hereinafter, each aspect of the vinyl-based polymer will be described, but the description in the section [Method for producing a vinyl-based polymer] is appropriately incorporated except for the matters described in detail below.

When the present vinyl-based polymer does not have a branched chain, the vinyl-based polymer has a structure represented by the formula (2) or (3), which is a total of one molecule of the structures represented by the formulas (2) and (3). Among them, (a) preferably has 0.20 or more, more preferably 0.30 or more, even more preferably 0.40 or more, and particularly preferably 0.50 or more. It is more preferably 0.70 or more, even more preferably 0.90 or more, most preferably 1.10 or more, and / or (b) 2.00 or less. ..

When the vinyl-based polymer has one branched chain, the vinyl-based polymer has the structure represented by the formula (2) or (3), and the total of the structures represented by the formulas (2) and (3) is one molecule. Among them, (a) preferably has 0.30 or more, more preferably 0.40 or more, even more preferably 0.60 or more, and particularly preferably 0.80 or more. 1. It is more preferable to have 10 or more, it is even more preferable to have 1.40 or more, it is most preferable to have 1.60 or more, and / or (b) 3.00 or less is preferable. ..

When the vinyl-based polymer has two branched chains, the vinyl-based polymer has the structure represented by the formula (2) or (3), and the total of the structures represented by the formulas (2) and (3) is one molecule. Among them, (a) preferably has 0.40 or more, more preferably 0.60 or more, even more preferably 0.80 or more, and particularly preferably 1.00 or more. It is more preferable to have 1.40 or more, even more preferably 1.80 or more, most preferably 2.20 or more, and / or (b) 4.0 or less. ..

The vinyl-based polymer preferably does not have a functional group containing a heteroatom such as a thioester group and / or a phosphorus atom. According to this configuration, the vinyl-based polymer fully exhibited the performance of the vinyl-based polymer without requiring a step of removing functional groups that could impair the performance of the vinyl-based polymer, for example, coloring and coloring. / Or it can be said that it is a practically excellent vinyl polymer having no odor.

(Main chain)
The vinyl polymer preferably has a structure in which the main chain is derived from one or more selected from the group consisting of divalent polyisoolefins, polyaromatic vinyl polymers and polyvinyl ethers. According to this configuration, there is an advantage that it can be suitably used as an industrially useful vinyl-based polymer in the fields of adhesives, pressure-sensitive adhesives, sealants, elastomer materials and the like. In the present specification, a structure containing 50 mol% or more of a structural unit derived from isoolefin and being divalent among all the structural units (100 mol%) constituting the structure is referred to as “polyisoolefin”. .. In the present specification, a structure containing 50 mol% or more of structural units derived from an aromatic vinyl-based monomer among all the structural units (100 mol%) constituting the structure is referred to as a "polyaromatic vinyl-based polymer". do. In the present specification, a structure containing 50 mol% or more of structural units derived from vinyl ether among all the structural units (100 mol%) constituting the structure is referred to as “polyvinyl ether”.

The main chain of this vinyl-based polymer has (a) a structure derived from a divalent polyisoolefin, and has a structure derived from a polyaromatic vinyl-based polymer and a structure derived from polyvinyl ether. It may not be necessary, and (b) it may not have a structure derived from a polyaromatic vinyl polymer and a structure derived from a divalent polyisoolefin and a structure derived from polyvinyl ether. (C) It does not have to have a structure derived from polyvinyl ether and a structure derived from a divalent polyisoolefin and a structure derived from a polyaromatic vinyl polymer, and (d) divalent. It does not have to have a structure derived from the polyisoolefin and a structure derived from the polyaromatic vinyl polymer and not having a structure derived from the polyvinyl ether, and the divalent polyisoolefin (e) It does not have to have a structure derived from a polyaromatic vinyl polymer and a structure derived from a polyvinyl ether, and (f) a structure derived from the polyaromatic vinyl polymer and a structure derived from the polyaromatic vinyl polymer. It does not have to have a structure derived from polyvinyl ether and a structure derived from a divalent polyisoolefin, and (g) a structure derived from a divalent polyisoolefin, a polyaromatic vinyl type. It may have a structure derived from a polymer and a structure derived from polyvinyl ether.

The main chain of this vinyl-based polymer may have only the structure derived from (a) divalent polyisoolefin, or (b) only the structure derived from the polyaromatic vinyl-based polymer. It may have (c) only a structure derived from polyvinyl ether, and (d) only a structure derived from a divalent polyisoolefin and a structure derived from a polyaromatic vinyl polymer. It may have (e) a structure derived from a divalent polyisoolefin and a structure derived from polyvinyl ether, and (f) a structure derived from a polyaromatic vinyl polymer. And may have only a structure derived from polyvinyl ether, and (g) only a structure derived from a divalent polyisoolefin, a structure derived from a polyaromatic vinyl polymer, and a structure derived from polyvinyl ether. You may have.

This vinyl polymer is derived from one or more selected from the group in which the main chain consists of polyisobutylene, polyisoprene, polybutadiene, polypinene, polystyrene, poly (α-methylstyrene), poly (methylstyrene) and polyinden. It is more preferable to have a structure. According to this configuration, there is an advantage that it can be more preferably used as an industrially useful vinyl-based polymer in the fields of adhesives, pressure-sensitive adhesives, sealants, elastomer materials and the like.

Examples of the vinyl-based polymer having a plurality of types of structures in the main chain include vinyl-based polymers which are block polymers as described later.

(Structure of vinyl polymer (random, block))
The vinyl-based polymer may be a random polymer, a block polymer, or a graft polymer. In the production of this vinyl-based polymer, two types of monomers (monomer (a) and monomer (b)) are used, and after the polymerization of one of the monomers is substantially completed, When the other monomer is reacted and polymerized, a block copolymer containing the polymer block (a) and the polymer block (b) can also be produced.

As a bonding mode of the polymer block (a) and the polymer block (b), examples of the linear structure include a diblock structure composed of (a)-(b) and (a)-(b)-(. Higher-order block structure higher than the triblock structure such as a) or (b)-(a)-(b), or the triblock structure such as (b)-(a)-(b)-(a)-(b) (Also called multi-block).

Further, as the bonding mode of the polymer block (a) and the polymer block (b), each polymer arm chain in the case of a branched and / or star-shaped structure has a diblock structure, a triblock structure, a multiblock structure, etc., respectively. Any of these can be selected.

As an example of a block copolymer, when a polymer block having a glass transition temperature above room temperature is referred to as a polymer block (a) and a polymer block having a glass transition temperature below room temperature is designated as a polymer block (b), The triblock copolymer having a)-(b)-(a) structure can be used as a thermoplastic elastomer, and can be suitably used as a pressure-sensitive adhesive, a sealant, a molding material, and the like. As used herein, "room temperature" is intended to be between 15 ° C and 25 ° C.

