JP2014047287A - Living cationic polymerization initiator system, and production method of polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a block copolymer of a cationic polymerizable vinyl monomer and a radical polymerizable vinyl monomer.SOLUTION: Provided is an initiator system that is used for living cationic polymerization of a cationic polymerizable vinyl monomer. A polymer subjected to cationic polymerization is subjected to living radical polymerization of at least one vinyl monomer under a living cationic polymerization initiator that includes: a proton acid (component (A)); and an RAFT cationic agent of the formula (1) (Ris a Calkyl group that may branch; Ris a Calkylene group that may branch; Ris a substitutable alkyl group, aryl group, arylalkyl group, alkylthio group, arylthio group, arylalkylthio group or acylamino group; Q is O or S; and p is 0, 1 or 2), and under the absence of a metal lewis acid.

Description

  The present invention relates to a method for producing a block copolymer of a cationically polymerizable vinyl monomer and a radically polymerizable vinyl monomer. More specifically, the present invention relates to a method for producing a polymer that is a reversible addition-cleavage chain transfer agent capable of radical polymerization by metal-free living cationic polymerization in which cationic polymerization is performed with a protonic acid without using a metal Lewis acid, The present invention relates to a polymer obtained by the method and a method for producing a block copolymer in which a radically polymerizable vinyl monomer is polymerized from the polymer.

  Alkenyl ethers, particularly vinyl ethers, are vinyl monomers having electron-donating substituents, and polymers thereof are one of useful monomers because they are used in adhesives, paints, lubricants, elastomers, greases, and the like. . A block copolymer in which a polymer of a different type from the polymer of the vinyl ether is joined can impart a different property of the other polymer to the property of the vinyl ether, so that a polymer surfactant, thermoplastic elastomer, paint It can be used as an adhesive, a lithographic template agent, and the like. In particular, if the function of a polymer produced from a cationically polymerizable vinyl monomer and the function of a polymer produced from a radical polymerization monomer can be combined, a wider variety of block copolymers can be provided. Therefore, the technology is required.

  In cationic polymerization, a metal halide generally called a metal Lewis acid is used to activate the polymerization. Therefore, it is necessary to remove a metal residue derived from the metal Lewis acid after the polymerization. Non-Patent Document 1 summarizes polymerization systems using metal Lewis acids. When such a method using a metal is used, there is a concern that trace metals may remain in the generated polymer, and there is a problem that it is not suitable for an electronic material. Moreover, since the washing | cleaning by acidic aqueous solution is required for metal removal, drainage contamination is also a concern. Therefore, a method without using a metal Lewis acid has been demanded.

  Meanwhile, block copolymers of cationically polymerizable vinyl ethers and radically polymerizable vinyl monomers are synthesized in the prior art by a combination of a living cationic polymerization method and a living radical polymerization method. In Patent Document 1 and Non-Patent Document 2, vinyl ethers are polymerized by living cationic polymerization using a reversible addition-cleavage chain transfer agent having a carboxyl group and a metal Lewis acid such as tin bromide or zinc chloride, A method of using the obtained polymer as a reversible addition-fragmentation chain transfer agent is disclosed. By this method, a block copolymer of a vinyl ether capable of cationic polymerization and a vinyl monomer capable of radical polymerization can be easily obtained. However, in this method, a metal Lewis acid must be used in the first stage living cationic polymerization.

  Non-Patent Document 3 reports a method of living cationic polymerization of isobutyl vinyl ether in the presence of a reversible addition-fragmentation chain transfer agent, and a reversible addition-cleavage chain transfer (RAFT) radical of methyl (meth) acrylate. It is described that a block copolymer can be obtained by combining with polymerization. However, even in this method, living cationic polymerization is carried out in the presence of a metal Lewis acid such as tin chloride, and has a problem of metal removal.

  On the other hand, Non-Patent Document 4 and Non-Patent Document 5 disclose living cationic polymerization of vinyl ethers by dissolving hydrogen chloride, which is a protonic acid, in ethers. Since this method does not use a metal Lewis acid, this living cationic polymerization is called metal-free living cationic polymerization. However, the both ends of the polymer obtained by the method are introduced with the proton acid-derived hydrogen atom used and the methanol-derived methoxy group used as the terminator, and no method for controlling both ends is described. Therefore, it is difficult to synthesize a block copolymer in combination with radical polymerization.

  Thus, a simple method for obtaining a block copolymer of a vinyl monomer capable of cationic polymerization and a vinyl monomer capable of radical polymerization without using a metal Lewis acid has not been found so far.

JP 2010-059231 A

Chemical Review, 109, 5245-5287 (2009) Macromolecules, 45, 794-804 (2012) Macromolecules, 43, 7523-7531 (2010) Journalof Polymer Science Part A: Polymer Chemistry, 46, 1913-1918 (2008) Polymer Bulletin, 64, 209-220 (2010)

  The present invention provides a method for producing a polymer that is a reversible addition-cleavage chain transfer agent capable of radical polymerization by a method of performing cationic polymerization with a protonic acid without using a metal Lewis acid. The present invention provides a polymer and a method for producing a block copolymer in which a radically polymerizable vinyl monomer is polymerized from the polymer, and further a block copolymer of a cationically polymerizable vinyl monomer and a radically polymerizable vinyl monomer. It is an object of the present invention to provide a method for producing a polymer.

  As a result of repeated researches to solve the above-mentioned problems, the present inventor made a metal-free living cationic polymerization of a cationically polymerizable vinyl monomer in the presence of a RAFT cation agent and radically polymerized the resulting living polymer. The present inventors have found that a polymer of a vinyl monomer capable of cationic polymerization and a vinyl monomer capable of radical polymerization can be obtained as a block copolymer by living radical polymerization of the system monomer.

