JPH11322847A - Production of alpha, beta-unsaturated carboxylic acid ester polymer and production of block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an α,β-unsaturated carboxylic acid ester having high general- purpose properties, a high molecular weight, slight discoloration, usable for various uses such as a coating material, molding, adhesive, fiber, fiber treatment, etc., and to provide a method for producing a block copolymer. SOLUTION: A first monomer (M-1) composed of an α,β-unsaturated carboxylic acid ester is polymerized in the presence of a phosphorus compound of the formula (R<1> and R<2> are each an alkyl, a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, and aryl or a substituted aryl; R<1> and R<2> may be bonded to form bivalent organic group; X is a halogen) and a tertiary amine compound and optionally a second monomer (M-2) and a third monomer (M-3) are successively polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an α, β-unsaturated carboxylic acid ester polymer, a method for producing a block copolymer, and a method for producing a block copolymer having a hydroxyl group. A method of polymerizing an α, β-unsaturated carboxylic acid ester in the presence of a specific phosphorus compound and an amine compound, or a method of polymerizing an α, β-unsaturated carboxylic acid ester in the presence of a specific phosphorus compound and an amine compound The method for the sequential polymerization of α, β-unsaturated carboxylic acid ester polymers or block copolymers useful for a wide range of applications such as paints, adhesives, moldings, fibers and fiber treatments. The present invention relates to a method for producing a polymer.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a polymer of α, β-unsaturated carboxylic acid esters, a radical polymerization method is generally used and used for producing various polymers. In order to produce a polymer, it is necessary to apply a bulk polymerization method or a suspension polymerization method, which is extremely difficult to control the generation of heat, and these methods cannot be applied to the production of a block copolymer. there were.

As a method for synthesizing polymers of α, β-unsaturated carboxylic esters, anionic polymerization has been widely studied. According to this method, synthesis of a block copolymer is possible, but low-temperature polymerization in an anhydrous state is essential, so synthesis of a block copolymer by this method has not been general-purpose.

In recent years, as a method for synthesizing a block copolymer, a method using ketene silyl acetal as an initiator {“Macromolecules” [No.
Pp. 1473-1488 (1987)], a method using a metal porphyrin complex as a polymerization initiator, “Polymer Preprints Japa”
n) "[Vol. 37 (No. 6), pp. 1327-1329 (1988)], and methods using a lanthanoid complex as an initiator have been developed. The synthesis is very complicated and its stability is low.
Low versatility of initiator, polymerization in anhydrous state is required, monomer containing active hydrogen cannot be polymerized, and the resulting polymer is significantly colored due to contamination with metal derived from the initiator. There was a problem that.

[0005]

As described above, in the prior art, since the versatility of the initiator is low, there is a problem in terms of industrialization, and the polymerization of α, β-unsaturated carboxylic acid ester is difficult. However, there is a problem in that the polymerization is inhibited by water or a compound containing active hydrogen such as alcohols in the polymerization process, and it is difficult to obtain a high molecular weight (meth) acrylate polymer.

An object of the present invention is to provide an α, β-unsaturated carboxylic acid ester having high versatility, capable of polymerizing a monomer having an active hydrogen atom, and having a high molecular weight and little coloring. It is intended to provide a method for producing a polymer or a block copolymer.Furthermore, it can be used for various applications such as paints, moldings, adhesives, fibers or fiber treatments produced by these methods. An object of the present invention is to provide a polymer of α, β-unsaturated carboxylic acid ester or a block copolymer having the polymer segment, which is highly practical.

[0007]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that α, β-unsaturation occurs in the presence of a specific phosphorus compound and a tertiary amine compound. By polymerizing carboxylic esters, it becomes possible to carry out a polymerization reaction in which the life of the polymerization active species at the growth terminal is extremely long, and when α, β-unsaturated carboxylic esters are successively polymerized, It is not subject to polymerization inhibition by a compound containing active hydrogen such as water or alcohols, and can also polymerize a monomer containing an active hydrogen atom, and has a high molecular weight and little coloration α It has been found that a polymer and a block copolymer of .alpha., .Beta.-unsaturated carboxylic acid ester can be produced, and the present invention has been completed.

That is, the present invention provides (1) a compound represented by the following general formula (I):

[0009]

Embedded image

(Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group, or an aryl group having a substituent. Wherein R ¹ and R ² may combine to form a divalent organic group; X represents a halogen atom.) And a tertiary amine compound (B ) In the presence of a monomer (M) selected from the group consisting of α, β-unsaturated carboxylic esters.
The present invention provides a method for producing an α, β-unsaturated carboxylic acid ester polymer by polymerizing -1) (hereinafter, referred to as a first production method).

In order to solve the above problems, the present invention provides (2) α, β in the presence of the phosphorus compound (A) and the tertiary amine compound (B) represented by the above general formula (I).
Polymerizing a first monomer (M-1) selected from the group consisting of unsaturated carboxylic esters;
A method for producing a diblock copolymer in which a second monomer (M-2) selected from the group consisting of unsaturated carboxylic esters is sequentially polymerized (hereinafter, referred to as a second production method).
I will provide a.

In order to solve the above problems, the present invention provides (3) α, β in the presence of the phosphorus compound (A) and the tertiary amine compound (B) represented by the general formula (I).
Polymerizing a first monomer (M-1) selected from the group consisting of unsaturated carboxylic esters;
A second monomer (M-2) selected from the group consisting of unsaturated carboxylic esters is polymerized, and a third monomer selected from the group consisting of α, β-unsaturated carboxylic esters is further polymerized.
A method for producing a triblock copolymer in which the monomer (M-3) is sequentially polymerized (hereinafter, referred to as a third production method).
I will provide a.

In order to solve the above-mentioned problems, the present invention provides (4) a method of producing a diblock copolymer having a protected hydroxyl group, and then subjecting the diblock copolymer to a treatment for removing a protecting group to have a free hydroxyl group. In the method for producing a diblock copolymer, a diblock copolymer having a protected hydroxyl group,
In the presence of the phosphorus compound (A) and the tertiary amine compound (B) represented by the general formula (I), a first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic acid esters ), And then a second monomer (M) selected from the group consisting of α, β-unsaturated carboxylic acid esters
-2), wherein α, β-unsaturated carboxylic acid ester having a protected hydroxyl group is used as the first monomer (M-1) or the second monomer (M-2). A method for producing a diblock copolymer having a free hydroxyl group, which is a diblock copolymer having a protected hydroxyl group, obtained by a method of
It is called a manufacturing method. )I will provide a.

In order to solve the above-mentioned problems, the present invention provides (5) a method for producing a triblock copolymer having a protected hydroxyl group, and then subjecting the triblock copolymer to a treatment for removing a protecting group to have a free hydroxyl group. In the method for producing a triblock copolymer, the triblock copolymer having a protected hydroxyl group is converted into a triblock copolymer in the presence of a phosphorus compound (A) represented by the general formula (I) and a tertiary amine compound (B). The first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized, and then the second monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters ( M-2) is polymerized, and a third monomer (M-3) selected from the group consisting of α, β-unsaturated carboxylic acid esters is polymerized successively. -1), second At least one of the monomer (M-2) and the third monomer (M-3) has a protected hydroxyl group obtained by a method of polymerizing using an α, β-unsaturated carboxylic acid ester having a protected hydroxyl group. A method for producing a triblock copolymer having a free hydroxyl group, which is a triblock copolymer having the same (hereinafter, referred to as a fifth production method).

In order to solve the above-mentioned problems, the present invention provides (6) a method for protecting a protected hydroxyl group in the presence of a phosphorus compound (A) and a tertiary amine compound (B) represented by the above general formula (I). Α, β-unsaturated carboxylic acid ester having a free hydroxyl group after polymerizing the first monomer (M-1) having a free hydroxyl group To produce a coalescence, then α, β
A method for producing a diblock copolymer having a hydroxyl group by which the second monomer (M-2) selected from the group consisting of unsaturated carboxylic acid esters is sequentially polymerized (hereinafter, referred to as a sixth production method). provide.

Furthermore, in order to solve the above-mentioned problems, the present invention provides (7) protected compounds in the presence of a phosphorus compound (A) and a tertiary amine compound (B) represented by the above general formula (I). Α, β-unsaturated carboxylic acid ester having a hydroxyl group After the first monomer (M-1) is polymerized, a treatment for removing a protecting group is performed to give an α, β-unsaturated carboxylic acid ester having a free hydroxyl group. A polymer is produced, and then α, β
-Polymerizing a second monomer (M-2) selected from the group consisting of unsaturated carboxylic esters, and further adding α, β-
A method for producing a triblock copolymer having a hydroxyl group by which the third monomer (M-3) selected from the group consisting of unsaturated carboxylic acid esters is sequentially polymerized (hereinafter, referred to as a seventh production method). I do.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION A trivalent phosphorus compound represented by the above general formula (I) used in all of the first to seventh production methods of the present invention, wherein R ¹ and R ² are each independently An alkyl group, an alkyl group having a substituent, a cycloalkyl group,
Compounds representing a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent include, for example, chlorodiethylphosphine, chlorodi-n-propylphosphine, chlorodi-n-butylphosphine, chloro-methyl- n-propylphosphine, bromodimethylphosphine, bromodiethylphosphine, bromodi-n-propylphosphine, chloro-n
Dialkylmonohalophosphos such as -butyl-n-propylphosphine, iododimethylphosphine, iododiethylphosphine, iododi-n-propylphosphine, iododi-n-butylphosphine, iodo-methyl-n-propylphosphine. Fins;

Monohalodicycloalkylphosphines such as chlorodicyclohexylphosphine and chlorodicyclopentylphosphine; chloro-methylphenylphosphine, chloro-methyl-p-tolylphosphine, chloro-ethylphenylphosphine, bromo-methyl Monohaloalkylaryl phosphines such as phenylphosphine, bromo-methyl-p-tolylphosphine, bromo-ethylphenylphosphine, iodo-methylphenylphosphine, iodo-methyl-p-tolylphosphine, iodo-ethylphenylphosphine Fins;

Chlorodiphenylphosphine, chlorodi-p-tolylphosphine, chloro-phenyl-p-tolylphosphine, bromodiphenylphosphine, bromodi-p-tolylphosphine, chloro-phenyl-
Monohalodiarylphosphines such as p-tolylphosphine, iododiphenylphosphine, iododi-p-tolylphosphine, iodo-phenyl-p-tolylphosphine, and the like.