When such a thermoplastic elastomer is oriented, the content of the polymer block (a) is 10 to 50% by weight, and the content of the polymer block (b) is from the viewpoint of physical properties and / or ease of handling. It is preferably 50 to 90% by weight. When the content of the polymer block (a) is 10% by weight or more, the handleability at the time of processing is good, and the mechanical properties tend to be sufficient. On the other hand, when the content of the polymer block (a) is 50% by weight or less, the hardness does not become too high, and a polymer having excellent flexibility tends to be obtained.

On the other hand, the diblock copolymer having the structures (a)-(b) can be suitably used in the fields of pressure-sensitive adhesives and / or compatibilizers and the like.

Further, block copolymers having different structures may be mixed and used.

(Number average molecular weight)
The vinyl-based polymer preferably has a number average molecular weight of 1000 to 1,000,000 (g / mol) in terms of standard polystyrene measured by size exclusion chromatography (also referred to as SEC measurement or GPC measurement). More preferably, it is 000 to 500,000 (g / mol). When the number average molecular weight is 1000 (g / mol) or more, the characteristics of the vinyl polymer tend to be easily obtained. On the other hand, when the number average molecular weight is 1,000,000 (g / mol) or less, the vinyl polymer tends to be suitable in terms of ease of handling such as fluidity and processability.

(Molecular weight distribution)
This vinyl polymer has a molecular weight distribution (measured by size exclusion chromatography and the weight average molecular weight Mw of the vinyl polymer converted by standard polystyrene, measured by size exclusion chromatography and converted by standard polystyrene. The number expressed by the ratio (Mw / Mn) to the number average molecular weight Mn of the vinyl polymer) can reduce the viscosity of the vinyl polymer and is 1.00 to 2 from the viewpoint of ease of handling during processing. .00 is preferable, 1.05 to 1.80 is more preferable, 1.05 to 1.70 is more preferable, 1.05 to 1.60 is further preferable, and 1.05 to 1.50 is even more preferable. 1.05 to 1.40 is particularly preferable, and 1.05 to 1.30 is most preferable. Molecular weight distribution When the molecular weight distribution is 2.00 or less, the vinyl-based polymer tends to be easy to handle, and the characteristics of the vinyl-based polymer tend to be sufficiently obtained.

In this vinyl-based polymer, it is preferable that the peak of the molecular weight distribution is monomodal.

(Production method)
This vinyl-based polymer is preferably produced by the method described in [Method for producing vinyl-based polymer], that is, it is obtained by cationically polymerizing a polymerizable monomer in the presence of the chemical formula (1). Is preferable. When compound (1) is used, it is not necessary to use a compound having a functional group containing a hetero atom such as a thioester group and / or a phosphorus atom. Therefore, a thioester residue or the like is essentially absent at the end of the main chain of the vinyl polymer, and instead, the structure (α-methylstyryl) represented by the formula (2) or (3) derived from the compound (1) is present. It is characterized by having a skeleton). As a result, various problems such as coloring and / or odor, which have been problems of the conventional vinyl polymer, do not occur. Further, since the vinyl-based polymer having the structure is generated in the system during the polymerization, the vinyl-based polymer obtained after the polymerization also has the structure (α-methylstyryl skeleton) represented by the formula (2) or (3). )have. The structure (α-methylstyryl skeleton) represented by the formula (2) or (3) has activity against various reactions such as radical polymerization, anionic polymerization, cationic polymerization, hydrosilylation, and various transition metal-catalyzed reactions. .. As a result, the present vinyl-based polymer can be suitably used as a reactive polymer without going through a functionalization step as conventionally known.

This vinyl-based polymer can be produced by a method other than the method described in [Method for producing vinyl-based polymer]. For example, the present vinyl-based polymer can be obtained by reacting a vinyl-based polymer obtained by a conventionally known cationic polymerization method (preferably a living cationic polymerization method) with the chemical formula (1). In this case, after forming the main chain (polymer skeleton) of the vinyl-based polymer by a conventionally known living cation polymerization method, the chemical formula (1) may be added to the same reactor and the reaction may be continued in one pot. After the polymerization is completed, the catalyst may be deactivated to isolate the vinyl polymer once, and the vinyl polymer and the chemical formula (1) may be added to another reactor for reaction.

[Compound (4)]
The compound according to one embodiment of the present invention has a structure represented by the following formula (4).

(In the formula (4), R ¹ is an independently monovalent organic group, and m represents an integer from 0 to 3. R ^{2 to R 7} are independently hydrogen or monovalent organic groups, respectively. Is.)
In the benzene rings according to the equation (4), the carbon atom which is not bonded to R ¹ or a methoxy group is bonded to a hydrogen atom.

The compound having the structure represented by the formula (4), that is, the compound (4) can be suitably used in the cationic polymerization of the polymerizable monomer. Specifically, compound (4) can be suitably used in living cationic polymerization of a polymerizable monomer. When compound (4) is used in polymerizable monomeric cationic polymerization, compound (4) functions as a chain transfer agent and is characterized by living polymerization in a cationic polymerization system through a reversible addition-desorption chain transfer (RAFT) mechanism. Can be granted. Further, when the compound (4) is used in the polymerizable monomer cationic polymerization, a part of the compound (4) may react during the polymerization to act like a polymerizable monomer. Compound (4) can also be referred to as a chain transfer agent and a RAFT agent. That is, one embodiment of the present invention can be said to be a chain transfer agent having a structure represented by the formula (4) and a RAFT agent having a structure represented by the formula (4).

Regarding the above-mentioned polymerizable monomer, the description in the section (Polymerable monomer) of [Method for producing a vinyl-based polymer] can be appropriately incorporated. That is, the mode of the polymerizable monomer includes a preferable mode, and may be the same as the mode described in the section (Polymeric monomer) of [Method for producing a vinyl-based polymer].

The compound (4) can be suitably used for cationic polymerization of one or more monomers selected from the group consisting of aromatic vinyl-based monomers among the polymerizable monomers, and is styrene or α-methylstyrene. , O-Methylstyrene, m-methylstyrene, p-methylstyrene, can be suitably used by cationic polymerization of one or more monomers selected from the group, and is particularly suitable for cationic polymerization of α-methylstyrene. Can be used. That is, one embodiment of the present invention is a chain transfer agent for cationic polymerization of an aromatic vinyl-based monomer having a structure represented by the formula (4), and an aromatic having a structure represented by the formula (4). It can also be said to be a RAFT agent for cationic polymerization of vinyl-based monomers.

The compound (4) is particularly preferably the compound (11) described above.

The method for producing the compound (4) is not particularly limited. Taking compound (11) as an example of compound (4), an example of a preferable production method of compound (4) (compound (11)) will be described. For compound (4) (compound (11)), (1) the gas in the flask is replaced with nitrogen, (2) 3,4-dimethoxy-α-methylstyrene and toluene are charged in the flask, and these are mixed. Then, (3) p-toluenesulfonic acid monohydrate was added to the system, and the reaction mixture was brought to 20 ° C. to start the reaction. (4) After reacting for a certain period of time, a small amount Methanol containing ammonia was added to the system to terminate the reaction, (5) then the reaction mixture was diluted with diethyl ether and washed with pure water to remove impurities, and (6) finally the solvent was reduced under reduced pressure. It can be obtained by distilling off.