（式中、Ｒ^１は分岐を有していてもよい炭素数１〜１０のアルキル基を示し、Ｒ^２
は分岐を有していてもよい炭素数１〜４のアルキレン基を示し、Ｒ^３は置換又
は非置換のアルキル基、置換又は非置換のアリール基、置換又は非置換のアリ
ールアルキル基、置換又は非置換のアルキルチオ基、置換又は非置換のアリー
ルチオ基、置換又は非置換のアリールアルキルチオ基、又は、置換又は非置換
のアシルアミノ基を示し、Ｑは各々独立に酸素原子又は硫黄原子であり、ｐは
０、１又は２である）
で表されるＲＡＦＴカチオン剤
を含むリビングカチオン重合開始剤系を提供するものである。 That is, the first invention of the present application is
An initiator system used for living cationic polymerization of a cationically polymerizable vinyl monomer, the following components (A) and (B):
(A) Protic acid dissolved in ethers; and (B) Formula (1)

(In the formula, ^{R 1} represents an alkyl group having 1 to 10 carbon atoms which may have a branch, ^{R 2}
Represents an optionally branched alkylene group having 1 to 4 carbon atoms, R ³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted Or an unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted arylalkylthio group, or a substituted or unsubstituted acylamino group, and each Q is independently an oxygen atom or a sulfur atom, p is 0, 1 or 2)
The living cationic polymerization initiator system containing the RAFT cationic agent represented by these is provided.

  In addition, the second invention of the present application is the production of a polymer for living cationic polymerization of one or more cationically polymerizable vinyl monomers in the presence of the living cationic polymerization initiator system and in the absence of a metal Lewis acid. A method is provided.

Furthermore, the third invention of the present application includes the following steps (i) and (ii):
(I) in the presence of the living cationic polymerization initiator system and in the absence of a metal Lewis acid;
A step of living cationically polymerizing one or more types of cationically polymerizable vinyl monomers to obtain a cationic polymer having a structure derived from the RAFT cationic agent (B) at the end; and (ii) the living cationic polymerization step A cationically polymerizable vinyl monomer and a radical that sequentially perform a radical radical polymerization step of one or more types of radically polymerizable vinyl monomers in the presence of the cationic polymer and radical polymerization initiator obtained in (i). The present invention provides a method for producing a block copolymer of a polymerizable vinyl monomer.

  According to the production method of the present invention, polyvinyl ether can be synthesized from cationically polymerizable vinyl ether by a metal-free polymerization method. Furthermore, a RAFT cation agent can be used for the synthesis of the polymer, and a site capable of reversible addition-cleavage chain transfer effective for radical polymerization can be introduced at the end of the polymer. Therefore, a block copolymer of a vinyl monomer capable of cationic polymerization and a vinyl monomer capable of radical polymerization can be provided. The resulting block copolymer comprises a polymer surfactant, an ink, a thermoplastic elastomer, It is also useful for applications such as paints, adhesives, additives to polymer resins (modifiers), and lithographic template agents.

1 is a diagram showing a ¹ H NMR analysis result of 1- (2-methoxyethoxy) ethyl acetate obtained in Synthesis Example 1. FIG. 4 is a diagram showing a ¹ H NMR analysis result of 1- (2-methoxyethoxy) ethyl benzoate obtained in Synthesis Example 2. FIG. 6 is a diagram showing a ¹ H NMR analysis result of 1- (2-methoxyethoxy) ethyl dithioacetate obtained in Synthesis Example 3. FIG. 1 is a diagram showing the ¹ H NMR analysis result of the isobutyl vinyl ether polymer obtained in Example 1. FIG. 2 is a diagram showing the MALDI-TOF-MS spectrum analysis result of the isobutyl vinyl ether polymer obtained in Example 1. FIG. FIG. 4 is a diagram showing the ¹ H NMR analysis result of the isobutyl vinyl ether polymer obtained in Example 3. FIG. 6 is a diagram showing ¹ H NMR analysis results of the isobutyl vinyl ether polymer obtained in Example 4. Is a diagram showing a ^{1 H} NMR analysis of the block copolymer comprising poly isobutyl vinyl ether and ethyl polyacrylic acid obtained in Example 5.

[1] Living cationic polymerization initiator system First, the living cationic polymerization initiator system of the present invention which is the first invention will be described.

The living cation initiator system of the present invention has the following components:
(A) a protonic acid dissolved in ethers;
(B) It contains the RAFT cation agent represented by said Formula (1).

  In the component (A), ethers for dissolving the protonic acid are not particularly limited as long as they have the ability to dissociate the protonic acid, but tetrahydrofuran, dioxane, dipropyl ether, cyclopentyl methyl ether, diisopropyl ether, dibutyl ether, methyl tert -Butyl ether etc. are mentioned. Of these, diethyl ether, dipropyl ether, and dioxane are preferably used.

  The protonic acid is not particularly limited as long as it is a strong acid, but hydrogen chloride, trifluoromethanesulfonic acid, and trifluoroacetic acid are preferable, and hydrogen chloride is particularly preferable.

On the other hand, in the RAFT cation agent of component (B), in the formula (1), the alkyl group having 1 to 10 carbon atoms which may have a branch represented by R ¹ includes a methyl group, an ethyl group, n- Propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, isobutyl group, sec-butyl group , Tert-butyl group and the like.

Examples of the alkylene group having 1 to 4 carbon atoms which may have a branch represented by R ² include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, and a 1,4-propylene group. And a butylene group.

Furthermore, in the formula (1), examples of the substituted or unsubstituted alkyl group represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n- Linear alkyl groups such as hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-eicosylthio group; branched structures such as isopropyl group, isobutyl group, sec-butyl group and tert-butyl group Alkyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 3-methoxycyclopentyl group, cyclohexyl group, 4-methylcyclohexyl Examples thereof include a cyclic alkyl group such as a syl group, 4-methoxycyclohexyl group, cycloheptyl group or cyclooctyl group.

  Examples of the substituted or unsubstituted aryl group include phenyl group, 2,4-xylyl group, 2,5-xylyl group, 3,4-xylyl group, 3,5-xylyl group, o-tolyl group, m- Tolyl group, p-tolyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 1-naphthyl group, 4-methyl-1-naphthyl group, 4-methoxy- And 11-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group and the like.

  Examples of the substituted or unsubstituted arylalkyl group include a benzyl group, a 4-methylbenzyl group, a 4-phenylbenzyl group, a naphthylmethyl group, a triphenylmethyl group, and a triphenylethyl group.