The trivalent phosphorus compound represented by the above general formula (I) is characterized in that R ¹ and R ² are bonded to form an alkylene chain,
A cyclic structure in which a divalent organic group is formed such as an alkylene chain interrupted by a hetero atom, an alkylene chain interrupted by an olefinic double bond, or an alkylene chain interrupted by a carbon-carbon bond of an aromatic ring. And a phosphorus compound having the formula:

Among the trivalent phosphorus compounds represented by the general formula (I), chlorodiphenylphosphine and chlorodi-p- are preferred from the viewpoints of availability and ease of handling.
The use of monochlorodiaryl phosphines represented by tolyl phosphine is particularly preferred.

The tertiary amine compound (B) used in all of the first to seventh production methods of the present invention includes, for example, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, and tri-amine. Non-proton-bonded tertiary amines such as n-octylamine, triallylamine and tetramethylethylenediamine; 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (Meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate, N- [2- (meth)
(Acryloyloxy] ethyl morpholine and other (meth) acrylates having a tertiary amino group;

2-dimethylaminoethyl crotonate,
2-di-n-propylaminoethyl crotonate, 3-
Crotonic esters having a tertiary amino group such as dimethylaminopropyl crotonate and 4-dimethylaminobutyl crotonate; maleic acid mono-2-dimethylaminoethyl-monomethyl ester, maleic acid mono-3
Maleic esters such as dimethylaminopropyl-monomethyl ester; itaconic acid mono-2-dimethylaminoethyl-monomethyl ester, itaconic acid mono-
Itaconic esters, such as 3-dimethylaminopropyl-monomethyl ester; fumaric acid mono-2-dimethylaminoethyl-monomethyl ester, fumaric acid mono-3
Fumaric esters such as dimethylaminopropyl-monomethyl ester;

Triethylenediamine, N-methylpiperidine, N, N'-dimethylpiperazine, N-methylmorpholine, 2-methyl-2-oxazoline, 2-ethyl-
2-oxazoline, 3-benzyloxazoline, 2-phenyl (2-oxazoline), 1,3-phenylenebisoxazoline, N, N'-dinitropentamethylenetetramine, pyridine, 2-propylpyridine, 2-cyanopyridine, 3- Cyanopyridine, 4-cyanopyridine,
2-chloropyridine, 2,6-dichloropyridine, 3-
Aldehyde pyridine, 2-vinyl pyridine, 4-vinyl pyridine, 4-pyrrolino pyridine, 4-piperidino pyridine, 2,2′-bipyridine, 2,4-bipyridine,
4,4′-bipyridine, α-picoline, β-picoline,
γ-picoline, 2,2′-bi-4-picoline, 6,6 ′
-Bi-2-picoline, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-
Lutidine, 2,4,6-collidine, 3,6-dichloropyridazine, pyrazine, 2-methylpyrazine, 2,5-
Dimethylpyrazine, 2-cyanopyrazine, triallyl cyanurate, triallyl isocyanurate, cyanuric chloride, 1-methylimidazole, 1-ethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-
Ethyl-4-methylimidazole, 1-cyanoethyl-
2-undecylimidazole, 1-cyanoethyl-2-
Non-proton bonded azas such as phenyl-4,5-bis (cyanoethoxymethyl) imidazole, N-methylindole, diazabicyclo [5,4,0] undecene-7, quinoline, isoquinoline and quinaldine; These tertiary amine compounds can be used alone or in combination of two or more.

Among these tertiary amine compounds, non-proton-bonded tertiary amines, (meth) acrylates having a tertiary amino group, and non-proton-bonded azas are particularly preferable from the viewpoint of polymerizability.

Α, β used in the first production method of the present invention
A monomer (M-1) selected from the group consisting of unsaturated carboxylic esters or a first monomer selected from the group consisting of α, β-unsaturated carboxylic esters used in the second to seventh production methods As (M-1), α, β
As long as it is an ester of an unsaturated carboxylic acid, various known and commonly used esters can be used. From the viewpoint of obtaining the obtained polymer or copolymer in good yield, α, β-unsaturated carboxylic acid Among the above esters, active hydrogen bonded to a hetero atom such as an active hydrogen atom bonded to an oxygen atom in a carboxyl group, a hydroxyl group, or the like, or an active hydrogen atom bonded to a nitrogen atom in a primary amino group, a secondary amino group, or the like. Particularly preferred are compounds that do not.

The monomer (M) used in the production method of the present invention
As -1), for example, α, such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
Examples include various esters derived from β-unsaturated monocarboxylic acids or α, β-unsaturated dicarboxylic acids.

Esters of α, β-unsaturated monocarboxylic acids such as (meth) acrylic acid or crotonic acid include, for example, methyl (meth) acrylate, methyl crotonic acid, ethyl (meth) acrylate, crotonic acid ethyl,
N-propyl (meth) acrylate, n-propyl crotonate, iso-propyl (meth) acrylate, iso-propyl crotonate, n-butyl (meth) acrylate,
N-butyl crotonate, iso-butyl (meth) acrylate, iso-butyl crotonate, tert-butyl (meth) acrylate, tert-butyl crotonate, n-pentyl (meth) acrylate, n-pentyl crotonate , 2-ethylhexyl (meth) acrylate, 2-ethylhexyl crotonate, n-octyl (meth) acrylate, n-octyl crotonate, n- (meth) acrylate
Decyl, n-decyl crotonate, n (meth) acrylate
(Meth) such as dodecyl, n-dodecyl crotonate, stearyl (meth) acrylate, stearyl crotonate
Esters of acrylic acid or crotonic acid with an alcohol having 1 to 18 carbon atoms;

Cyclopentyl (meth) acrylate, cyclopentyl crotonate, cyclohexyl (meth) acrylate, cyclohexyl crotonate, 4-methylcyclohexyl (meth) acrylate, 4-methylcyclohexyl crotonate, isobornyl (meth) acrylate, croton Esters of (meth) acrylic acid or crotonic acid with alicyclic alcohols, such as isobornyl acid;

Phenyl (meth) acrylate, phenyl crotonate, 4-methylphenyl (meth) acrylate, 4-methylphenyl crotonate, 4- (meth) acrylate
Aryl esters of (meth) acrylic acid or crotonic acid such as chlorophenyl and 4-chlorophenyl crotonic acid; benzyl (meth) acrylate, benzyl crotonic acid, 1-phenylethyl (meth) acrylate, 1-phenylethyl crotonic acid, Esters of (meth) acrylic acid or crotonic acid with aralkyl alcohols, such as 2-phenylethyl (meth) acrylate and 2-phenylethyl crotonic acid;

2,2-dimethyl (meth) acrylate
1,3-dioxolan-4-ylmethyl, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl crotonate, 2- (1-methoxyethoxy) ethyl (meth) acrylate, 2- (1- Methoxyethoxy)
Ethyl, 2- (1-ethoxyethoxy) ethyl (meth) acrylate, 2- (1-ethoxyethoxy) crotonate
Ethyl, 2-trimethylsilyloxyethyl (meth) acrylate, 2-trimethylsilyloxyethyl crotonate, 4-trimethylsilyloxybutyl (meth) acrylate, 2-trimethylsilyloxybutyl crotonate,
2- (dimethyl-tert-butylsilyloxy) ethyl (meth) acrylate, 2- (dimethyl-t-crotonate)
esters of (meth) acrylic acid or crotonic acid such as tert-butylsilyloxy) ethyl with alcohols having a protected hydroxyl group;

Trimethylsilyl (meth) acrylate, trimethylsilyl crotonate, dimethyl-tert-butylsilyl (meth) acrylate, dimethyl-t-crotonate
tert-butylsilyl, 1-ethoxyethyl (meth) acrylate, 1-ethoxyethyl crotonate, 1-n-butoxyethyl (meth) acrylate, 1-n-crotonate
Having a protected carboxyl such as butoxyethyl, tetrahydrofuran-2-yl (meth) acrylate, tetrahydrofuran-2-yl crotonic acid, tetrahydropyran-2-yl (meth) acrylate, tetrahydropyran-2-yl crotonic acid Monomers; (meth) acrylic acid such as 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxyethyl crotonate, 4-acetoacetoxybutyl (meth) acrylate, 4-acetoacetoxybutyl crotonate or Esters of crotonic acid and alcohols having an acetoacetoxy group;