〔Composition〕
One embodiment of the present invention is a vinyl-based polymer produced by the method for producing a vinyl-based polymer according to the section [Method for producing a vinyl-based polymer], and / or a section of [Vinyl-based polymer]. A composition containing the present vinyl-based polymer described in the above is also provided. The "composition according to one embodiment of the present invention" is also hereinafter referred to as "the present composition".

Since this composition has the above-mentioned structure, there is no possibility of coloring and / or generation of odor. Therefore, this composition can be suitably used for various uses described in [Use] described later.

The composition is not particularly limited as long as it contains the vinyl-based polymer produced by the present production method and / or the present vinyl-based polymer. The present composition preferably contains, in total, 20% by weight or more, preferably 30% by weight, of the vinyl-based polymer produced by the present production method and / or the present vinyl-based polymer in 100% by weight of the composition. It is more preferable to contain more than 40% by weight, more preferably 40% by weight or more, and particularly preferably 50% by weight or more. According to this structure, the advantage of a polymer having a narrow molecular weight distribution is utilized, and the obtained composition has an advantage that the viscosity is low and a composition that is easy to handle can be obtained.

The present composition may be a curable resin composition, and may contain a curing agent and a curing catalyst. The curing agent and curing catalyst contained in the present composition are not particularly limited and may be appropriately selected from known substances according to the type of functional group contained in the vinyl polymer contained in the present composition.

The present composition may contain various compounding agents in order to improve the physical characteristics according to the desired physical characteristics. The compounding agent is not particularly limited, and examples thereof include known thermoplastic resins, rubbers, thermoplastic elastomers, composite rubber particles, stabilizers, plasticizers, lubricants, flame retardants, pigments, fillers, and the like. ..

The present composition is known to include (a) a vinyl-based polymer produced by the present production method and / or the present vinyl-based polymer, and (b) a curing agent, a curing catalyst, and various compounding agents, if necessary. It can be produced by mixing by the method. Suitable examples of the apparatus used for producing the present composition include a Banbury mixer, a roll mill, and a twin-screw extruder.

[Use]
The uses of the vinyl-based polymer, the present vinyl-based polymer, and the present composition obtained by the present production method are not particularly limited, but the following uses are preferably mentioned. That is, the vinyl-based polymer, the present vinyl-based polymer, and the present composition obtained by the present production method are a sealing material, a sealing material, a coating material, a potting material, a fixing gasket, an in-situ molded gasket, an adhesive, an adhesive, and the like. It can be suitably used for various applications such as fillers, polymers, foams, films, casting materials, inks, anti-vibration materials, anti-vibration materials, sound-insulating materials, seismic isolation materials, dampers and gaskets.

The vinyl-based polymer, the present vinyl-based polymer, and the present composition obtained by the present production method can be suitably used for electric and electronic applications. In electrical and electronic applications, for example, LED materials, various battery peripheral materials, sensors, semiconductor peripheral materials, circuit board peripheral materials, display peripheral materials such as liquid crystal displays, optical communication and optical circuit peripheral materials, optical recording peripheral materials, magnetic recording. It can be used as a material.

As the LED material, it can be suitably used as a molding material, a sealing material, a sealing film, a die bond material, a coating material, a sealing material, an adhesive, an adhesive, a lens material and the like of an LED element. As the LED material, it can be suitably used for LED bulbs, LED indicator lamps, LED display boards, sealing materials for LED indicators and the like, adhesives, adhesives, coating materials and the like.

Battery peripheral materials include lithium ion batteries, sodium batteries, sulfur batteries, sodium molten salt batteries, nickel hydrogen batteries, nickel cadmium batteries, redox flow batteries, lithium sulfur batteries, air batteries, electrolytic capacitors, electric double layer capacitors, and lithium ions. Sealing materials for capacitors, fuel cells, solar batteries, dye-sensitized solar cells, etc., backside encapsulants, molding materials for each element, adhesives, adhesives, encapsulants, encapsulating films, coating materials, potting materials, It can be suitably used for fillers, separators, catalyst fixing films, protective films, electrode binders, refrigerant oil sealing materials, hose materials, and the like.

Sensors include force, load, pressure, rotation, vibration, flow rate, solar radiation, light, odor, time, temperature, humidity, wind speed, distance, position, inertia, inclination, speed, acceleration, angular velocity, hardness, distortion, sound.・ Magnetic, current, voltage, power, electron, radiation, infrared, X-ray, ultraviolet, liquid amount, weight, gas amount, ion amount, metal amount, color, etc. Encapsulant, encapsulating film, lens material for various sensors , Adhesives, adhesives, coating agents, films and the like.

Circuit board peripheral materials include rigid, flexible wiring boards or MEMS (microelectromechanical system) sealing materials on which various elements such as ICs, LSIs, semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, and coils are mounted. , Coating material, Potting material, Molding material for each of the above elements, Underfill material, Die bond material, Die bonding film, Adhesive, Adhesive, Encapsulant, Encapsulating film.

As display peripheral materials, molds for each element such as liquid crystal display, plasma display, LED display device, organic EL (electroluminescence) display, field emission display, electronic paper, flexible display, 3D hologram, organic thin film display, and head mount display. Materials, various filters, protective films, antireflection films, viewing angle correction films, polarizing element protective films, optical correction films and other films, sealants, adhesives, adhesives, encapsulants, encapsulants, substrates and members It can be suitably used as a coating material, a potting material, a filler, a visibility improving material, a lens material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, and a liquid crystal dam material.

Optical communication and optical circuit peripheral materials include organic photorefractive elements, optical fibers, optical switches, lenses, optical waveguides, light emitting elements, photodiodes, optical amplification elements, optical electron integrated circuits, optical connectors, optical couplers, optical arithmetic elements, and photoelectric devices. Molding materials, sealing materials, adhesives, adhesives, sealing materials, sealing films, coating materials, potting materials, fillers, protective films, lens materials, light guide plates, prisms for each element such as converters and laser elements. It can be suitably used as a sheet, a polarizing plate, and a ferrule.

Examples of optical recording materials include VD (video disc), CD, CD-ROM, CD-R, CD-RW, DVD, DVD-ROM, DVD-R, DVD-RW, BD, BD-ROM, BD-R, BD-RE, MO, MD, PD (Phase Change Disc), Hologram, Disc Substrate Material for Optical Cards, Protective Films for Pickup Lenses, Sealing Materials, Adhesives, Adhesives, Encapsulants, Encapsulating Films, Coatings It can be suitably used as a material, a vibration isolator, and a vibration damping material.

As a magnetic recording material, it is suitable as a vibration isolator, a vibration damping material, a sealing material, an adhesive, an adhesive, a sealing material, a coating material, a cover gasket, and a card material for magnetic cards such as hard disks, magnetic tapes, and credit cards. It is available.