  Examples of the substituted or unsubstituted alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, an n-pentylthio group, an n-hexylthio group, an n-heptylthio group, an n-octylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, linear alkylthio groups such as n-octadecylthio group, n-nonadecylthio group, n-eicosylthio group; branched alkylthio groups such as isopropylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group; cyclopropylthio group Group, cyclobutylthio group, cyclopentylthio group, 3-methyl Ropenchiruchio group, 3-methoxy cyclopentylthio group, cyclohexylthio group, 4-methylcyclohexyl-thio group, 4-methoxy-cyclohexyl-thio group, etc. and cyclic alkylthio groups such as cycloheptyl thio group or cyclooctyl thio group.

  Examples of the substituted or unsubstituted arylthio group include a phenylthio group, 2,4-xylylthio group, 2,5-xylylthio group, 3,4-xylylthio group, 3,5-xylylthio group, o-tolylthio group, m- Tolylthio group, p-tolylthio group, 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 1-naphthylthio group, 4-methyl-1-naphthylthio group, 4-methoxy-1-naphthylthio group Group, 2-naphthylthio group, 1-anthracenylthio group, 9-anthracenylthio group and the like.

  Examples of the substituted or unsubstituted arylalkylthio group include a benzylthio group, a 4-methylbenzylthio group, a 4-phenylbenzylthio group, a naphthylmethylthio group, a triphenylmethylthio group, and a triphenylethylthio group.

  Examples of the substituted or unsubstituted acylamino group include an acetylamino group, a benzoylamino group, and a methylureido group.

Among the above, preferable R ³ includes a linear or branched alkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group, and in particular, a methyl group, an ethyl group, and an n-propyl group. , Isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, o-tolyl, m-tolyl, p-tolyl and benzyl are preferred.

  In formula (1), each Q is independently an oxygen atom or a sulfur atom, but in order to continue radical polymerization, Q is preferably a sulfur atom rather than an oxygen atom.

（式中、Ｒ^１、Ｒ^２及びｐは、前記式（１）と同義である）
で示されるビニルエーテルと、下記式（３）

（式中、Ｒ^３及びＱは、前記式（１）と同義である）
で示される化合物を反応させることにより得ることができる。 The RAFT cation agent represented by the above formula (1) is represented by the following formula (2):

(In the formula, R ¹ , R ² and p are as defined in the formula (1)).
And vinyl ether represented by the following formula (3)

(In the formula, R ³ and Q have the same meanings as the formula (1)).
It can obtain by making the compound shown by react.

  In the living cation initiator system of the present invention, the protonic acid of component (A) causes an initiating reaction, and further, the growing cation that has partially initiated polymerization acts on the cationic RAFT agent (B), and reversible addition cleavage. Chain transfer cationic polymerization proceeds. For this reason, the amount of the protonic acid described above must be less than that of the RAFT cation agent (B). That is, the amount of the protonic acid used is preferably 0.001 mol or more and less than 1 mol, more preferably 0.01 mol or more and less than 1 mol, based on 1 mol of the RAFT cation agent. More preferably, it is 1 mol or more and less than 1 mol.

  The living cationic polymerization initiator system of the present invention can perform a living cationic polymerization of a vinyl monomer that can be cationically polymerized in the absence of a metal Lewis acid, thereby eliminating a metal removal step after the reaction. Moreover, since the obtained polymer has a site capable of reversible addition-fragmentation chain transfer effective for radical polymerization at the terminal, it is preferably used for the production of a block copolymer with a vinyl monomer capable of radical polymerization. it can.

[2] Production of polymer for living cationic polymerization of cationically polymerizable vinyl monomers
Production method will now be described cationically polymerizable vinyl monomer is a second aspect of the invention a method for manufacturing the living cationic polymerization is to polymer.

  In the present invention, a cationically polymerizable vinyl monomer is subjected to living cationic polymerization in the presence of the living cationic polymerization initiator system of the first invention and in the absence of a metal Lewis acid (hereinafter referred to as “metal-free living cationic polymerization”). "). As a result, a reversible addition-cleavage chain transferable site effective for radical polymerization can be introduced at the end of the polymer. Thus, the cationically polymerizable vinyl monomer, the radically polymerizable vinyl monomer and the block copolymer can be obtained.

  In this metal-free living cationic polymerization, the amount of the living cationic polymerization initiator system used must be such that the RAFT cationic agent (B) is less than the vinyl monomer capable of cationic polymerization. Specifically, the RAFT cation agent (B) is preferably used in an amount of 0.001 mol or more and less than 1 mol with respect to 1 mol of the cation polymerizable vinyl monomer.

  In the living cationic polymerization initiator system, the amount of the ethers contained as the component (A) is preferably 0.01 to 100 mol with respect to 1 mol of the cationically polymerizable vinyl monomer. In addition, ethers may be used as the solvent, but when the total amount of ethers exceeds the above range, the polymerization rate becomes slow.

（式中、Ｒ^４は、水素原子、メチル基又はエチル基を示し、Ｒ^５は、ケイ素又は１５
族から１７族の元素のうち少なくとも一つの原子を含んでいてもよい１価の有機
基を示す）
で示されるアルケニルエーテルが好ましく使用される。 The monomer used for metal-free living cationic polymerization is not particularly limited as long as it is a vinyl monomer capable of cationic polymerization, and examples thereof include alkenyl ether, indene, N-vinylcarbazole, and styrenes. Preferably, styrenes such as styrene, methoxystyrene (o, m, p isomer), methylstyrene (o, m, p isomer), chlorostyrene (o, m, p isomer), and the following formula (4)

(Wherein R ⁴ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁵ represents silicon or 15
A monovalent organic group which may contain at least one atom from elements of group 17 to group 17)
An alkenyl ether represented by is preferably used.

In the above formula (4), examples of the basic skeleton of the monovalent organic group represented by R ⁵ include a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms. Examples of the Group 15 to 17 elements include oxygen, nitrogen, phosphorus, sulfur, and halogen, with oxygen, nitrogen, sulfur, and halogen being preferred, and oxygen and halogen being particularly preferred. Among these, as a substituent containing oxygen, a C1-C12 alkoxy group is preferable. Examples of the substituent containing silicon include an alkylsilyl group, a dialkylsilyl group, and a trialkylsilyl group. As the halogen, fluorine is particularly preferable.