Esters of (meth) acrylic acid or crotonic acid such as glycidyl (meth) acrylate, glycidyl crotonate, 2-methyl glycidyl (meth) acrylate and 2-methyl glycidyl crotonate with alcohols having an epoxy group 2,3-carbonatepropyl (meth) acrylate, 2,3-carbonatepropyl crotonate, 2-methyl-2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl crotonate Esters of (meth) acrylic acid or crotonic acid with alcohols having a cyclic carbonate group, such as 3,4-carbonate butyl (meth) acrylate and 3,4-carbonate butyl crotonate; (meth)
2-methoxyethyl acrylate, 2-methoxyethyl crotonate, 2-ethoxyethyl (meth) acrylate, 2-ethoxyethyl crotonate, 2- (meth) acrylic acid
(2-methoxyethoxy) ethyl, crotonic acid 2- (2
Esters of (meth) acrylic acid or crotonic acid such as -methoxyethoxy) ethyl with alcohols having an ether linkage;

Esters of (meth) acrylic acid with polyethylene glycol having one end capped with an alkoxyl group or the like, esters of crotonic acid with polyethylene glycol having one end capped with an alkoxyl group or the like,
An ester of (meth) acrylic acid and polypropylene glycol having one end blocked with an alkoxyl group or the like,
Esters of crotonic acid and polypropylene glycol, one end of which is blocked with an alkoxyl group, etc., (meth)
(Meth) such as an ester of acrylic acid and polytetramethylene glycol in which one end is blocked with an alkoxyl group or the like, and an ester of crotonic acid with polytetramethylene glycol in which one end is blocked with an alkoxyl group or the like Esters of acrylic acid or crotonic acid with polyethers having a hydroxyl group at one end, and the like.

Esters of α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid include, for example, monomethyl maleate, monomethyl fumarate, monomethyl itaconate, dimethyl maleate, fumarate Dimethyl acid, dimethyl itaconate, monoethyl maleate, monoethyl fumarate, monoethyl itaconate, diethyl maleate, diethyl fumarate, diethyl itaconate, mono-n-propyl maleate, mono-n-propyl fumarate, mono-itaconate -N-propyl, di-n-propyl maleate, di-n-propyl fumarate, di-n-propyl itaconate, mono-iso-propyl maleate, mono-iso-propyl fumarate, mono-iso itaconate -Propyl, di-iso-propyl maleate, Di-iso-propyl fumarate,
Di-iso-propyl itaconate,

Mono-n-butyl maleate, mono-n-butyl fumarate, mono-n-butyl itaconate, di-n-butyl maleate, di-n-butyl fumarate, di-n-butyl itaconate Mono-iso-butyl maleate, mono-iso-butyl fumarate, mono-itaconate
iso-butyl, di-iso-butyl maleate, di-iso-butyl fumarate, di-iso-butyl itaconate, mono-tert-butyl maleate, mono-tert-butyl fumarate, mono-tert-itaconate Butyl, di-tert-butyl maleate, di-t-fumarate
tert-butyl, di-tert-butyl itaconate, mono-n-pentyl maleate, mono-n-pentyl fumarate, mono-n-pentyl itaconate, di-maleate
n-pentyl, di-n-pentyl fumarate, di-n-pentyl itaconate,

Mono-2-ethylhexyl maleate, mono-2-ethylhexyl fumarate, mono-2 itaconic acid
-Ethylhexyl, di-2-ethylhexyl maleate, di-2-ethylhexyl fumarate, di-itaconate
2-ethylhexyl, mono-n-octyl maleate,
Mono-n-octyl fumarate, mono-n-octyl itaconate, di-n-octyl maleate, di-n fumarate
-Octyl, di-n-octyl itaconate, mono-n-decyl maleate, mono-n-decyl fumarate, mono-n-decyl itaconate, di-n-decyl maleate, di-n-decyl fumarate Di-n-decyl itaconate, mono-n-dodecyl maleate, mono-n-dodecyl fumarate, mono-n-dodecyl itaconate, di-maleic acid
n-dodecyl, di-n-dodecyl fumarate, di-n-dodecyl itaconate, monostearyl maleate, monostearyl fumarate, monostearyl itaconate, distearyl maleate, distearyl fumarate, distearyl itaconate Monoesters or diesters of maleic acid, fumaric acid or itaconic acid with alcohols having 1 to 18 carbon atoms, such as;

Monocyclopentyl maleate, monocyclopentyl fumarate, monocyclopentyl itaconate,
Dicyclopentyl maleate, dicyclopentyl fumarate, dicyclopentyl itaconate, monocyclohexyl maleate, monocyclohexyl fumarate, monocyclohexyl itaconate, dicyclohexyl maleate, dicyclohexyl fumarate, dicyclohexyl itaconate, monocyclohexyl maleate Mono-4-methylcyclohexyl fumarate, mono-4-methylcyclohexyl itaconate, di-4-methylcyclohexyl maleate, di-4-methylcyclohexyl fumarate, di-4-methylcyclohexyl itaconate, monoisobornyl maleate, Monoisobornyl fumarate,
Monoesters or diesters of maleic acid, fumaric acid or itaconic acid with alicyclic alcohols such as monoisobornyl itaconate, diisobornyl maleate, diisobornyl fumarate, diisobornyl itaconate;

Monophenyl maleate, monophenyl fumarate, monophenyl itaconate, diphenyl maleate, diphenyl fumarate, diphenyl itaconate, mono-4-methylphenyl maleate, mono-4-fumarate
Methylphenyl, mono-4-methylphenyl itaconate, di-4-methylphenyl maleate, di-fumarate
4-methylphenyl, di-4-methylphenyl itaconate, mono-4-chlorophenyl maleate, mono-4-chlorophenyl fumarate, mono-4-chlorophenyl itaconate, di-4-chlorophenyl maleate, di-fumarate Monoesters or diesters of maleic acid, fumaric acid or itaconic acid with phenols such as 4-chlorophenyl, di-4-chlorophenyl itaconate;

The maleic acid bis (2,2-dimethyl-
1,3-dioxolan-4-ylmethyl ester), fumaric acid bis (2,2-dimethyl-1,3-dioxolan-4-ylmethyl ester), itaconic acid bis (2,2-dimethyl-1, 3-dioxolan-4-ylmethyl ester), bis [2- (1-methoxyethoxy) ethyl ester of maleic acid], bis [2
-(1-methoxyethoxy) ethyl ester], itaconic acid bis [2- (1-methoxyethoxy) ethyl ester], maleic acid bis [2- (1-ethoxyethoxy) ethyl ester], fumaric acid bis [ 2- (1-ethoxyethoxy) ethyl ester], bis [2- (1-ethoxyethoxy) ethyl ester] of itaconic acid, bis (2-trimethylsilyloxyethyl ester) of maleic acid, bis (2-trimethylsilyl) of fumaric acid Oxyethyl ester), itaconic acid bis (2-trimethylsilyloxyethyl ester), maleic acid bis (4-trimethylsilyloxybutyl ester), fumaric acid bis (4-trimethylsilyloxybutyl ester), itaconic acid bis (4 -Trimethylsilyloxybutyl ester), Bis maleic acid [2- (dimethyl -tert- butyl silyl oxy) ethyl ester,
Bis [2- (dimethyl-tert-butylsilyloxy) ethyl ester of fumaric acid, bis [2
-(Dimethyl-tert-butylsilyloxy) ethyl ester], and diesters of maleic acid, fumaric acid or itaconic acid with protected hydroxyl-containing alcohols;

Bis (trimethylsilyl ester) of maleic acid, bis (trimethylsilyl ester) of fumaric acid, bis (trimethylsilyl ester) of itaconic acid, bis (dimethyl-tert-butylsilyl ester) of maleic acid, bis (dimethyl of fumaric acid −ter
t-butylsilyl ester), bis (dimethyl-tert-butylsilyl ester) of itaconic acid, bis (1-ethoxyethyl ester) of maleic acid, bis (1-ethoxyethyl ester) of fumaric acid, bis (1-ethoxyethyl ester) of itaconic acid Monomers containing a block carboxyl, such as 1-ethoxyethyl ester);

Monobenzyl maleate, monobenzyl fumarate, monobenzyl itaconate, dibenzyl maleate, dibenzyl fumarate, dibenzyl itaconate, mono-1-phenylethyl maleate, mono-1-fumarate
Phenylethyl, mono-1-phenylethyl itaconate, di-1-phenylethyl maleate, di-fumarate
1-phenylethyl, di-1-phenylethyl itaconate, mono-2-phenylethyl maleate, mono-2-phenylethyl fumarate, mono-2-phenylethyl itaconate, di-2-phenylethyl maleate, Monoesters or diesters of maleic acid, fumaric acid or itaconic acid with aralkyl alcohols, such as di-2-phenylethyl fumarate, di-2-phenylethyl itaconate;