In addition, antifouling film for touch panel, lubricating film, mold material for IC chip, mold material for Perche element, sealant for electrolytic capacitor, cable joint potting material, potting material for IGBT (vehicle propulsion control device), semiconductor wafer processing Dying tape, die bond agent, die bond film, underfill, anisotropic conductive adhesive, anisotropic conductive film, conductive adhesive, conductive paste, heat conductive adhesive, heat conductive paste, temporary fixing film, It can be suitably used for a fixing film, a sealing film, and the like.

In automobile applications, as body parts, it can be suitably used as a sealing material for maintaining airtightness, a vibration preventing material for glass, a vibration isolating material for a vehicle body part, particularly a wind seal gasket and a gasket for door glass. As a chassis component, it can be suitably used for an engine and suspension rubber for vibration isolation and soundproofing, particularly an engine mount rubber and a sealing material for vibration isolation mount. As engine parts, it can be suitably used for hoses for cooling, fuel supply, exhaust control, gaskets for engine covers and oil pans, sealing materials for engine oil, and the like. Further, as the tire parts, in addition to the bead portion, the sidewall portion, the shoulder portion, and the tread portion, it can be suitably used as a resin for an inner liner or a sealing material for an air pressure sensor and a puncture sensor. Further, it can be suitably used as a sealing material, a sealing material, a gasket, a coating material, a molding member, an adhesive, and an adhesive for various electronic parts and control parts. Further, it can be suitably used as a covering material for copper and aluminum wire harnesses and a sealing material for a connector portion. In addition, lamps, batteries, window washer fluid units, air conditioner units, coolant units, brake oil units, electrical components, various interior and exterior parts, sealing materials for oil filters, adhesives, adhesives, gaskets, O-rings and packing, It can also be suitably used as a molded part such as a belt, a potting material for an igniter HIC or a hybrid IC for automobiles, and the like.

In industrial applications, it can be suitably used for resist applications such as permanent resist applications, solder resist applications, dry film resist applications, and electrodeposition resist applications.

As information and electrical equipment, sealing materials for mobile phones, media players, tablet terminals, smartphones, portable game machines, computers, printers, scanners, projectors, inkjet tanks, etc., sealing materials, adhesives, adhesives, packings, O-rings, etc. It can be suitably used for belts, anti-vibration materials, anti-vibration materials, sound-insulating materials, and the like.

Various recorders such as TVs, Blu-ray recorders and HDD recorders in the home appliances field, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, FAX, copy machines, telephones, doorphones, rice cookers, Microwave oven, microwave oven, refrigerator, dishwasher, dishwasher, IH cooking heater, hot plate, vacuum cleaner, washing machine, charger, sewing machine, iron, dryer, electric bicycle, air purifier, water purifier, electric toothbrush, For various electric products such as lighting equipment, air conditioners, outdoor units of air conditioners, dehumidifiers, humidifiers, etc., for sealing materials, adhesives, adhesives, packings, O-rings, belts, vibration isolators, vibration damping materials, soundproofing materials, etc. It is preferably available.

For leisure use, it can be suitably used for swimming members such as swimming caps, diving masks and earplugs, gel cushioning members such as sports shoes and baseball gloves, adhesives for golf balls, clubs and rackets, and shock absorbers. be.

As a molded body, it can be suitably used for packings, O-rings, belts, tubes, hoses, valves, seats and the like.

In addition, reactive hot melt adhesives for wiring connectors, reactive hot melt adhesives, OCA (transparent optical adhesives), elastic adhesives, contact adhesives, anaerobic adhesives, ultraviolet curable adhesives, electron beam curable It can be suitably used as various adhesives such as adhesives.

It can be suitably used as various adhesives for modifying butyl adhesives, masking tapes, pipe anticorrosion tapes, construction waterproof tapes, self-bonding tapes for electricity, adhesives for re-peeling, fusion tapes for electric wires, etc. be.

Various coating applications such as electric wire, cable coating material or its repair material, insulation sealing material for wiring, in-pipe lining material for gas pipes, water pipes, etc., inorganic filler, organic filler coating material, epoxy mold release material, etc. Can be suitably used for.

It can be suitably used as various sheets such as a heat conductive sheet, a heat radiating sheet, an electromagnetic wave absorbing sheet, a conductive sheet, a waterproof sheet, a protective sheet for automobiles, and a shock absorbing sheet for panels.

In addition, shock absorbing gels, shock absorbing materials such as beds and shoes, laminated glass interlayer films, elastic paints, paints such as water-based emulsions, prepregs, various rollers for OA equipment and transportation, cap liners, ink repellents, etc. It can be suitably used as a sealing material for inks, various refrigerants, a sealing material and gasket for industrial cans and food cans, a foam gasket, a primary seal for laminated glass, and a secondary seal. For medical applications, transdermal absorbents and adhesives for application, pharmaceutical and medical sealants, medical adhesives, medical rubber stoppers, impression materials, dental fillers, syringe gaskets, and vacuum vascular rubber stoppers, artificial For O-rings or flat gaskets for dialysis machines, packaging materials for pharmaceuticals and medical devices, caps, cap liners, caps for vacuum blood collection tubes, sealants and adhesives for catheters, sealants and adhesives for implantable medical devices, etc. It is preferably available.

For damping materials and damping materials, stepping motors, magnetic disks, hard disks, dishwashers, dryers, washing machines, fan heaters, sewing machines, vending machines, speaker frames, BS antennas, damping materials for VTR covers, etc. For electrical and electronic equipment applications; roofs, floors, shutters, curtain rails, floors, piping ducts, deck plates, curtain walls, stairs, doors, vibration isolation isolators, vibration damping materials for structural materials, viscous elastic dampers, seismic mats, etc. Construction applications; Ship applications such as damping materials for engine rooms and measurement rooms; Engines (oil pans, front covers, rocker covers), vehicle bodies (dashes, floors, doors, roofs, panels, wheel houses), transmissions, parking brake covers , Automotive applications such as seat back damping materials; Camera / office equipment applications such as TV cameras, copying machines, computers, printers, registers, cabinet damping materials; Shooters, elevators, escalator, conveyors, tractors, bulldozers, Industrial machinery-related applications such as generators, compressors, containers, hoppers, soundproof boxes, and damping materials for motor covers of mowing machines; It can be suitably used as a vibration damping material for precision vibration damping devices for railway applications, semiconductor applications, etc .; as a soundproofing material for low-frequency sound and high-frequency sound near the audible range threshold.

Hereinafter, one embodiment of the present invention will be specifically described with reference to Examples. The present invention is not limited to the following examples.

First, the method for analyzing the vinyl polymer obtained in the examples will be described below.

(Polymerization conversion rate)
In the production of vinyl-based polymers, the conversion rate of the polymerizable monomer to the vinyl-based polymer polymer is determined by gas chromatography (Gas Chromatograph, GC (manufactured by Agent Technologies, 7890B)) or a proton nuclear magnetic resonance apparatus ( ^1). Measurement was performed using H Nuclear Magnetic Resonance, ¹ H NMR (manufactured by JEOL Ltd., ECS-400). HP-1 manufactured by Agilent Technologies was used as the GC column.