As a preferred example of R ⁵ , a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms which may be substituted with a fluorine atom or an alkoxy group is preferable. Here, as a hydrocarbon group, a C1-C12 linear or branched alkyl group, a C5-C12 cycloalkyl group, a C6-C10 aryl group, a C6-C14 aryl Alkyl groups are preferred.

（ここで、ｑは０、１、２又は３であり、Ｙは未置換のフェニル基、又は、一つ又は
それ以上の炭素数１〜４の直鎖又は分岐鎖アルキル基、１〜４の直鎖又は分岐鎖ア
ルキル基であって全部又は一部の水素がフッ素に置換されたフルオロアルキル基、
炭素数１〜４のアルコキシ基又はハロゲン原子によって置換されたフェニル基で
ある）
で表されるアリール基又はアリールアルキル基を挙げることができる。 In the above formula (4), the monovalent organic group represented by R ⁵ is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and all Or a fluoroalkyl group in which part of hydrogen is substituted with fluorine, an alkoxyalkyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or the following formula (5)

(Where q is 0, 1, 2 or 3; Y is an unsubstituted phenyl group or one or more straight or branched alkyl groups having 1 to 4 carbon atoms; A fluoroalkyl group which is a straight-chain or branched-chain alkyl group in which all or a part of hydrogen is substituted with fluorine,
A phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms or a halogen atom)
The aryl group or arylalkyl group represented by these can be mentioned.

Specifically, as a linear or branched alkyl group having 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group N-amyl group, isoamyl group, etc., and examples of the fluoroalkyl group having 1 to 6 carbon atoms include trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, carbon Examples of the alkoxyalkyl group having 2 to 6 include methoxy group methyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group and the like. Examples of the cycloalkyl group having 5 to 10 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a bicyclo [2 2.1] heptyl, bicyclo [2.2.2] octyl group, a tricyclo [5.2.1.0 ^{2, 6]} decanyl group, adamantyl group, and examples of the aryl group include phenyl group, methylphenyl Group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, trifluoromethylphenyl group, etc., and arylalkyl groups include benzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, ethoxybenzyl Group, fluorobenzyl group, trifluoromethylbenzyl group and the like.

Specific examples of the alkenyl ether represented by the above formula (4) include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, n-amyl. Alkyl vinyl ethers such as vinyl ether and isoamyl vinyl ether; fluoroalkyl vinyl ethers such as trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether and 2,2,2-trifluoroethyl vinyl ether; 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2 -Alkoxy such as tetrahydropyranyl vinyl ether and 2-tetrahydrofuranyl vinyl ether Alkyl vinyl ethers; cyclopentyl vinyl ether, cyclohexyl vinyl ether, cycloheptyl vinyl ether, cyclooctyl vinyl ether, 2-bicyclo [2.2.1] heptyl vinyl ether, 2-bicyclo [2.2.2] octyl vinyl ether, 8-tricyclo [5. 2.1.0 ^2,6 ] decanyl vinyl ether, 1-adamantyl vinyl ether, cycloalkyl vinyl ethers such as 2-adamantyl vinyl ether; phenyl vinyl ether, 4-methylphenyl vinyl ether, 4-trifluoromethylphenyl vinyl ether, 4-fluorophenyl Aryl vinyl ethers such as vinyl ether; arylalkyl vinyl ethers such as benzyl vinyl ether and 4-fluorobenzyl vinyl ether And the like. Of these, lower alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, n-amyl vinyl ether, and isoamyl vinyl ether are preferably used. be able to.

  As the cationically polymerizable vinyl monomer, one kind may be selected from the above monomers, or two or more kinds may be mixed and used.

  The metal-free living cationic polymerization may be performed in the presence of a solvent. The solvent is not particularly limited as long as it is inert to the reaction. For example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as methyl chloride, methylene chloride, and 1,2-dichloroethane, nitromethane, Examples thereof include nitro compounds such as nitroethane, saturated hydrocarbons such as hexane, heptane, octane and nonane, and mixed solvents thereof. Among them, hexane and toluene are preferably used.

  The temperature of metal-free living cationic polymerization is usually between -40 and 100 ° C, preferably between 0 and 35 ° C. These must not exceed the boiling point of the ethers used.

  The metal-free living cationic polymerization time is not particularly limited, and it can be prepared according to the type and usage of a vinyl monomer capable of cationic polymerization or a RAFT cationic agent. After a living polymer of a vinyl monomer capable of target cationic polymerization is obtained by metal-free living cationic polymerization, alcohol or water can be added to the reaction solution to stop the polymerization.

  Specific examples of the alcohol used for terminating the polymerization are methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, etc. Among them, methanol is preferably used. The amount of the polymerization terminator used is preferably 1 mol to 100 mol with respect to 1 mol of Lewis acid.

  When polymerized in this way, metal-free living cationic polymerization proceeds and at the same time a reversible addition-fragmentation chain transfer polymerization mechanism is introduced into the cationic polymerization, so that cationic polymerization with the structure of the above formula (1) arranged at both ends is possible. A living polymer of vinyl monomer is obtained. That is, when described using the above formula (4) representing an alkenyl ether, the following formula (6)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｑ及びｐは、式（１）と同義であり、Ｒ^４及びＲ^５は、式
（４）と同義であり、ｎは各構造単位の繰り返し数を表す）
で表される該ポリマーが得られる。

(Wherein R ¹ , R ² , R ³ , Q and p are as defined in formula (1), R ⁴ and R ⁵ are as defined in formula (4), and n is a repeat of each structural unit. Represents a number)
The polymer represented by is obtained.

  The obtained polymer can be used as a metal-free polymer or as a raw material for copolymerization with a vinyl monomer polymerization capable of radical polymerization.

[3] of cationically polymerizable vinyl monomers and radically polymerizable vinyl monomers
Process for Producing Block Copolymer Finally, the process for producing a block copolymer according to the third invention is described.