Monoglycidyl maleate, monoglycidyl fumarate, monoglycidyl itaconate, diglycidyl maleate, diglycidyl fumarate, diglycidyl itaconate, mono-2-methyl glycidyl maleate, mono-2-methyl glycidyl fumarate, itaconic acid Mono-2
Mono-monomers of maleic acid, fumaric acid or itaconic acid and alcohols having an epoxy group, such as methyl glycidyl, di-2-methyl glycidyl maleate, di-2-methyl glycidyl fumarate, di-2-methyl glycidyl itaconate; Esters or diesters;

Mono (2,3-carbonatepropyl) maleate, Mono (2,3-carbonatepropyl) fumarate, Mono (2,3-carbonatepropyl) itaconate, Di (2,3-carbonatepropyl) maleate , Di (2,3-carbonate propyl) fumarate,
Di (2,3-carbonate propyl itaconate), mono (2-methyl-2,3-carbonate propyl) maleate, mono (2-methyl-2,3-carbonate propyl fumarate), mono (2-methyl itaconate) Methyl-2,3-
Carbonate propyl), di (2-methyl-maleate)
2,3-carbonate propyl), di (2-methyl-2,3-carbonate propyl) fumarate, di (2-methyl-2,3-carbonate propyl) itaconate, mono (3,4-carbonate butyl maleate) ), Mono (3,4-carbonate butyl fumarate), mono (3,4-carbonate butyl) itaconate, di (3,4-carbonate maleate)
Monomers of maleic acid, fumaric acid or itaconic acid and alcohols having a cyclic carbonate group, such as 4-carbonate butyl), di (3,4-carbonate butyl) fumarate, and di (3,4-carbonate butyl) itaconate Esters or diesters;

Mono (2-methoxyethyl) maleate,
Mono (2-methoxyethyl) fumarate, mono (2-methoxyethyl) itaconate, di (2-methoxyethyl) maleate, di (2-methoxyethyl) fumarate, di (2-methoxyethyl) itaconate, Maleic acid mono (2-
Ethoxyethyl), mono (2-ethoxyethyl) fumarate, mono (2-ethoxyethyl) itaconate, di (2-ethoxyethyl) maleate, di (2-ethoxyethyl) fumarate, di (2-ethoxyethyl) itaconate Ethoxyethyl),
Mono (2- (2-methoxyethoxy) ethyl maleate), mono (2- (2-methoxyethoxy) ethyl fumarate), mono (2- (2-methoxyethoxy) ethyl) itaconate, di (2 Maleic acid, fumaric acid or itaconic acid such as-(2-methoxyethoxy) ethyl), di (2- (2-methoxyethoxy) ethyl) fumarate or di (2- (2-methoxyethoxy) ethyl) itaconate; Monoester or diester with an alcohol having an ether bond;

Monoester or diester of maleic acid, fumaric acid or itaconic acid and polyethylene glycol in which one end is blocked with an alkoxyl group or the like, maleic acid, fumaric acid or itaconic acid and one end blocked with an alkoxyl group or the like. (Meth) acrylic acid or crotonic acid such as an ester of polypropylene glycol in the form of a mixture, maleic acid, fumaric acid or itaconic acid and an ester of polytetramethylene glycol in which one end is blocked by an alkoxyl group or the like Monoesters and diesters with polyethers having a hydroxyl group at the terminal are exemplified.

The esters of α, β-unsaturated dicarboxylic acids may be mixed esters of various alcohols used in the esters described above.

Further, (M-
As 1), α, β-unsaturated carboxylic esters having a tertiary amino group exemplified as the amine compound (B) can also be used.

In carrying out the production method of the present invention,
Among the various α, β-unsaturated carboxylic esters described above, the use of (meth) acrylic esters is particularly preferred.

The water and the polymerization inhibitor contained in the various α, β-unsaturated carboxylic esters described above can be used without removing them, but from the viewpoint of obtaining a higher polymerization yield, From the viewpoint of obtaining a polymer having a high polymerization rate, and from the viewpoint of obtaining a polymer having a narrower molecular weight distribution,
It is preferable to remove water and the polymerization inhibitor by a known and commonly used method before use.

The second monomer (M-2) and the third monomer (M-3) of the α, β-unsaturated carboxylic esters used in the second to seventh production methods of the present invention include:
Various known and used ones can be used, and any of α, β-unsaturated carboxylic acid esters having no active hydrogen or α, β-unsaturated carboxylic acid esters having active hydrogen can be used. can do.

Among the second monomer (M-2) and the third monomer (M-3) used in the second to seventh production methods of the present invention, α, β-unsaturated carboxylic acid having no active hydrogen As the esters, those listed as α, β-unsaturated carboxylic esters usable in the first monomer (M-1) can be used.

Among the second monomer (M-2) and the third monomer (M-3) used in the second to seventh production methods of the present invention, α, β-unsaturated carboxylic acid ester having active hydrogen Examples of the class include 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl crotonic acid, di-2-hydroxyethyl maleate, di-2-hydroxyethyl phthalate, di-2-hydroxyethyl itaconate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl crotonate, di-2-hydroxypropyl maleate, di-2-hydroxypropyl phthalate, di-2-hydroxypropyl itaconate, (meth)
4-hydroxybutyl acrylate, 4-hydroxybutyl crotonate, di-4-hydroxybutyl maleate,
Di-4-hydroxybutyl phthalate, di-4 itaconate
-Hydroxybutyl, 2,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl crotonic acid, di-2,3-dihydroxypropyl maleate, di-2,3-dihydroxypropyl phthalate, di-itaconate An α, β-unsaturated carboxylic acid ester having a hydroxyl group such as -2,3-dihydroxypropyl;

2-Carboxyethyl (meth) acrylate, 2-carboxyethyl crotonate, mono-2-carboxyethyl maleate, di-2-carboxyethyl maleate, mono-2-carboxyethyl phthalate, di-2-phthalate -2-carboxyethyl, itaconic acid mono-2-
Carboxyethyl, di-2-carboxyethyl itaconate, mono-2-hydroxyethyl maleate, mono-2-hydroxyethyl phthalate, mono-2-hydroxyethyl itaconate, mono-2-hydroxyethyl hexahydrophthalate, Mono-2-hydroxyethyl trimellitate, di-2-hydroxyethyl trimellitate, mono-2-hydroxypropyl maleate, mono-phthalate
2-hydroxypropyl, mono-2-hydroxypropyl itaconate, mono-2-hydroxypropyl hexahydrophthalate, mono-2-hydroxypropyl trimellitate, di-2-hydroxypropyl trimellitate,
Mono-4-hydroxybutyl maleate, mono-4-hydroxybutyl phthalate, mono-4-hydroxybutyl itaconate, mono-4-hydroxybutyl hexahydrophthalate, mono-4-hydroxybutyl trimellitate, trimellitate 4-hydroxybutyl acid, mono-2,3-dihydroxypropyl maleate, mono-2,3-dihydroxypropyl phthalate, mono-itaconate
It has a carboxyl group such as 2,3-dihydroxypropyl, mono-2,3-dihydroxypropyl hexahydrophthalate, mono-2,3-dihydroxypropyl trimellitate, and di-2,3-dihydroxypropyl trimellitate. α, β-unsaturated carboxylic acid esters, and the like.

In carrying out the production method of the present invention,
Among the various α, β-unsaturated carboxylic esters described above, the use of (meth) acrylic esters is particularly preferred.

In general, in the anionic polymerization and other living polymerizations, the polymerization reaction is stopped when water is present, but in the method for producing a block polymer according to the present invention, the second monomer (M-2) and the subsequent monomers are successively used. Surprisingly, even when water or a compound having active hydrogen coexists, the polymerization reaction is not affected, such as termination, so that the polymerization reaction is carried out in the coexistence of water and alcohols. It is possible to polymerize a material having a group having an active hydrogen such as a hydroxyl group as α, β-unsaturated carboxylic acid esters to be polymerized.

Accordingly, the above-mentioned second monomer (M-2)
Or α, β- used as the third monomer (M-3)
Unsaturated carboxylic acid esters can be used as they are without removing water, polymerization inhibitor and the like contained in the esters.

When adjusting the target nuclear block copolymer, the first monomer (M-1) and the second monomer (M-1) which form each segment in the nuclear block copolymer are prepared.
As the monomer (M-2) and the third monomer (M-3), various α, β-unsaturated carboxylic esters may be used alone, and two or more arbitrary α, β-unsaturated esters may be used. Carboxylic esters may be used in combination.

The first monomer (M-1) and the second monomer (M-2), or the second monomer (M-2) and the third monomer (M-3) are different monomer units. It must be a mixture of different monomers or different monomers. On the other hand, the first monomer (M-1) and the third monomer (M
-3) may be the same monomer or a mixture of the same monomers.

In the first to seventh production methods of the present invention, α, and α are added in the presence of the phosphorus compound (A) and the amine compound (B).
The reaction for polymerizing the β-unsaturated carboxylic acid ester may be performed in a solventless system or may be performed in the presence of a solvent. When a polymerization reaction is carried out using solvents, various known and common solvents having no active hydrogen bonded to a hetero atom can be basically used.