(Molecular weight measurement)
The "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn))" of a vinyl polymer are determined by Size Exclusion Chromatography (SEC). ) Was calculated by the standard polystyrene conversion method.

As the SEC measuring device, a GPC system manufactured by Waters was used. As the measurement conditions for SEC, chloroform was used as the mobile phase and the column temperature was 35 ° C. As a sample, a solution in which the vinyl polymer was dissolved in chloroform so that the concentration of the vinyl polymer was 4 mg / ml was used. Regarding the results obtained by SEC, hereinafter, the peak top molecular weight is also expressed as Mp, the number average molecular weight is Mn, the weight average molecular weight is Mw, and the molecular weight distribution is Mw / Mn.

(Calculation of the number of structures (Fn) represented by the formulas (2) and (3) at the ends of the main chain of the vinyl polymer)
The structure represented by the formulas (2) and (3) at the end of the main chain of the vinyl polymer, in other words, the number of functional groups (Fn) derived from the compound (1) introduced into the vinyl polymer is determined. It was calculated as follows. First, the molecular weight of the vinyl polymer was calculated by the above SEC measurement, and the number average molecular weight (Mn) was determined. ^{Next, 1} H NMR measurement of the vinyl polymer was performed. In the obtained ¹ H NMR chart, the integrated value (area) of the peaks attributed to the two methyl groups in the polyisobutylene skeleton near 1.3 ppm was calculated using the value of the number average molecular weight Mn in the following equation. As per.
(Integral value of peak near 1.3 ppm) = ((number average molecular weight Mn) / 56.11) x 6H.

At the same time, in the above ¹ H NMR chart, the area of the peak derived from the exomethylene group appearing near 5.0 ppm and 5.2 ppm was determined, and the average integrated value was taken as the functional group number Fn.

(Comparative Example 1) Polymerization of Isobutylene Hexane and dichloromethane were mixed at a volume ratio (hexane / dichloromethane) of 6/4 to prepare a hexane / dichloromethane mixed solvent at room temperature. After replacing the gas in the 25 mL flask with nitrogen, 0.95 mL (10.0 mmol) of isobutylene and 3.55 mL of the hexane / dichloromethane mixed solvent were charged into the flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.50 mL (0.10 mmol) of titanium tetrachloride (dichloromethane solution of titanium tetrachloride 200 mM) was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 210 minutes from the start of the polymerization, 1.00 mL of methanol containing a small amount of ammonia was added to the system to terminate the polymerization. The reaction mixture was diluted with 50 mL of hexane and washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (X-1) (Mn = 100,700, Mw). / Mn = 6.23).

(Example 1) Cationic RAFT polymerization of isobutylene After replacing the gas in a 25 mL flask with nitrogen, 0.95 mL (10.0 mmol) of isobutylene, α-methylstyrene dimer (α-methylstyrene dimer) which is compound (7). 0.17 mL (0.16 mmol) of 927 mM toluene solution) and 3.38 mL of the above hexane / dichloromethane mixed solvent were placed in a flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.50 mL (0.10 mmol) of titanium tetrachloride (dichloromethane solution of titanium tetrachloride 200 mM) as a Lewis acid component was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 20 hours from the start of the polymerization, 1.00 mL of methanol containing a small amount of ammonia was added to the system to terminate the polymerization. The reaction mixture was diluted with 50 mL of hexane and washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-1) (Mn = 5,400, Mw /). Mn = 1.55 and monomodal, Fn = 1.23). The main chain of the obtained vinyl polymer (P-1) had a structure derived from polyisobutylene, which is a divalent polyisoolefin. Further, the obtained vinyl polymer (P-1) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

From the results of Comparative Example 1 and Example 1, when the compound (7) included in the compound (1) was not used, the Mw / Mn of the obtained vinyl polymer (X-1) was 6.23. , It can be seen that the free cationic polymerization of isobutylene proceeded. On the other hand, in Example 1 using the compound (7) included in the compound (1), the obtained vinyl-based polymer (P-1) had a monomodal molecular weight distribution with a Mw / Mn of 1.55. From the above, it can be seen that the living cationic polymerization has proceeded. Further, in the obtained vinyl polymer (P-1), an α-methylstyryl skeleton having a structure represented by the formula (2) or (3) is contained in one molecule at the end of the main chain of the vinyl polymer. 1.23 were introduced in.

(Example 2) Cationic RAFT polymerization of isobutylene After replacing the gas in a 25 mL flask with nitrogen, 0.95 mL (10.0 mmol) of isobutylene, α-methylstyrene dimer (α-methylstyrene dimer) which is compound (7). 54.0 μL (50.0 μmol) of a 927 mM toluene solution) and 3.50 mL of the above hexane / dichloromethane mixed solvent were placed in a flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.50 mL (0.10 mmol) of titanium tetrachloride (dichloromethane solution of titanium tetrachloride 200 mM) as a Lewis acid component was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 10 hours from the start of the polymerization, 1.00 mL of methanol containing a small amount of ammonia was added to the system to terminate the polymerization. The reaction mixture was diluted with 50 mL of hexane and washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-2) (Mn = 14,300, Mw /). Mn = 1.90 and monomodal, Fn = 1.12). The main chain of the obtained vinyl polymer (P-2) had a structure derived from polyisobutylene, which is a divalent polyisoolefin. Further, the obtained vinyl-based polymer (P-2) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

(Example 3) Cationic RAFT polymerization of isobutylene After replacing the gas in a 25 mL flask with nitrogen, 0.95 mL (10.0 mmol) of isobutylene, α-methylstyrene dimer (α-methylstyrene dimer) which is compound (7). 0.50 mL (20.0 μmol) of a 40.0 mM toluene solution and 3.05 mL of the above hexane / dichloromethane mixed solvent were placed in a flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.50 mL (0.10 mmol) of titanium tetrachloride (dichloromethane solution of titanium tetrachloride 200 mM) as a Lewis acid component was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 24 hours from the start of the polymerization, 1.00 mL of methanol containing a small amount of ammonia was added to the system to terminate the polymerization. The reaction mixture was diluted with 50 mL of hexane and washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-3) (Mn = 30,300, Mw /). Mn = 1.66 and monomodal, Fn = 0.81). The main chain of the obtained vinyl polymer (P-3) had a structure derived from polyisobutylene, which is a divalent polyisoolefin. Further, the obtained vinyl polymer (P-3) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

(Example 4) Cationic RAFT polymerization of isobutylene After replacing the gas in a 25 mL flask with nitrogen, 0.95 mL (10.0 mmol) of isobutylene, α-methylstyrene dimer (α-methylstyrene dimer) which is compound (7). 0.50 mL (10.0 μmol) of 20.0 mM toluene solution) and 3.05 mL of the above hexane / dichloromethane mixed solvent were placed in a flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.50 mL (0.10 mmol) of titanium tetrachloride (dichloromethane solution of titanium tetrachloride 200 mM) as a Lewis acid component was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 20 hours from the start of the polymerization, 1.00 mL of methanol containing a small amount of ammonia was added to the system to terminate the polymerization. The reaction mixture was diluted with 50 mL of hexane and washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-4) (Mn = 53,600, Mw /). Mn = 1.62 and monomodal, Fn = 0.63). The main chain of the obtained vinyl polymer (P-4) had a structure derived from polyisobutylene, which is a divalent polyisoolefin. Further, the obtained vinyl polymer (P-4) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

From these results, according to the present production method, according to the present production method, there is no odor and / or coloring due to the functional group derived from the chain transfer agent, that is, the functional group derived from the chain transfer agent has the performance of the polymer. It can be seen that a vinyl-based polymer that does not impair can be provided by a simple production method. Further, the molecular weight distribution of the obtained vinyl polymer is significantly narrower and monomodal than the molecular weight distribution of the vinyl polymer obtained by free cationic polymerization, and living cationic polymerization is proceeding. You can see that. As described above, according to this production method, it has become possible to carry out cationic RAFT polymerization of a polymerizable monomer (particularly, isobutylene which is an isoolefin).