The method for producing a block copolymer of the present invention includes the following steps (i) and (ii):
(I) in the presence of the living cationic polymerization initiator system and in the absence of a metal Lewis acid;
A step of living cationically polymerizing one or more types of cationically polymerizable vinyl monomers to obtain a cationic polymer having a structure derived from the RAFT cationic agent (B) at the end; and (ii) the living cationic polymerization step In the presence of the cationic polymer obtained in (i) and a radical polymerization initiator, one or more radically polymerizable vinyl monomers are sequentially subjected to a radical radical polymerization step, and the cationically polymerizable vinyl A block copolymer of a monomer and a vinyl monomer capable of radical polymerization can be obtained.

  The living cationic polymerization step (i) is as described in the second invention. In the present invention, the living polymer from the cationically polymerizable vinyl monomer thus obtained, that is, the above formula (6) From the polymer shown in the above, reversible addition-fragmentation chain transfer polymerization, which is one of living radical polymerization, is carried out to polymerize one or more types of radically polymerizable vinyl monomers.

  The step (ii) of synthesizing a radically polymerizable vinyl monomer by reversible addition-fragmentation chain transfer polymerization from the living polymer represented by the above formula (6) is performed on the living polymer represented by the above formula (6). This is achieved by adding a radically polymerizable vinyl monomer and a radical polymerization initiator and heating.

  Here, in order to perform reversible addition-fragmentation chain transfer polymerization, a compound in which Q is a sulfur atom in general formula (6) is desirable.

  The vinyl monomer that can be radically polymerized is not particularly limited as long as it can be radically polymerized, but is preferably one represented by the general formula (7).

（式中、Ｒ^６、Ｒ^７及びＲ^８は、同一又は異なり、水素原子又はハロゲン置換もしくは
非置換の低級アルキルを示し、Ｒ^９は有機基を示す）

(Wherein R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a halogen-substituted or unsubstituted lower alkyl, and R ⁹ represents an organic group)

  Specifically, styrene and styrene derivatives, (meth) acrylic acid and (meth) acrylic acid derivatives, (meth) acrylamide and (meth) acrylamide derivatives, (meth) acrylonitrile, isoprene, 1,3-butadiene, ethylene, acetic acid Examples thereof include vinyl, vinyl chloride, vinylidene chloride, N-vinyl indole, N-vinyl phthalimide, N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl caprolactam and the like.

  Among these, radically polymerizable conjugated monomers such as styrene and styrene derivatives, (meth) acrylic acid and (meth) acrylic acid derivatives, (meth) acrylamide and (meth) acrylamide derivatives are preferable.

  Specific examples of styrene and derivatives thereof include styrene, tert-butylstyrene (o, m, p isomer), tert-butoxystyrene (o, m, p isomer), and acetoxystyrene (o, m, p isomer). , Hydroxystyrene (o, m, p isomer), isopropenylphenol (o, m, p isomer), α-methylstyrene, vinyl toluene, chlorostyrene (o, m, p isomer), styrene sulfonic acid (o, m) , P-form) and salts thereof. Among these, styrene, tert-butylstyrene, and tert-butoxystyrene are more preferably used.

  Specific examples of (meth) acrylic acid and derivatives thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic 2-methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, ( (Meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoro Methylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, permethacrylate (meth) acrylate Fluoromethyl, (meth) acrylic acid diperfluoromethyl Rumethyl, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluorohexadecylethyl etc. are mentioned. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are more preferably used.

  Examples of (meth) acrylamide and derivatives thereof include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N -N-alkyl (meth) acrylamides such as tert-butyl (meth) acrylamide; N, N-dialkylacrylamides such as N, N-dimethylacrylamide and the like, among which N-isopropyl (meth) acrylamide and the like are more preferable. used.

  As the vinyl monomer capable of radical polymerization, one type may be selected from the above monomers, or two or more types may be mixed and used.

  Any appropriate radical polymerization initiator can be adopted as the radical polymerization initiator. Preferably, it is an initiator that generates radicals by heat. Typical examples of such radical polymerization initiators include various azo compounds and organic peroxides.

  Specific examples of the azo compound include 2,2′-azobisbutyronitrile such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis (2-methylbutyronitrile). Nitriles; 2,2′-azobisvaleronitriles such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2′-azobispropionitriles such as 2,2′-azobis (2-hydroxymethylpropionitrile); 1,1 ′ such as 1,1′-azobis (cyclohexane-1-carbonitrile); -Azobis-1-alkanenitriles; 2,2'-azobis (isobutyric acid) dimethyl and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, and α, α'-bis (t-butylperoxy-m-isopropyl) benzene. Dialkyl peroxides such as 2,5-di (t-butylperoxy) hexyne-3; t-butylperoxybenzoate, t-butylperoxyacetate, 2,5-dimethyl-2,5-di (benzoyl) Peroxy) peroxyesters such as hexane; ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; 2,2-bis (4,4-di-t -Butylperoxycyclohexyl) propane, 1,1-bis (t-butyl) Peroxyketals such as peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valate; cumene Hydroperoxides such as hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylcyclohexane-2,5-dihydroperoxide; benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, 2,4-dichloro Examples thereof include diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as bis (t-butylcyclohexyl) peroxydicarbonate.

  Of these, azo compounds are preferred, and AIBN or 2,2'-azobis (isobutyric acid) dimethyl is particularly easy to obtain and handle.

  In carrying out the reversible addition-fragmentation chain transfer polymerization according to the present invention, a solvent may or may not be used. Any solvent may be used as long as it does not inhibit the polymerization reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; fats such as pentane, hexane, heptane, octane, nonane and decane. Aromatic hydrocarbon solvents; cycloaliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; chlorinated carbonization such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene Hydrogen solvents; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; vinegar Ester solvents such as ethyl and dimethyl phthalate; dimethyl ether, diethyl ether, di -n- amyl ether, may be mentioned ether solvents such as tetrahydrofuran and dioxy anisole and the like. Water can also be used as a solvent. These solvents may be used alone or in combination of two or more.

  The reaction temperature of the reversible addition-cleavage chain transfer polymerization reaction is preferably 20 to 120 ° C, more preferably 40 to 100 ° C. The reaction time for the above reaction varies depending on the reagent amount and the reaction temperature, but is preferably 2 to 50 hours, more preferably 2 to 24 hours.

  The block copolymer is recovered from the reaction mixture by stopping the polymerization by lowering the polymerization reaction temperature or the like, and then removing the volatile matter from the reaction mixture or adding a large amount of poor solvent to remove the polymer. In the case of precipitation and separation, or in the case of a water-soluble polymer, dialysis in water or the like is performed.