Examples of such a solvent include hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, n-hexane and n-octane; methyl formate, ethyl formate, methyl acetate, methyl acetate, ethyl acetate, acetic acid Ester solvents such as n-butyl, isobutyl acetate, methyl propionate, ethylene glycol monoethyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, di-iso-propyl ether, di- n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol di-n-butyl ether, diethylene glycol Ether solvents such as dimethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether; halogenated hydrocarbons such as chloroform, carbon tetrachloride, and 1,2-dichloroethane; dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropion Amide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N,
Aprotic polar solvents such as N'-dimethylethylene urea; Among these solvents, ether solvents, from the viewpoint of giving a polymer at a high polymerization rate,
Particularly preferred are linear or cyclic amide solvents and ester solvents. These solvents can be used alone,
Two or more kinds can be used in combination.

If these solvents have a water content of a certain level or less, they can be used without being subjected to a dehydration treatment. However, from the viewpoint that a higher polymerization rate can be achieved, and that the solvent is narrower. From the viewpoint of obtaining a polymer having a molecular weight distribution, it is preferable to use a polymer which has been subjected to various known and common dehydration treatments suitable for the respective solvents in advance to reduce the water content.

Next, a method for producing a polymer of an α, β-unsaturated carboxylic acid ester or a block copolymer of the present invention will be described.

In the presence of the phosphorus compound (A) and the amine compound (B), a monomer (M-1) or a first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters. And (1) a method in which the monomer (M-1), the phosphorus compound (A), and the amine compound (B) are charged together and reacted.
(2) a method of dropping an amine compound (B) to a mixture of a monomer (M-1) and a phosphorus compound (A); (3) a method of adding a mixture of a monomer (M-1) and an amine compound (B) (4) a method of dropping a phosphorus compound (A); (4) a method of dropping a monomer (M-1) into a mixture of a solvent, a phosphorus compound (A) and an amine compound (B); (5) a solvent and a monomer (M).
-1) and a method of dropping a phosphorus compound (A) into a mixture of an amine compound (B) and the like.

In order to obtain the desired diblock copolymer using the first monomer (M-1) and the second monomer (M-2), first, the phosphorus compound (A) and the amine compound (B ), The first monomer (M-1) is polymerized to form a polymer having a polymer segment composed of the monomer (M-1) and having a polymerization active group at one end thereof. I do. At that time, the method described above can be applied as a polymerization method of the first monomer (M-1).

The second monomer (M-2) is added to the thus-prepared polymer segment composed of the monomer (M-1) having a polymerization active group at one end, and the second polymer is polymerized. A diblock copolymer having a polymer segment composed of one monomer (M-1) and a polymer segment composed of the second monomer (M-2) can be obtained.

In the case of producing a diblock copolymer, the first
The usage ratio of the monomer (M-1) and the second monomer (M-2) can be set at any ratio, but preferably ranges from 2:98 to 98: 2 by weight, and is preferably 5:95. ~
A range of 95: 5 is particularly preferred.

Using the first monomer (M-1), the second monomer (M-2) and the third monomer (M-3),
In order to prepare the desired triblock copolymer,
First, a phosphorus compound (A) and an amine compound (B) are prepared in the same manner as in the case of preparing the diblock copolymer as described above.
, The first monomer (M-1) as an α, β-unsaturated carboxylic acid ester is polymerized, and then the second monomer (M-2) and the third monomer (M-3) may be sequentially added to the polymerization system for polymerization.

The ratio of the first monomer (M-1), the second monomer (M-2) and the third monomer (M-3) used for producing the triblock copolymer can be set arbitrarily. Although it is possible, the proportion of each monomer group is preferably set to be 2% by weight or more of the total amount of the monomers constituting the triblock copolymer, and particularly preferably set to be 5% by weight or more. preferable.

In the production method of the present invention, when a solvent is used for preparing a polymer or a block copolymer, the amount used is 20 to 1,50 of the total amount of monomers to be polymerized.
A range of 0% by weight is preferred.

In the production method of the present invention, the amount of the phosphorus compound (A) used in preparing the polymer or the block copolymer is based on 1 mole of the total amount of the monomers to be polymerized. The amount in which the number of equivalents of phosphorus atoms contained in the phosphorus compound (A) is in the range of 0.0001 to 0.2 mol is preferred, and the amount in which the equivalent number is in the range of 0.001 to 0.1 mol is particularly preferred.

In the production method of the present invention, the amount of the amine compound (B) used for preparing the polymer or the block copolymer is based on 1 mol of the total amount of the monomer to be polymerized. The amount in which the equivalent number of the nitrogen atom constituting the amino group contained in (B) is in the range of 0.0001 to 1.0 mol is preferable, and the amount in the range of 0.001 to 0.5 mol is particularly preferable. .

The ratio of the phosphorus compound (A) to the amine compound (B) is such that the equivalent number of phosphorus atoms contained in the phosphorus compound (A) and the amino group contained in the amine compound (B) are included. The ratio to the number of equivalents of the nitrogen atom is 1: 100 to 100:
A ratio in the range of 1 is preferred, and a ratio in the range of 1:10 to 10: 1 is particularly preferred.

In the production method of the present invention, the polymerization reaction temperature for preparing a polymer or a block copolymer is -20.
The range is preferably from 130 to 130 ° C, particularly preferably from 0 to 100 ° C, more preferably from 20 to 90 ° C. When the reaction temperature is lower than -20 ° C, the polymerization rate tends to be extremely low, and when the reaction temperature is higher than 130 ° C, the polymerization active site at the growth terminal tends to be easily deactivated by a side reaction, This is not preferable because the yield of the polymer is significantly reduced.

In the production method of the present invention, the polymerization reaction is carried out under an atmosphere of a so-called inert gas such as argon or nitrogen throughout the polymerization reaction when preparing the polymer or the block copolymer. Is preferred.

In addition, at least a part of the monomer (M-1) component has 2-dimethylaminoethyl (meth) as described above.
When an α, β-unsaturated carboxylic acid ester having a tertiary amino group such as acrylate or 2-diethylaminoethyl (meth) acrylate is used, this monomer plays a role as the amine compound (B). It is not necessary to use a tertiary amine compound other than a monomer having a tertiary amino group.

The time of the polymerization reaction for preparing the polymer comprising the first monomer (M-1) varies depending on the ratio of the phosphorus compound (A) to the monomer (M-1), the polymerization temperature, and the like. And a range of 3 to 72 hours is preferred.

The time of each polymerization reaction when preparing each block copolymer varies depending on the type of the phosphorus compound (A), tertiary amine compound (B), monomer and solvent, the reaction temperature and the like. However, the time is preferably such that the polymerization rate in each polymerization step is about 90% or more, and particularly preferably the time when the polymerization rate is 95% or more.

In this manner, a diblock copolymer or a triblock copolymer having a segment composed of a polymer composed of α, β-unsaturated carboxylic acid esters can be prepared.

In the above-described method for producing a diblock copolymer, the first monomer (M-1) and / or the second monomer (M-2) may have the α, β- By using an unsaturated carboxylic acid ester, a diblock copolymer having a protected hydroxyl group can be obtained.

In the method for producing a triblock copolymer described above, the first monomer (M-1) and the second monomer (M
-2) and at least one of the third monomers (M-3) has α, β- having a protected hydroxyl group as described above.
By using an unsaturated carboxylic acid ester, a triblock copolymer having a protected hydroxyl group can be obtained.

The thus-prepared diblock or triblock copolymer having a protected hydroxyl group is subjected to a treatment for removing a known protecting group to give a diblock or triblock containing a free hydroxyl group. A copolymer can be obtained.

Representative treatment methods for removing the protecting group include a method by alcoholysis and a method by hydrolysis. In the deprotection group treatment by alcoholysis or hydrolysis, if necessary, various known and commonly used catalysts such as an acidic catalyst or a basic catalyst may be co-present.

In carrying out the above-mentioned deprotection treatment by alcoholysis, various conventional alcohols can be used. Such alcohols include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, n-octanol,
Alternatively, alcohols such as 2-ethylhexanol may be used. Among these alcohols, the use of lower alkyl alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol is particularly preferred.

The deprotection treatment by alcoholysis or hydrolysis is carried out by subjecting the diblock or triblock copolymer to alcohol or water in an amount equal to or more than the same mole as the protected hydroxyl group to be subjected to the deprotection treatment. The treatment may be performed at a temperature of about 0 to 100 ° C, preferably about 10 to 80 ° C.

In the above-mentioned method for producing a diblock copolymer and a triblock copolymer, a monomer having a protected hydroxyl group as described above is used as the first monomer (M-1). A polymer having a free hydroxyl group is obtained by subjecting a polymer having a protected hydroxyl group to a treatment for removing the protecting group by the method described above, and then obtaining a polymer having a free hydroxyl group. Further, by sequentially polymerizing the third monomer (M-3), a diblock copolymer or a triblock copolymer having a free hydroxyl group can be obtained.

Furthermore, after the first monomer (M-1) of the α, β-unsaturated carboxylic acid esters is polymerized by the above-mentioned method for producing a triblock copolymer, the above-mentioned protection is effected. Hydroxyl group-containing second monomer (M
-2), which is polymerized successively to obtain a diblock copolymer having a protected hydroxyl group, which is freed by subjecting it to a treatment for removing the protecting group by the method described above. After obtaining a diblock copolymer having a hydroxyl group, a third monomer (M-3) is sequentially polymerized again, whereby a triblock copolymer having a free hydroxyl group can be obtained.