Next, polymerization was carried out by coexisting p-diquemilk lolide, which is generally used as a polymerization initiator in living cationic polymerization, with compound (1).

(Comparative Example 2) Polymerization of Isobutylene Butyl chloride and hexane were mixed at a volume ratio (butyl chloride / hexane) of 9/1 to prepare a butyl chloride / hexane mixed solvent at room temperature. After substituting the gas in the 500 mL flask with nitrogen, 100 mL (1.06 mol) of isobutylene, 0.245 g (1.06 mmol) of p-dicumyl lolide and 216 mL of the above butyl chloride / hexane mixed solvent are charged into the flask and mixed. bottom. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.58 mmL (5.30 mmol) of titanium tetrachloride was added to the system in the flask to initiate polymerization.

After stirring the reaction mixture for 2 hours from the start of polymerization, the reaction mixture was added to a mixture of 500 g of pure water heated to 50 ° C. and 200 g of the above butyl chloride / hexane mixed solvent, and obtained at 50 ° C. for 2 hours. The reaction mixture was stirred. After that, stirring was stopped and the reaction mixture was allowed to stand to separate the organic phase and the aqueous phase, and the aqueous phase was discarded. Subsequently, the obtained organic phase was washed twice with 500 g of pure water. The solvent was distilled off under reduced pressure to obtain a vinyl polymer (X-2) (Mn = 41,367, Mw / Mn = 2.14).

(Example 5) Cationic RAFT polymerization of isobutylene After substituting the gas in a 500 mL flask with nitrogen, 100 mL (1.06 mol) of isobutylene, 0.245 g (1.06 mmol) of p-dicmilk lolide, and compound (7) are used. 2.53 mL (10.6 mmol) of a certain α-methylstyrene polymer and 216 mL of the above butyl chloride / hexane mixed solvent were charged into a flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.58 mL (5.30 mmol) of titanium tetrachloride as a Lewis acid component was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 2 hours from the start of polymerization, the reaction mixture was added to a mixture of 500 g of pure water heated to 50 ° C. and 200 g of the above butyl chloride / hexane mixed solvent, and obtained at 50 ° C. for 2 hours. The reaction mixture was stirred. After that, stirring was stopped and the reaction mixture was allowed to stand to separate the organic phase and the aqueous phase, and the aqueous phase was discarded. Subsequently, the obtained organic phase was washed twice with 500 g of pure water. The solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-5) (Mn = 7,234, Mw / Mn = 1.42 and monomodal). The main chain of the obtained vinyl polymer (P-5) had a structure derived from polyisobutylene, which is a divalent polyisoolefin. Further, the obtained vinyl polymer (P-5) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

In Comparative Example 2 in which p-diquemilk lolide, which is generally used as a polymerization initiator in living cationic polymerization, was used and compound (1) was not used, the obtained vinyl-based polymer (X-2) was used. Mw / Mn was 2.14, indicating a multimodal molecular weight distribution. On the other hand, in Example 2 in which p-dimethylyl lolide, which is generally used as a polymerization initiator in living cationic polymerization, was used and compound (1) was also used, the obtained vinyl-based polymer (P-2) was used. Mw / Mn was 1.42 and showed a monomodal molecular weight distribution. From this, it can be seen that the controlled cationic polymerization, that is, the living cationic polymerization proceeded even when p-dicumyl lolide was allowed to coexist with the compound (1).

Next, a block copolymer was produced using isobutylene and styrene as polymerizable monomers in the coexistence of p-dimeric glycolide and compound (1).

(Example 6) Production of block copolymerization of isobutylene and styrene by cation RAFT polymerization After replacing the gas in a 500 mL flask with nitrogen, 100 mL (1.06 mol) of isobutylene and 0.245 g (1) of p-dikumilk lolide are used. .06 mmol), 2.53 mL (10.6 mmol) of α-methylstyrene dimer as compound (7), and 216 mL of the above butyl chloride / hexane mixed solvent were charged into a flask and mixed. Subsequently, the mixture in the flask was cooled to about −78 ° C. Next, 0.58 mL (5.30 mmol) of titanium tetrachloride as a Lewis acid component was added to the system in the flask to initiate polymerization. After stirring the reaction mixture for 2 hours from the start of polymerization, a small amount of the reaction mixture was sampled for various analyses. When the residual amount of isobutylene in the system was quantified by gas chromatography using the obtained sample, it was 1% by weight or less of the isobutylene used (100% by weight). Then 15 ml of styrene was added to the system in the flask. Immediately after the addition of styrene, 15 minutes and 30 minutes later, a small amount of the reaction mixture was sampled for analysis. After 120 minutes from the start of the polymerization, the reaction mixture was added to a mixture of 500 g of pure water heated to 50 ° C. and 200 g of the above butyl chloride / hexane mixed solvent, and the reaction mixture was stirred at 50 ° C. for 2 hours. After that, stirring was stopped and the reaction mixture was allowed to stand to separate the organic phase and the aqueous phase, and the aqueous phase was discarded. Subsequently, the obtained organic phase was washed twice with 500 g of pure water. The solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-6) (Mp = 18,859, Mn = 11,475, Mw / Mn = 1.81 and monomodal). The main chain of the obtained vinyl-based polymer (P-6) has a structure derived from polyisobutylene, which is a divalent polyisoolefin, and a structure derived from polystyrene, which is a polyaromatic vinyl-based polymer. Was. Further, the obtained vinyl polymer (P-6) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

The sixth embodiment will be described below. It can be considered that the residual amount of isobutylene is 1% by weight or less of the charged amount (100% by weight) 2 hours after the start of the polymerization and that the polymerization of isobutylene is completed 2 hours after the start of the polymerization. When the polymerization of isobutylene was completed, the peak top molecular weight of the vinyl polymer was Mp = 10,115, the number average molecular weight was Mn = 7,234, and the molecular weight distribution was Mw / Mn = 1.42. When 15 minutes had passed after the addition of styrene, the peak top molecular weight of the vinyl polymer was Mp = 12,687, the number average molecular weight was Mn = 9,317, and the molecular weight distribution was Mw / Mn = 1.75. When 30 minutes had passed after the addition of styrene, the peak top molecular weight of the vinyl polymer was Mp = 14,678, the number average molecular weight was Mn = 10,313, and the molecular weight distribution was Mw / Mn = 1.71.