  The number average molecular weight of the block copolymer produced by the production method of the present invention is 1,000 to 5,000,000, although it depends on the ratio of the reversible addition-cleavage chain transfer agent to the added monomer. It is preferably 2,000 to 3,000,000.

  The block copolymer obtained by the production method of the present invention is used for polymer surfactants, inks, thermoplastic elastomers, paints, adhesives, additives to polymer resins (modifiers), lithography templates, etc. Also useful. Moreover, the polyvinyl ether which does not contain a metal can be obtained by using the manufacturing method of this invention. Furthermore, a RAFT cation initiator can be introduced into both ends of the obtained polymer, and by using the polymer, block copolymers of various cationic polymerizable monomers and radical polymerizable monomers can be provided.

  EXAMPLES Next, although an Example and a synthesis example demonstrate this invention still in detail, this invention is not restrict | limited at all by these Examples. In the following examples, each measurement method followed the following method.

(1) Number average molecular weight Mn, weight average molecular weight Mw, and ratio of weight average molecular weight to number average molecular weight (Mw / Mn) were measured by gel filtration chromatography (GPC) in terms of polystyrene gel [RI detector, column ( Tosoh Corp. TSKgel column G _HR- M × 3), eluent tetrahydrofuran].

(2) ¹ H NMR was measured by dissolving a sample in deuterated chloroform using JMN AL-300 manufactured by JEOL.

(3) For Fourier transformable spectroscopic altimeter (FT-IR) measurement, a Varian FTS3000 was used, and a sample was sandwiched between calcium fluoride plates and measured by a liquid film method.

(4) For MALDI-TOF-MS measurement, an Autoflex Spectrometer manufactured by Bruker Daltonics was used. In the measurement, dithranol was used as a matrix, sodium trifluoroacetate was used as an ionizing agent, and measurement was performed in a linear mode.

Synthesis example 1
Synthesis of 1- (2-methoxyethoxy) ethyl acetate (MOEA) To a 200 ml eggplant flask, 25.6 mL (0.23 mol) of 2-methoxyethyl vinyl ether and 8.7 mL (0.15 mol) of acetic acid were added, and the mixture was stirred at 70 ° C. Refluxed for 10 hours. The obtained crude product was washed with water in a separatory funnel, pre-dried over anhydrous sodium sulfate, and purified by distillation under reduced pressure in the presence of calcium hydride to obtain MOEA at 58 ° C. (5 mmHg). ^{From 1} H NMR and FT-IR measurement, the structure was estimated as shown in the following formula (8).

FIG. 1 shows the results of ¹ H NMR [CDCl ₃ ] of MOEA obtained in Synthesis Example 1.

Synthesis example 2
Synthesis of 1- (2-methoxyethoxy) ethyl benzoate (MOBA) To a 200 ml eggplant flask, 22.9 mL (0.20 mol) of 2-methoxyethyl vinyl ether and 12.2 g (0.1 mol) of benzoic acid were added. Reflux at 10 ° C. for 10 hours. Thereafter, it was allowed to cool to room temperature. The obtained crude product was washed once with a 1.0 M aqueous sodium hydroxide solution in a separatory funnel, washed with water until neutral, and then pre-dried over anhydrous sodium sulfate. Thereafter, the residue was purified by distillation under reduced pressure in the presence of calcium hydride to obtain MOBA at 98 ° C (1 mmHg). ^{From 1} H NMR and FT-IR measurement, the structure was estimated as shown in the following formula (9).

FIG. 2 shows the results of ¹ H NMR [CDCl ₃ ] of MOBA obtained in Synthesis Example 2.

Synthesis example 3
Synthesis of 1- (2-methoxyethoxy) ethyl dithioacetate (MO-RAFT) To a round bottom flask equipped with a reflux condenser was added 60 mL of a 3.0 M methylmagnesium chloride / tetrahydrofuran solution (manufactured by Aldrich) and 30 mL of tetrahydrofuran. Warmed up. Next, 10.9 mL (0.12 mol) of carbon disulfide was dropped into the same container over 15 minutes. After 1 hour, the mixture was allowed to cool to room temperature, 150 mL of 150 mL of ice water was added, and further 100 mL of diethyl ether (hereinafter Et ₂ O) was added and stirred. Thereafter, when the stirring was stopped, the aqueous layer and the ether layer were separated, and the ether layer was removed and stored (a).

To the remaining aqueous layer, 100 mL of Et ₂ O was added, a small amount of hydrochloric acid was added to adjust the pH of the aqueous layer to about 2, and the mixture was vigorously stirred. The resulting ether layer was separated and stored (b).

When both (a) and (b) were put into a flask and a low-boiling component centering on Et ₂ O was evaporated, dithioacetic acid was obtained. This dithioacetic acid 3.0
g (0.033 mol) and 4.3 g (0.42 mol) of 2-methoxyethyl vinyl ether were put into a flask and stirred at 70 ° C. for 6 hours to be reacted. After standing to cool, the residue was purified by distillation under reduced pressure in the presence of calcium hydride to obtain MO-RAFT at 60 ° C. (5.25 mmHg). ^{From 1} H NMR and FT-IR measurement, the structure was estimated as shown in the following formula (10).

FIG. 3 shows the results of ¹ H NMR [CDCl ₃ ] of MO-RAFT obtained in Synthesis Example 3.

Example 1
Hydrogen chloride dissolved in MOEA (40.0 mM) and diethyl ether (hereinafter,
HCl / Et ₂ O) with isobutyl vinyl ether (hereinafter referred to as IBVE)
Metal-free living cationic polymerization (1)
The polymerization was carried out by the following operation in a test tube with a three-way stopcock under dry conditions. First, 1M and HCl (0.3 mL) of (factor = 0.975) was diluted with _Et 2 O10mL as components of the initiator (A), was prepared HCl · Et ₂ O cooled to 0 ° C.. Further, MOEA synthesized in Synthesis Example 1 as a component (B) of the initiator was dissolved in hexane and diluted to 200 mM. Next, hexane (2.97 mL), IBVE (0.53 mL), and 200 mM MOEA (1 mL) were added into the test tube. Thereafter, the test tube was cooled to 0 ° C., and 0.5 mL of HCl · Et ₂ O was added thereto to initiate polymerization. (Overall polymerization concentrations are [IBVE] ₀ = 0.8 M, [MOEA] ₀ = 40.0 mM, [HCl] ₀ = 2.8 mM, [Et ₂ O] ₀ = 0.96 M).