In the case where the polymer having a free hydroxyl group is introduced again into the polymerization system by performing the treatment for removing the protecting group as in this case, the polymer may be introduced without drying the inside of the reaction apparatus. . Further, the obtained polymer having an advantageous hydroxyl group may be used as it is, or may be subjected to any other known and commonly used treatment. For example, a polymer that has been subjected to treatment by a method as described below to isolate a polymer may be used as it is, or the isolated polymer may be used after being dissolved again in the above-described solvent. . Also, after performing the treatment to remove the protecting group,
When sequentially polymerizing the second monomer (M-2) or the third monomer (M-3) among the α, β-unsaturated carboxylic acid esters, the second monomer (M-2) or the third monomer (M-2) The monomer (M-3) can be used without performing a treatment such as dehydration treatment or removal of a stabilizer,
The polymerization system can be polymerized by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Even when using solvents in the polymerization system, it can be used without performing dehydration treatment and the like.Moreover, even in the introduction method when each monomer and the solvents are introduced into the polymerization system, there is no need to use a syringe operation or the like. It is also possible to use a known and commonly used introduction method, for example, a method of directly charging a chemical bottle into a flask or a method of using a pipette or the like.

The polymer, diblock copolymer and triblock copolymer obtained by the production method of the present invention are:
It can be used for various applications as it is, or can be used for various applications after subjecting to a known and commonly used treatment.
For example, the obtained polymerization reaction solution may be used as it is, or solvent exchange or the like may be performed according to a known and commonly used method. Further, a polymer may be obtained by removing the solvent, or the obtained α, β- The treatment can also be carried out using a solvent having poor solubility in the unsaturated carboxylic acid ester polymer, diblock copolymer or triblock copolymer.

Representative examples of the poorly soluble solvent include, for example, alcohols used in the above-mentioned method of subjecting a protected diblock or triblock copolymer having a hydroxyl group to deblocking treatment, ethylene glycol, and ethylene glycol. Organic solvents containing a hydroxyl group, such as monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether and propylene glycol mono-n-propyl ether, and water are listed.

In all the polymerization methods of the production method of the present invention, the polymerization form may be polymerization in a state of being uniformly dissolved in a medium (solution polymerization) or polymerization in a state of being dispersed or emulsified in a medium (solution polymerization). Suspension polymerization or emulsion polymerization).

In the polymerization in a state of being dispersed or emulsified in a medium, the polymerization system can be stabilized by using a known and commonly used dispersion stabilizer or emulsifier, if necessary.

The polymer or block copolymer obtained by the production method of the present invention is mainly used for paints, adhesives,
It can be used for various applications such as molding, textiles, and fiber treatment, and the objects or base materials to be applied to the respective applications are known and commonly used ones.

[0094]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these ranges.

<Example 1> (Production example of polymer of α, β-unsaturated carboxylic acid ester) The pressure in the reaction vessel of the reaction apparatus shown in FIG. Argon was introduced into the vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Then, while flowing argon through the three-way cock (1), 9.9 ml of dry dimethylformamide (DMF) and 1.80 ml (12.94 mmol) of triethylamine (TEA) were introduced into the reaction vessel using a syringe. )
And chlorodiphenylphosphine (CDP) 2.00
ml (10.79 mmol) were added sequentially. The contents of the reaction vessel were shaken well and left overnight in a cool, dark place. The mixture was colored brown. (Hereinafter, this mixture is referred to as (CDP / TE
A / DMF). )

Next, the pressure inside the reaction vessel of the separately prepared reactor shown in FIG. 1 was reduced using a vacuum pump.
Argon was introduced into the reaction vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Then, 25.0 ml of dry DMF, 12.27 ml (70.4 mmol) of dry DMF, cyclohexyl methacrylate (c-HMA) were placed in a reaction vessel using a syringe while flowing argon through the three-way cock (1). 0.56 ml of (CDP / TEA / DMF) mixture (CD
(P: 0.44 mmol), the temperature was raised to 60 ° C. while stirring the contents, and the polymerization reaction was continued while stirring at the same temperature for 24 hours. After completion of the reaction, 60 ml of tetrahydrofuran (THF) was added to the reaction mixture to dilute it, and the mixture was poured into 600 ml of water to precipitate a polymer. After filtering off the polymer, washing with methanol,
After air-drying overnight, it was further vacuum-dried at 50 ° C. for 12 hours to obtain 6.16 g (yield = 52%) of white poly-c-HMA. Average molecular weight: Mn: 360,000, M
w: 1,040,000 and Mw / Mn: 2.89 (from GPC measurement).

<Example 2> (Production example of polymer of α, β-unsaturated carboxylic acid ester) Using the same reaction vessel as in Example 1, and operating in the same manner as in Example 1, the inside of the reaction vessel was The air was replaced with argon. Then, while flowing argon through the three-way cock, 9.9 ml of dry DMF and diazabicyclo [5,4,0] -7-undecene (DBU) were introduced into the reaction vessel using a syringe.
1.94 ml (12.94 mmol) and CDP2.00
ml (10.79 mmol) were added sequentially. After shaking the contents well, it was left overnight in a cool and dark place. The mixture was colored yellow. (Hereinafter, this mixture is referred to as (CDP / DBU / D
MF). )

Next, the inside of the reaction vessel of the separately prepared reactor shown in FIG. 1 was evacuated using a vacuum pump.
Argon was introduced into the reaction vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Then, while flowing argon through the three-way cock (1), 25.0 ml of dry DMF and 12.27 ml of c-HMA (70.
4 mmol) and 0.57 ml of a (CDP / DBU / DMF) mixture (CDP: 0.44 mmol) were added in sequence, and then the temperature was raised to 60 ° C. while stirring the contents. The polymerization reaction was continued while stirring. After completion of the reaction, the reaction mixture was diluted by adding 60 ml of THF,
This was poured into 600 ml of water to precipitate a polymer. The polymer was separated by filtration, washed with methanol, air-dried overnight, and further vacuum-dried at 50 ° C. for 12 hours to give 3.67 g (yield = 31%) of white poly.
c-HMA was obtained. The average molecular weight is Mn: 600,000, Mw:
1,540,000, Mw / Mn: 2.57 (from GPC measurement).

<Example 3> (Production example of polymer of α, β-unsaturated carboxylic acid ester) Using the same reaction vessel as in Example 1, and operating in the same manner as in Example 1, the inside of the reaction vessel was The air was replaced with argon. Then, while flowing argon through the three-way cock portion, 9.9 ml of dry DMF, 1.05 ml (12.94 mmol) of pyridine (Py) and C
2.00 ml (10.79 mmol) of DP were added sequentially. The contents were shaken well and left overnight in a cool, dark place. The mixture was colored brown. (This mixture is referred to below as (CDP /
Py / DMF). )

Next, the inside of the reaction vessel of the separately prepared reactor shown in FIG. 1 was evacuated using a vacuum pump.
Argon was introduced into the reaction vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Then, while flowing argon through the three-way cock (1), 25.0 ml of dry DMF and 12.27 ml of c-HMA (70.
4 mmol) and (CDP / Py / DMF) mixture.
After sequentially adding 53 ml (CDP: 0.44 mmol),
While stirring the mixture, the temperature was raised to 60 ° C.
The polymerization reaction was continued while stirring for an hour. After the reaction was completed, 60 ml of THF was added to the reaction mixture to dilute it, and the mixture was poured into 600 ml of water to precipitate a polymer. The polymer was separated by filtration, washed with methanol, air-dried overnight, and further vacuum-dried at 50 ° C. for 12 hours to obtain 9.24 g (yield = 78%) of white poly-c- H
MA was obtained. Average molecular weight: Mn: 120,000, Mw: 32
Mw / Mn: 2.67 (from GPC measurement).

<Example 4> (Production example of polymer of α, β-unsaturated carboxylic acid ester) Using the same reaction vessel as in Example 1, and operating in the same manner as in Example 1, the inside of the reaction vessel was The air was replaced with argon. Then, while flowing argon through the three-way cock, dry toluene (tol) was introduced into the reaction vessel using a syringe.
9.9 ml and CDP 2.00 ml (10.79 mmol) were added sequentially. (Hereinafter, this mixture is referred to as (CDP / to
l). )

Next, the pressure inside the reaction vessel of the separately prepared reactor shown in FIG. 1 was reduced using a vacuum pump.
Argon was introduced into the reaction vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Next, 25.0 ml of dry DMF and 12.27 ml of c-HMA (71.2 ml) were introduced into the reaction vessel using a syringe while flowing argon through the three-way cock (1).
0 mmol), 0.12 ml (0.88 mmol) of TEA
And (CDP / tol) mixed solution 0.49 ml (CDP:
(0.44 mmol), and the temperature was raised to 60 ° C. while stirring the content, and the polymerization reaction was continued with stirring at the same temperature for 24 hours. After the reaction is completed, 60
The mixture was diluted by adding THF (ml) and poured into 600 ml of water to precipitate a polymer. After filtering off the polymer,
After washing with methanol and air-drying overnight, 5
After vacuum drying at 0 ° C. for 12 hours, 6.40 g (yield =
54%) of white poly-c-HMA. Average molecular weight: Mn: 550,000, Mw: 1.14 million, Mw / Mn: 2.0
7 (from GPC measurement).