From this result, it can be seen that a block copolymer of isobutylene and styrene was obtained in Example 6.

Next, the compounds (10) and (11) were synthesized, and cationic RAFT polymerization using α-methylstyrene as a polymerizable monomer was carried out.

(Production Example 1) Synthesis of compound (10) After replacing the gas in a 25 mL flask with nitrogen, 5.16 g (34.8 mmol) of 4-methoxy-α-methylstyrene and 6.00 mL of toluene were charged in the flask. , Mixed. Next, 60.0 mg (0.32 mmol) of p-toluenesulfonic acid monohydrate was added to the system, and the reaction mixture was brought to 20 ° C. to initiate the reaction. After stirring the reaction mixture for 50 minutes from the start of the reaction, 1.50 mL of methanol containing a small amount of ammonia was added to the system to stop the reaction. The reaction mixture was diluted with 50 mL of hexane, washed with pure water to remove impurities, and then the solvent was evaporated under reduced pressure. Next, hexane and diethyl ether were mixed in a volume ratio (hexane / diethyl ether) (19/1) to prepare a hexane / diethyl ether mixed solution. The obtained product was purified using the silica gel column using the above hexane / diethyl ether mixed solution as an eluent to obtain compound (10) (1.75 g, 5.90 mmol) (yield 34). %).

(Production Example 2) Synthesis of compound (11) After replacing the gas in a 25 mL flask with nitrogen, 4.32 g (24.5 mmol) of 3,4-dimethoxy-α-methylstyrene and 3.81 mL of toluene were added to the flask. And mixed. Next, 42.2 mg (0.22 mmol) of p-toluenesulfonic acid monohydrate was added to the system, and the reaction mixture was brought to 20 ° C. to initiate the reaction. After stirring the reaction mixture for 2 hours from the start of the reaction, 1.50 mL of methanol containing a small amount of ammonia was added to the system to stop the reaction. The reaction mixture was diluted with 50 mL of diethyl ether, washed with pure water to remove impurities, and then the solvent was evaporated under reduced pressure. The obtained product was purified using the silica gel column using the above hexane / diethyl ether mixed solution as an eluent to obtain compound (11) (1.41 g, 4.00 mmol) (yield 33). %).

(Example 7) Cationic RAFT polymerization of α-methylstyrene using compound (10) After replacing the gas in a 25 mL flask with nitrogen, 0.20 mL (1.54 mmol) of α-methylstyrene, compound (10). (Compound (10) 525 mM toluene solution) 0.06 mL (31.5 μmol), 0.10 mL of 1,2-dichlorobenzene and 2.34 mL of dichloromethane were charged into a flask and mixed. Subsequently, the mixture in the flask was cooled to about −40 ° C. Next, (a) a hydrogen chloride adduct of isobutyl vinyl ether as compound (34), (b) silver hexafluoroantimonate as a Lewis acid component, and (c) dichloromethane are mixed, and a hydrogen chloride adduct of isobutyl vinyl ether is mixed. A dichloromethane solution (hereinafter referred to as mixed solution A) containing 5 mM each of and silver hexafluoroantimonate was prepared. Next, 0.30 mL of the mixed solution A (that is, corresponding to 1.50 μmol each of the hydrogen chloride adduct of isobutyl vinyl ether and silver hexafluoroantimonate) was added to the system to initiate polymerization. After stirring the reaction mixture for 2 hours from the start of the polymerization, 1.50 mL of methanol containing a small amount of ammonia was added to the system to stop the reaction. The reaction mixture was diluted with 50 mL of toluene, washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-7) (Mn = 4,200, Mw). / Mn = 1.38 and monomodal, Fn = 0.12). The main chain of the obtained vinyl-based polymer (P-7) had a structure derived from poly-α-methylstyrene, which is a poly-aromatic vinyl-based polymer. Further, the obtained vinyl polymer (P-7) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

(Example 8) Cationic RAFT polymerization of α-methylstyrene using compound (10) (example using _{SnCl 4)}
Dichloromethane and methylcyclohexane were mixed in a volume ratio (dichloromethane / methylcyclohexane) (1/1) to prepare a mixed solvent of dichloromethane / methylcyclohexane at room temperature. After replacing the inside of the 25 mL flask with nitrogen, 0.20 mL (1.54 mmol) of α-methylstyrene, 0.06 mL (31.5 μmol) of compound (10) (toluene solution of compound (10) 525 mM), 1, 0.05 mL of 2-dichlorobenzene and 2.39 mL of the above dichloromethane / methylcyclohexane mixed solvent were charged into a flask and mixed. Subsequently, the mixture in the flask was cooled to about −40 ° C. Next, 0.30 mL of tin tetrachloride solution (dichloromethane solution of tin tetrachloride 10.0 mM) (equivalent to 3.00 μmol of tin tetrachloride) was added to the system as a Lewis acid component to initiate polymerization. After stirring the reaction mixture for 150 minutes from the start of the polymerization, 1.50 mL of methanol containing a small amount of ammonia was added to the system to stop the reaction. The reaction mixture was diluted with 50 mL of toluene, washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-8) (Mn = 5,100, Mw). / Mn = 1.35 and monomodal, Fn = 0.53). The main chain of the obtained vinyl-based polymer (P-8) had a structure derived from poly-α-methylstyrene, which is a poly-aromatic vinyl-based polymer. Further, the obtained vinyl polymer (P-8) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

(Example 9) Cationic RAFT polymerization of α-methylstyrene using compound (11) After replacing the gas in a 25 mL flask with nitrogen, 0.20 mL (1.54 mmol) of α-methylstyrene, compound (11). (Compound (11) 538 mM toluene solution) 0.06 mL (32.3 μmol), 1,2-dichlorobenzene 0.05 mL and dichloromethane 2.39 mL were charged into a flask and mixed. Subsequently, the mixture in the flask was cooled to about −40 ° C. Next, 0.30 mL of the mixed solution A (that is, 1.50 μmol each of hydrogen chloride adduct of isobutyl vinyl ether and silver hexafluoroantimonate) was added to the system to initiate polymerization. After stirring the reaction mixture for 20 minutes from the start of the polymerization, 1.50 mL of methanol containing a small amount of ammonia was added to the system to stop the reaction. The reaction mixture was diluted with 50 mL of toluene, washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a vinyl polymer (P-9) (Mn = 12,300, Mw). / Mn = 1.97 and monomodal, Fn = 0.63). The main chain of the obtained vinyl-based polymer (P-9) had a structure derived from poly-α-methylstyrene, which is a poly-aromatic vinyl-based polymer. Further, the obtained vinyl polymer (P-9) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

(Comparative Example 3) Cationic polymerization of α-methylstyrene After replacing the gas in a 25 mL flask with nitrogen, 0.20 mL (1.54 mmol) of α-methylstyrene, 0.05 mL of 1,2-dichlorobenzene and dichloromethane 2 .45 mL was placed in a flask and mixed. Subsequently, the mixture in the flask was cooled to about −40 ° C. Next, 0.30 mL of the mixed solution A (that is, 1.50 μmol each of hydrogen chloride adduct of isobutyl vinyl ether and silver hexafluoroantimonate) was added to the system to initiate polymerization. After stirring for 5 seconds from the start of the polymerization, 1.50 mL of methanol containing a small amount of ammonia was added to the system to stop the reaction. The reaction mixture was diluted with 50 mL of toluene, washed with pure water to remove impurities, and then the solvent was distilled off under reduced pressure to obtain a polymer (X-3) (Mn = 19,000, Mw / Mn). = 2.23).