After 24 hours, add 3 mL or more of methanol to the test tube, transfer to a separatory funnel, add 25 mL of hexane, wash twice with 5 mL of ion-exchanged water, and evaporate at 80 ° C. under reduced pressure to remove volatile residues and purify. did. Thereafter, it was dried at room temperature under reduced pressure. The number average molecular weight Mn of the obtained polymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight to the number average molecular weight were Mn = 2300 and Mw / Mn = 1.38. Moreover, the structure was determined like following formula (11) from < ¹ > H NMR and a MALDI-TOF-MAS measurement.

（式中、ｎは各構造単位の繰り返し数を表す）

(Wherein n represents the number of repeating each structural unit)

FIG. 4 shows the result of ¹ H NMR [CDCl ₃ ] of the polymer obtained in Example 1. FIG. 5 shows the MALDI-TOF-MS spectrum of the polymer obtained in Example 1.

Example 2
Isobutyl vinyl ether using MOEA (6.0 mM) and HCl · Et ₂ O
Metal-free living cationic polymerization of IBVE (2)
The polymerization was carried out by the following operation in a test tube with a three-way stopcock under dry conditions. First, 1M and HCl (0.3 mL) of (factor = 0.975) was diluted with _Et 2 O10mL as components of the initiator (A), was prepared HCl · Et ₂ O cooled to 0 ° C.. Further, MOEA synthesized in Synthesis Example 1 as a component (B) of the initiator was dissolved in hexane and diluted to 200 mM. Next, hexane (3.67 mL), IBVE (0.53 mL), and 200 mM MOEA (0.3 mL) were added into the test tube. Thereafter, the test tube was cooled to 0 ° C., and 0.5 mL of HCl · Et ₂ O was added thereto to initiate polymerization. (Overall polymerization concentrations are [IBVE] ₀ = 0.8 M, [MOEA] ₀ = 6.0 mM, [HCl] ₀ = 2.8 mM, [Et ₂ O] ₀ = 0.96 M).

After 0.33, 1, 2, 3.5, 10, 16, 24 hours, add 3 mL or more of methanol to the test tube, transfer to a separatory funnel, add 25 mL of hexane, wash twice with 5 mL of ion-exchanged water, and reduce the pressure. Evaporation was performed at 80 ° C. to remove volatile residues and purify. Thereafter, it was dried at room temperature under reduced pressure. It was determined by ¹ H NMR and MALDI-TOF-MAS measurements that both had the same structure as formula (11). Further, Mn and Mw / Mn for each polymerization time were as shown in Table 1.

Example 3
Isobutyl vinyl using MOBA (20.0 mM) and HCl · Et ₂ O
The metal-free living cationic polymerization polymerization of ether (IBVE) was performed by the following operation in a test tube with a three-way cock under dry conditions.
First, 1M and HCl (0.3 mL) of (factor = 0.975) was diluted with _Et 2 O10mL as components of the initiator (A), was prepared HCl · Et ₂ O cooled to 0 ° C.. Further, MOBA synthesized in Synthesis Example 2 as the initiator component (B) was dissolved in hexane and diluted to 200 mM. Next, hexane (3.47 mL), IBVE (0.53 mL), 200 mM MOBA (0.5 mL) were added into the test tube. Thereafter, the test tube was cooled to 0 ° C., and 0.5 mL of HCl · Et ₂ O was added thereto to initiate polymerization. (Overall polymerization concentrations are [IBVE] ₀ = 0.8 M, [MOBA] ₀ = 20.0 mM, [HCl] ₀ = 2.8 mM, [Et ₂ O] ₀ = 0.96 M).

After 24 hours, add 3 mL or more of methanol to the test tube, transfer to a separatory funnel, add 25 mL of hexane, wash twice with 5 mL of ion-exchanged water, and evaporate at 80 ° C. under reduced pressure to remove volatile residues and purify. did. Thereafter, it was dried at room temperature under reduced pressure. The number average molecular weight Mn of the obtained polymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight to the number average molecular weight were Mn = 11000 and Mw / Mn = 1.34. Moreover, the structure was determined like following formula (12) from < ¹ > H NMR and a MALDI-TOF-MAS measurement.

（式中、ｎは各構造単位の繰り返し数を表す）

(Wherein n represents the number of repeating each structural unit)

FIG. 6 shows the result of ¹ H NMR [CDCl ₃ ] of the polymer obtained in Example 3.

Example 4
Isobutyl vinyl with MO-RAFT (6.0 mM) and HCl • Et ₂ O
The metal-free living cationic polymerization polymerization of ruether (IBVE) was performed by the following operation in a test tube with a three-way stopcock under dry conditions. First, 1M and HCl (0.3 mL) of (factor = 0.975) was diluted with _Et 2 O10mL as components of the initiator (A), was prepared HCl · Et ₂ O cooled to 0 ° C.. Moreover, MO-RAFT synthesized in Synthesis Example 3 as the component (B) of the initiator was dissolved in hexane and diluted to 200 mM. Next, hexane (3.67 mL), IBVE (0.53 mL), and 200 mM MO-RAFT (0.3 mL) were added into the test tube. Thereafter, the test tube was cooled to 0 ° C., and 0.5 mL of HCl · Et ₂ O was added to initiate polymerization. (Overall polymerization concentrations are [IBVE] ₀ = 0.8 M, [MOEA] ₀ = 6.0 mM, [HCl] ₀ = 2.8 mM, [Et ₂ O] ₀ = 0.96 M).

After 10 hours, add 3 mL or more of methanol to the test tube, transfer to a separatory funnel, add 25 mL of hexane, wash twice with 5 mL of ion-exchanged water, evaporate at 80 ° C. under reduced pressure to remove volatile residues and purify. did. Thereafter, it was dried at room temperature under reduced pressure. The number average molecular weight Mn of the obtained polymer and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight to the number average molecular weight were Mn = 12000 and Mw / Mn = 1.20. Moreover, the structure was determined like following formula (13) from < ¹ > H NMR measurement.