<Example 5> (Production example of polymer of α, β-unsaturated carboxylic acid ester) Using the same reaction vessel as in Example 1, and operating in the same manner as in Example 1, the inside of the reaction vessel was The air was replaced with argon. Then, while flowing argon through the three-way cock, 10.0 ml of dry DMF and 4.56 ml of cyclohexyl acrylate (c-HA) were placed in a reaction vessel using a syringe.
9.0 mmol), prepared in Example 4 (CDP / to
l) 0.23 ml of the mixture (CDP: 0.208 mmol)
Then, 0.057 ml (0.41 mmol) of TEA were added in sequence, then the temperature was raised to 60 ° C. while stirring the contents, and the polymerization reaction was continued with stirring at the same temperature for 24 hours. After completion of the reaction, the reaction mixture was diluted by adding 60 ml of THF,
This was poured into 600 ml of water to precipitate a polymer. The polymer was separated by filtration, washed with methanol, air-dried overnight, and further dried under vacuum at 50 ° C. for 12 hours to obtain 4.47 g (yield = 100%) of white poly-c. -HA was obtained. Average molecular weight: Mn: 13,000, M
w: 49,000 and Mw / Mn: 3.77 (from GPC measurement).

<Example 6> (Production example of polymer of α, β-unsaturated carboxylic acid ester) In Example 5, 4.73 ml of tetrahydrofurfuryl methacrylate (TFMA) (2) was used in place of c-HA.
4.84 g (yield = 98%) of white poly-TFM in the same manner as in Example 5, except that 9.0 mmol) was used.
A was obtained. Average molecular weight: Mn: 570000, Mw: 46
Mw / Mn: 8.07 (from GPC measurement).

<Example 7> (Production example of polymer of α, β-unsaturated carboxylic acid ester) In Example 5, instead of c-HA, 3.10 ml of methyl methacrylate (MMA) (29.0 mmol) was used. ) Was used in the same manner as in Example 5 to obtain 2.58 g (yield = 89%) of white poly MMA. The average molecular weights were as follows: Mn: 46,000, Mw: 90,000, Mw / Mn: 1.96.
(From GPC measurement).

<Example 8> (Production example of polymer of α, β-unsaturated carboxylic acid ester) In Example 5, instead of c-HA, 3.92 ml (29.0 mmol) of allyl methacrylate (AlMA) was used. ), And 2.56 g (yield = 70%) of white poly-AlMA was obtained in the same manner as in Example 5 except that the polymerization reaction time was shortened to 10 hours. The average molecular weight is Mn: 720,000,
Mw: 1.82 million, Mw / Mn: 2.56 (from GPC measurement).

<Example 9> (Production example of polymer of α, β-unsaturated carboxylic acid ester) In Example 5, MMA 3.10 was used instead of c-HA.
ml (29.0 mmol), and dimethylaminoethyl methacrylate (DAEMA) 0.07 was used instead of TEA.
0.90 g (yield = 31%) of white poly-M in the same manner as in Example 5 except that ml (0.41 mmol) was used.
MA was obtained. Average molecular weight: Mn: 46,000, Mw: 9
Mw / Mn: 1.96 (from GPC measurement).

Example 10 (Production Example of Diblock Copolymer) Using the same reaction vessel as in Example 1 and operating in the same manner as in Example 1, the air in the reaction vessel was replaced with argon. Then, while flowing argon through the three-way cock, using a syringe, 9.9 ml of dry DMF, TE
A 1.80 ml (12.94 mmol) and 2.
00 ml (10.79 mmol) were sequentially added, and the mixture was allowed to stand overnight in a cool dark place to obtain a mixture. (Hereinafter, this mixture is abbreviated as (CDP / TEA / DMF).)

Next, after the pressure inside the reaction vessel of the separately prepared reactor shown in FIG. 1 was reduced using a vacuum pump,
Argon was introduced into the reaction vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Next, while flowing argon through the three-way cock (1), 10.0 ml of dry DMF and n-butyl methacrylate (n-butyl methacrylate) were introduced into the reaction vessel using a syringe.
BMA) 4.50 ml (28.2 mmol) and (CDP
/ TEA / DMF) mixed solution 0.22 ml (CDP: 0.1
76 mmol), the temperature was raised to 60 ° C. while stirring the contents, and the polymerization reaction was continued with stirring at the same temperature for 24 hours to obtain poly (n) having a polymerization active group at the terminal. -BMA). Here, by analyzing the reaction mixture by ¹ H-NMR, n-B
It was confirmed that the conversion of MA exceeded 95%.

Then, while flowing argon through the three-way cock (1), 10.0 ml of dry DMF and 6.10 ml of trimethylsiloxyethyl methacrylate (TSEMA) (28.
2 mmol) in sequence, and while stirring the mixture,
The temperature was raised to 60 ° C., and the polymerization reaction was continued while stirring at the same temperature for 36 hours. After the reaction is completed, 100
The mixture was diluted by adding THF (ml) and poured into 800 ml of water to precipitate a polymer. After filtering off the polymer,
After washing with methanol and air-drying overnight, 5
After vacuum drying at 0 ° C. for 12 hours, 7.26 g (yield =
95%) of a white (n-BMA / TSEMA) diblock copolymer. The average molecular weight is Mn: 150,000, Mw:
400,000, Mw / Mn: 2.67 (from GPC measurement).

The composition of the thus obtained diblock copolymer was calculated from ¹ H-NMR analysis data, and the molar ratio of n-BMA units / TSEMA units was 54.
/ 46.

Example 11 (Production Example of Triblock Copolymer) Using the same reaction vessel as in Example 1 and operating in the same manner as in Example 1, the air in the reaction vessel was replaced with argon. Then, while flowing argon through the three-way cock, using a syringe, 9.9 ml of dry DMF, TE
A 1.80 ml (12.94 mmol) and 2.
00 ml (10.79 mmol) were sequentially added, and the mixture was allowed to stand overnight in a cool and dark place to obtain a mixture. (Hereinafter, this mixture is referred to as (C
DP / TEA / DMF). )

Next, the pressure inside the reaction vessel of the separately prepared reactor shown in FIG. 1 was reduced using a vacuum pump.
Argon was introduced into the reaction vessel. This operation was further performed twice to replace the air in the reaction vessel with argon.

Next, 10.0 ml of dry DMF and 4.50 ml of n-BMA (28.2) were introduced into the reaction vessel using a syringe while flowing argon through the three-way cock (1).
Mmol) and (CDP / TEA / DMF) mixture.
After sequentially adding 22 ml (CDP: 0.176 mmol), the contents were heated to 60 ° C. while stirring, and the polymerization reaction was continued while stirring at the same temperature for 24 hours.

After completion of the reaction, 10.0 ml of dry DMF and 3.41 ml (28%) of hydroxyethyl methacrylate (HEMA) were placed in a reaction vessel using a syringe while flowing argon through the three-way cock (1). .2 mmol) were added successively, and the mixture was stirred for 60
C., and the polymerization reaction was continued while stirring at the same temperature for 24 hours to obtain a (n-BMA / HEMA) diblock copolymer having a polymerization active group at the terminal. Here, by analyzing the reaction mixture by ¹ H-NMR, the conversion of n-BMA and HEMA was 9
It was confirmed that it exceeded 5%.

Thereafter, 10.0 ml of dry DMF and 4.91 ml of c-HMA were further introduced into the reaction vessel using a syringe while flowing argon through the three-way cock (1).
(28.2 mmol) was sequentially added, and then the temperature was raised to 60 ° C. while stirring the content, and the polymerization reaction was continued with stirring at the same temperature for 36 hours. After the reaction was completed, 100 ml of THF was added to the reaction mixture to dilute it, and the mixture was poured into 800 ml of water to precipitate a polymer. The polymer was separated by filtration, washed with methanol, air-dried overnight, and further vacuum-dried at 50 ° C. for 12 hours to obtain 12.03 g.
(Yield = 97%) white (n-BMA / HEMA / c)
-HMA) triblock copolymer was obtained. Average molecular weight: Mn: 220,000, Mw: 570,000, Mw / Mn: 2.59
(From GPC measurement).

The composition of the obtained triblock copolymer was calculated from ¹ H-NMR analysis data.
The molar ratio of n-BMA units / HEMA units / c-HMA units was 36/30/34.

<Example 12> (Production example of triblock copolymer) Using the same reaction vessel as in Example 1 and operating in the same manner as in Example 1, the air in the reaction vessel was replaced with argon. Then, while flowing argon through the three-way cock portion, 10.0 ml of dry DMF, T
6.10 ml (28.2 mmol) of SEMA and Example 1
(CDP / TEA / DMF) mixture prepared in Step 0.2
After sequentially adding 2 ml (CDP: 0.176 mmol),
While stirring the contents, the temperature was raised to 60 ° C.
By continuing the polymerization reaction with stirring for a time, poly (TSEMA) having a polymerization active group at a terminal was obtained. Here, by analyzing the reaction mixture by ¹ H-NMR, it was confirmed that the conversion rate of TSEMA exceeded 95%.

The obtained polymerization reaction solution of poly (TSEMA) was diluted by adding 20 ml of THF.
The poly-hydroxyethyl methacrylate was precipitated by pouring into ml of water to eliminate the trimethylsilyl group. The polymer was separated by filtration, washed with methanol, and dried.