From the results of Examples 7 to 9 and Comparative Example 3, when compound (10) and compound (11) were used, cationic RAFT polymerization of α-methylstyrene, which is an aromatic vinyl-based monomer, proceeded and the molecular weight distribution was distributed. It was found that a narrow vinyl-based polymer can be obtained.

Next, it was examined to react the obtained vinyl-based polymer with the compound (1) after the polymerization of the monomer was substantially completed.

(Example 10) Synthesis of polyisobutylene having an α-methylstyryl group at the end After replacing the gas in a 500 mL flask with nitrogen, 122 mL (1.29 mol) of isobutylene and 2.30 g (9. 95 mmol), 0.30 ml (2.59 mmol) of 2,6-dimethylpyridine and 414 mL of the above butyl chloride / hexane mixed solvent were placed in a flask and mixed. Subsequently, the mixture in the flask was cooled to about −70 ° C. Next, 0.82 mL (7.46 mmol) of titanium tetrachloride as Lewis acid was added to the system in the flask to initiate polymerization. When the polymerization conversion rate of isobutylene was determined by GC measurement 1 hour after the start of polymerization, the polymerization conversion rate was 99.6% by weight. From this, it was found that 99.6% by weight of isobutylene charged in the system was consumed to become polyisobutylene. After further stirring the mixture in the flask for about 20 minutes from this point, it was determined that the polymerization of isobutylene was substantially completed.

Next, 11.9 mL (49.7 mmol) of α-methylstyrene dimer of compound (7) was added to the system, and stirring of the reaction mixture was continued for another 1 hour at the same temperature (−70 ° C.). In parallel with stirring the reaction mixture, 500 g of pure water and the above-mentioned butyl chloride / hexane mixed solvent were added to another flask, and the mixture in the flask was heated with stirring and heated to 50 ° C. Then, the entire amount of the reaction mixture for which stirring was completed was added to the mixture of pure water and the butyl chloride / hexane mixed solvent in the above-mentioned separate flask. The resulting reaction mixture was then stirred at 50 ° C. for 1 hour to inactivate the catalyst. After that, the stirring of the reaction mixture was stopped, and the reaction mixture was allowed to stand to separate the organic phase and the aqueous phase, and the aqueous phase was discarded. Subsequently, the obtained organic phase was washed twice with 500 g of pure water. The solvent was distilled off from the washed organic phase under reduced pressure to obtain a vinyl polymer (P-10) (Mn = 8,307, Mw / Mn = 1.34 and monomodal, Fn = 0). .127). The main chain of the obtained vinyl polymer (P-10) had a structure derived from polyisobutylene, which is a divalent polyisoolefin. Further, the obtained vinyl-based polymer (P-10) was a colorless and transparent liquid resin, did not contain a thioester group, and did not have a characteristic odor derived from a sulfur atom or the like.

From Example 10, the obtained vinyl-based polymer (P-10) has an α-methylstyryl skeleton having a structure represented by the formula (2) or (3) at the end of the main chain of the vinyl-based polymer. It was found that 0.127 were introduced into one molecule. Therefore, the vinyl-based polymer according to the embodiment of the present invention can also be obtained by reacting the obtained vinyl-based polymer with the compound (1) after the polymerization of the monomer is substantially completed. I found that I could do it.

According to one embodiment of the present invention, it is possible to easily provide a plurality of types of vinyl polymers having (a) no thioester group and (b) main chains having various compositions. Therefore, one embodiment of the present invention includes sealing materials, encapsulants, coating materials, potting materials, fixing gaskets, on-site molded gaskets, adhesives, adhesives, fillers, molded bodies, foams, films, castings. It can be suitably used for various applications such as materials, inks, anti-vibration materials, anti-vibration materials, sound-insulating materials, seismic isolation materials, dampers, and gaskets.

Claims (9)

A method for producing a vinyl-based polymer, which comprises a cationic polymerization step of cationically polymerizing a polymerizable monomer in the presence of a compound having a structure represented by the following formula (1):

(In the formula (1), R ¹ is an independently monovalent organic group, n represents an integer from 0 to ^{5. R 2 to} R 5 are independently hydrogen or monovalent organic groups, respectively. It is.). The production method according to claim 1, wherein the polymerizable monomer is one or more selected from the group consisting of an isoolefin, a conjugated diene-based monomer, an aromatic vinyl-based monomer, and a vinyl ether. The production method according to claim 1 or 2, wherein in the formula (1), R ¹ is independently a methyl group, a methoxy group, a dimethylamino group or a diethylamino group. The production method according to any one of claims 1 to 3, wherein the cationic polymerization step is a step of cationically polymerizing a polymerizable monomer in the presence of a Bronsted acid component and / or a Lewis acid component. .. At least one end of the main chain has the structures represented by the following formulas (2) or (3), and the total of the structures represented by the following formulas (2) and (3) is 0.10 or more in one molecule. Have and
Vinyl-based polymers measured by size exclusion chromatography and converted to standard polystyrene with a number average molecular weight of 1000-1,000,000:

(In formulas (2) and (3), R ¹ is an independently monovalent organic group, n represents an integer from 0 to 5, and R ^{2 to} R ⁵ are independently hydrogen or 1 respectively. It is an organic group of valence.). The vinyl-based polymer according to claim 5, wherein in the formulas (2) and (3), R ¹ is independently a methyl group, a methoxy group, a dimethylamino group or a diethylamino group. The vinyl polymer according to claim 5 or 6, wherein the main chain has a structure derived from one or more selected from the group consisting of a divalent polyisoolefin, a polyaromatic vinyl polymer and a polyvinyl ether. .. The vinyl polymer according to any one of claims 5 to 7, wherein the vinyl polymer has Mw / Mn of 1.00 to 2.00.
Here, the Mw is the weight average molecular weight of the vinyl polymer measured by size exclusion chromatography and converted into standard polystyrene.
The Mn is the number average molecular weight of the vinyl polymer measured by size exclusion chromatography and converted into standard polystyrene.
The Mw / Mn is the ratio of Mw to Mn. A compound having a structure represented by the following formula (4).

(In the formula (4), R ¹ is an independently monovalent organic group, and m represents an integer from 0 to 3. R ^{2 to R 7} are independently hydrogen or monovalent organic groups, respectively. Is.)