（式中、ｎは各構造単位の繰り返し数を表す）

(Wherein n represents the number of repeating each structural unit)

FIG. 7 shows the result of ¹ H NMR [CDCl ₃ ] of the polymer obtained in Example 4.

Example 5
Block copolymer composed of polyisobutyl vinyl ether and polyethyl acrylate
Synthesis of coalescence Polyisobutyl vinyl ether (PIBVE), ethyl acrylate (EA) and AIBN obtained in Example 4 were put in a test tube with a three-way stopcock, and toluene was added to prepare 3.0 mL. Each molar concentration ratio at this time was [PIBVE]: [EA]: [AIBN] = 1: 200: 0.2, and the EA concentration was adjusted to 15% by mass. The test tube was degassed and polymerized at 70 ° C. under nitrogen.

After 24 hours, the test tube was cooled in ice water, air was introduced, and the polymerization was stopped. The conversion rate of EA is 98%, and the number average molecular weight Mn and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight to the number average molecular weight of the obtained polymer are Mn = 25000, Mw / Mn = 1.80. Further, the structure was determined as shown in the following formula (14) from ¹ H NMR measurement.

（式中、ｎおよびｍは各構造単位の繰り返し数を表す）

(Wherein n and m represent the number of repetitions of each structural unit)

FIG. 8 shows the result of ¹ H NMR [CDCl ₃ ] of the polymer obtained in Example 5.

Example 6
Block copolymer of polyisobutyl vinyl ether and polystyrene
Put formation example poly isobutyl vinyl ether obtained in 4 and (PIBVE) and styrene (St) AIBN in a test tube with a three-way stopcock was adjusted to 3.0mL by adding toluene. Each molar concentration ratio at this time was [PIBVE]: [St]: [AIBN] = 1: 200: 0.2, and the St concentration was adjusted to 15% by mass. The test tube was degassed and polymerized at 70 ° C. under nitrogen.

  After 24 hours, the test tube was cooled in ice water, air was introduced, and the polymerization was stopped. The conversion rate of St is 80%, and the number average molecular weight Mn and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight to the number average molecular weight of the obtained polymer are Mn = 17000, Mw / Mn = 1.53. The structure was determined as in the following formula (15) in the same manner as in Example 5.

（式中、ｎおよびｍは各構造単位の繰り返し数を表す）

(Wherein n and m represent the number of repetitions of each structural unit)

  According to the production method of the present invention, polyvinyl ether synthesized from a cationically polymerizable vinyl ether can be synthesized by a polymerization method not containing a metal. Furthermore, a RAFT cation agent can be used for the synthesis of the polymer, and a site capable of reversible addition-cleavage chain transfer effective for radical polymerization can be introduced at the end of the polymer. Therefore, a block copolymer of a vinyl monomer capable of cationic polymerization and a vinyl monomer capable of radical polymerization can be provided.

The block copolymer obtained by this method has a wide range of polymer surfactants, inks, thermoplastic elastomers, paints, adhesives, additives (modifiers) to polymer resins, lithography template agents, etc. It is useful for applications.

Claims (10)

An initiator system used for living cationic polymerization of a cationically polymerizable vinyl monomer, the following components (A) and (B):
(A) a protonic acid dissolved in ethers; and (B) the following formula (1)

(Wherein R ¹ represents an optionally branched alkyl group having 1 to 10 carbon atoms, R ² represents an optionally branched alkylene group having 1 to 4 carbon atoms, and R ³ Is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryl An alkylthio group, or a substituted or unsubstituted acylamino group, Q is independently an oxygen atom or a sulfur atom, and p is 0, 1 or 2)
A living cationic polymerization initiator system comprising a RAFT cationic agent represented by:   The living cationic polymerization initiator system according to claim 1, wherein the protonic acid is hydrogen chloride.   The living cationic polymerization initiator system according to claim 1 or 2, wherein the amount of the protonic acid used is 0.001 mol or more and less than 1 mol with respect to 1 mol of the RAFT cation agent.   A method for producing a polymer in which one or more cationically polymerizable vinyl monomers are subjected to living cationic polymerization in the presence of the living cationic polymerization initiator system according to claim 1 or 2 and in the absence of a metal Lewis acid. A cationically polymerizable vinyl monomer is represented by the following formula (4).

(Wherein R ⁴ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁵ represents silicon or 15
A monovalent organic group which may contain at least one atom from elements of group 17 to group 17)
The method for producing a polymer according to claim 4, wherein the polymer is an alkenyl ether represented by the formula: The following steps (i) and (ii):
(I) In the presence of the living cationic polymerization initiator system according to claim 1 or 2, and in the absence of a metal lauric acid, one or more types of cationically polymerizable vinyl monomers are subjected to living cationic polymerization, and then terminated. A step of obtaining a cationic polymer having a structure derived from the RAFT cationic agent (B); and (ii) one type in the presence of the cationic polymer and radical polymerization initiator obtained in the living cationic polymerization step (i). A method for producing a block copolymer of a cationically polymerizable vinyl monomer and a radically polymerizable vinyl monomer, comprising sequentially performing the above-mentioned radical polymerization of the radically polymerizable vinyl monomer. A cationically polymerizable vinyl monomer is represented by the following formula (4).

(Wherein R ⁴ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁵ represents silicon or 15
A monovalent organic group which may contain at least one atom from elements of group 17 to group 17)
The manufacturing method of the block copolymer of Claim 6 which is alkenyl ether represented by these.   The radically polymerizable vinyl monomer is at least one selected from the group consisting of styrene, styrene derivatives, (meth) acrylic acid, (meth) acrylic acid derivatives, (meth) acrylamides and (meth) acrylamide derivatives. The manufacturing method of the block copolymer of Claim 6 or 7.   The method for producing a block copolymer according to any one of claims 6 to 8, wherein the radical polymerization initiator is an azo compound. In the said RAFT cation agent (B), the manufacturing method of the block copolymer as described in any one of Claims 6-9 whose Q is a sulfur atom in Formula (1).

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