Thereafter, DMF2 was placed in the untreated reaction vessel.
0 ml, 5.56 g of the polyhydroxyethyl methacrylate obtained above and 4.50 ml of n-BMA (28.2
Mmol), and the contents are stirred while stirring.
The temperature was raised to 0 ° C., and the polymerization reaction was continued with stirring at the same temperature for 36 hours. After completion of the reaction, 50 ml of T
HF was added for dilution, and the resulting mixture was poured into 800 ml of water to precipitate a polymer. The polymer was separated by filtration, washed with methanol, air-dried overnight, and further dried under vacuum at 50 ° C. for 12 hours to obtain 8.71 g (yield = 96).
%) Of a white (TSEMA / n-BMA) diblock copolymer. Average molecular weight: Mn: 130,000, Mw: 36
Mw / Mn: 2.77 (from GPC measurement).

The composition of the diblock copolymer obtained here was calculated from the ¹ H-NMR analysis data.
The molar ratio of SEMA units / n-BMA units is 52/48.
Met.

[0128]

According to the production method of the present invention, an α, β-unsaturated carboxylic acid ester is polymerized in the presence of a specific phosphorus compound and a specific amine compound to obtain an α, β-unsaturated carboxylic acid ester. By successively polymerizing the saturated carboxylic acid esters, it is possible to obtain a (meth) acrylate polymer or a block copolymer having high versatility and high molecular weight.

Further, a monomer having a hydroxyl group protected as an α, β-unsaturated carboxylic acid ester is used,
After homopolymerization or after obtaining a block copolymer, a block copolymer having a free hydroxyl group in the molecule can be produced by removing the protecting group.

Further, the polymer or block copolymer obtained by the production method of the present invention is useful mainly for various uses such as paints, adhesives, moldings, fibers and fiber treatments.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a reaction apparatus used in Examples.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Three-way cock 2 Argon or nitrogen introduction pipe 3 Heater 4 Magnetic stirrer 5 Oil berth 6 Thermosensor 7 Stirrer

Claims (28)

[Claims] 1. A compound of the general formula (I) (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) A method for producing an α, β-unsaturated carboxylic acid ester polymer, comprising polymerizing a monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic acid esters below. 2. The phosphorous compound (A) represented by the general formula (I) is chlorodiarylphosphine.
The method for producing the α, β-unsaturated carboxylic acid ester polymer described in the above. 3. An α, β-unsaturated carboxylic acid ester,
The method for producing an α, β-unsaturated carboxylic acid ester polymer according to claim 1 or 2, which is an acrylic acid ester and / or a methacrylic acid ester. 4. An α, β-unsaturated carboxylic acid ester (M
The method for producing an α, β-unsaturated carboxylic acid ester polymer according to claim 1, 2 or 3, wherein -1) has no active hydrogen bonded to a hetero atom. 5. A compound of the general formula (I) (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) Below, the first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized, and then the first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized. 2. A method for producing a diblock copolymer, comprising sequentially polymerizing two monomers (M-2). 6. The second monomer (M-2) is an α, β-unsaturated carboxylic acid ester having a hydroxyl group.
A method for producing the diblock copolymer according to the above. 7. The phosphorus compound (A) represented by the general formula (I) is a chlorodiarylphosphine.
Or a method for producing a diblock copolymer according to 6. 8. An α, β-unsaturated carboxylic acid ester,
The method for producing a diblock copolymer according to claim 5, 6 or 7, which is an acrylic ester and / or a methacrylic ester. 9. The method according to claim 5, wherein the first monomer (M-1) has no active hydrogen bonded to a hetero atom.
The method for producing a diblock copolymer according to 6, 7, or 8. 10. A compound of the formula (I) (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) Below, the first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized, and then the first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized. A triblock, characterized by polymerizing two monomers (M-2) and further sequentially polymerizing a third monomer (M-3) selected from the group consisting of α, β-unsaturated carboxylic esters. A method for producing a copolymer. 11. The production of the triblock copolymer according to claim 10, wherein the second monomer (M-2) or the third monomer (M-3) is an α, β-unsaturated carboxylic acid ester having a hydroxyl group. Method. 12. The phosphorous compound (A) represented by the general formula (I) is chlorodiarylphosphine.
12. The method for producing a triblock copolymer according to 0 or 11. 13. The method for producing a triblock copolymer according to claim 10, wherein the α, β-unsaturated carboxylic acid ester is an acrylic acid ester and / or a methacrylic acid ester. 14. The method according to claim 1, wherein the first monomer (M-1) has no active hydrogen bonded to a hetero atom.
14. The method for producing a triblock copolymer according to 0, 11, 12 or 13. 15. A method for producing a diblock copolymer having a free hydroxyl group by producing a diblock copolymer having a protected hydroxyl group and then subjecting the diblock copolymer to a treatment for removing a protecting group, the method comprising the steps of: Is a diblock copolymer having the general formula (I): (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) Below, a first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized, and then a second monomer selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized. A method of sequentially polymerizing the monomer (M-2), wherein the first monomer (M-1)
Alternatively, it is a diblock copolymer having a protected hydroxyl group obtained by a method of polymerizing using an α, β-unsaturated carboxylic acid ester having a protected hydroxyl group as the second monomer (M-2). A method for producing a diblock copolymer having a free hydroxyl group. 16. The phosphorus compound (A) represented by the general formula (I) is chlorodiarylphosphine.
6. The method for producing a diblock copolymer having a free hydroxyl group according to 5. 17. The method for producing a diblock copolymer having a free hydroxyl group according to claim 15, wherein the α, β-unsaturated carboxylic acid ester is an acrylic acid ester and / or a methacrylic acid ester. 18. The method according to claim 1, wherein the first monomer (M-1) has no active hydrogen bonded to a hetero atom.
18. The method for producing a diblock copolymer having a free hydroxyl group according to 5, 16, or 17. 19. A method for producing a triblock copolymer having a free hydroxyl group by producing a triblock copolymer having a protected hydroxyl group and then subjecting the triblock copolymer to a process of removing a protecting group, the method comprising the steps of: Is a triblock copolymer having the general formula (I): (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) Below, the first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized, and then the first monomer (M-1) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized. A method of polymerizing a second monomer (M-2) and further sequentially polymerizing a third monomer (M-3) selected from the group consisting of α, β-unsaturated carboxylic esters, Monomer (M-
1), the second monomer (M-2) and the third monomer (M-
At least one of 3) is a triblock copolymer having a protected hydroxyl group obtained by a method of polymerizing using an α, β-unsaturated carboxylic acid ester having a protected hydroxyl group. A method for producing a triblock copolymer having a free hydroxyl group. 20. The phosphorus compound (A) represented by the general formula (I) is chlorodiarylphosphine.
10. The method for producing a triblock copolymer having a free hydroxyl group according to 9 above. 21. The method for producing a triblock copolymer having a free hydroxyl group according to claim 19 or 20, wherein the α, β-unsaturated carboxylic acid ester is an acrylic acid ester and / or a methacrylic acid ester. 22. The method according to claim 1, wherein the first monomer (M-1) has no active hydrogen bonded to a hetero atom.
22. The method for producing a triblock copolymer having a free hydroxyl group according to 9, 20, or 21. 23. A compound of the formula (I) (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) Below, α, β having a protected hydroxyl group
-Polymerizing the unsaturated carboxylic acid ester first monomer (M-1), and subjecting the first monomer (M-1) to a treatment for removing a protecting group to produce an α, β-unsaturated carboxylic acid ester polymer having a free hydroxyl group; Subsequently, a second monomer (M-2) selected from the group consisting of α, β-unsaturated carboxylic esters is sequentially polymerized, thereby producing a diblock copolymer having a hydroxyl group. 24. The phosphorus compound (A) represented by the general formula (I) is chlorodiarylphosphine.
4. The method for producing a diblock copolymer having a hydroxyl group according to 3. 25. The method for producing a hydroxyl group-containing diblock copolymer according to claim 23, wherein the α, β-unsaturated carboxylic acid ester is an acrylic acid ester and / or a methacrylic acid ester. 26. A compound of the general formula (I) (Wherein R ¹ and R ² each independently represent an alkyl group, an alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an aryl group or an aryl group having a substituent, R ¹ and R ² may combine to form a divalent organic group, and X represents a halogen atom.) And a tertiary amine compound (B) Below, α, β having a protected hydroxyl group
-Polymerizing the unsaturated carboxylic acid ester first monomer (M-1), and subjecting the first monomer (M-1) to a treatment for removing a protecting group to produce an α, β-unsaturated carboxylic acid ester polymer having a free hydroxyl group; Next, a second monomer (M-2) selected from the group consisting of α, β-unsaturated carboxylic esters is polymerized, and a third monomer selected from the group consisting of α, β-unsaturated carboxylic esters is further polymerized. A method for producing a hydroxyl-containing triblock copolymer, which comprises sequentially polymerizing the monomer (M-3). 27. The phosphorus compound (A) represented by the general formula (I) is chlorodiarylphosphine.
7. The method for producing a triblock copolymer having a hydroxyl group according to 6. 28. The method for producing a hydroxyl-containing triblock copolymer according to claim 26, wherein the α, β-unsaturated carboxylic acid ester is an acrylic acid ester and / or a methacrylic acid ester.