JP2002256076A - Production method for (meth)acrylic ester based polymer having vinyl ether as side chain - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing, in good yield, (meth)acrylic esters having a vinyl ether group as a side chain, and to provide a method for effectively displaying a polymerization property of the vinyl ether group as the side chain. SOLUTION: This production method for (meth)acrylic esters comprises reacting a (meth)acrylic polymer having a structural unit expressed by a general formula (1), with vinyl ethers expressed by the general formula (2): R<3> -CH= CH-(OA)n -X. (R<1> denotes H or a methyl group, and Z denotes a-OH group, a halogen atom, a -OR<2> group (R<2> denotes an organic residual group.), a -OM group (M denotes an alkaline (earth) metal.), or CH2 =CR<1> COO- group, R<3> denotes H or the organic residual group, A denotes a -CHR<4> CHR<5> - group (R<4> and R<5> denote independently H or the organic residual group), a plurality of A are the same or different, and a bonding style where a plurality of oxyalkylene group (OA) is composed of 2 or above kinds of oxyalkylene groups, is either block or random. n denotes an integer of 2 or above, and X denotes the -OH group or the halogen atom.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a (meth) acrylate polymer having a vinyl ether group in a side chain. For more information, see (Meta)
The present invention relates to a method for producing a (meth) acrylate polymer having a vinyl ether group in a side chain, which comprises reacting an acrylic polymer with a vinyl ether having an oligoalkylene glycol as a spacer.

(Meth) having a vinyl ether group in the side chain
Acrylic ester-based polymers are used as raw materials for pharmaceuticals and agrochemicals, synthetic intermediates, crosslinking agents, resins for powder coatings, and as polymerizable materials, adhesives, adhesives, biomaterials, dental materials, optical members, information recording materials, and optical fibers. Material, resist material, insulator, sealing material, printing ink, paint, casting material, decorative board, W
PC, coating material, lining material, civil engineering building material, putty, repair material, floor material, pavement material gel coat, overcoat, hand lay-up, spray-up, pultrusion molding, filament winding, SMC, BMC and other molding materials, sheets, etc. It is a useful compound that is widely used in applications.

[0003]

2. Description of the Related Art As a method for producing a (meth) acrylate polymer having a vinyl ether group in a side chain, there are the following methods.
A method is known in which a vinyl group on the (meth) acrylate side of vinyl ether group-containing (meth) acrylates is selectively radically or anionically polymerized.

Further, a method of transesterifying an alkyl (meth) acrylate polymer with a hydroxyl group-containing alkyl vinyl ether is disclosed in Japanese Patent No. 28676.
No. 44.

However, in the above conventional manufacturing method,
In the case of radical polymerization of vinyl ether group-containing (meth) acrylates, not only the vinyl group on the (meth) acrylate side but also the vinyl group on the vinyl ether side may be polymerized, and a crosslinked insoluble polymer may be formed. . Also, anionic polymerization is not industrially advantageous.

According to the method of transesterification between a (meth) acrylic acid alkyl ester polymer and a hydroxyl group-containing alkyl vinyl ether, the distance between the main chain of the obtained polymer and the vinyl ether group is short, and the polymerizability of the vinyl ether group is reduced. It is difficult to fully demonstrate.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a (meth) acrylate polymer having a vinyl ether group in a side chain in good yield. It is intended to sufficiently exhibit the polymerizability of the vinyl ether group in the side chain.

[0008]

Means for Solving the Problems The inventors of the present invention have developed a method for producing a (meth) acrylate polymer having a vinyl ether group in a side chain in a high yield, and a method for sufficiently polymerizing the vinyl ether group in the side chain. As a result of intensive studies to provide a method of exerting the effect, a (meth) acrylic compound having a vinyl ether group in a side chain is obtained by reacting a (meth) acrylic polymer with a vinyl ether having an oligoalkylene glycol as a spacer. That an acid ester polymer can be produced in good yield, and that the distance between the main chain and the vinyl ether group is sufficient by introducing an oligoalkylene glycol between the main chain and the vinyl ether group, and that the cationic polymerization initiator is used. Cation polymerizability of the side chain vinyl ether group It found that you can, and have completed the present invention.

That is, the present invention provides the following general formula (1):

[0010]

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(Wherein, R ¹ represents a hydrogen atom or a methyl group, Z represents an —OH group, a halogen atom, an —OR ² group (R ²
Represents an organic residue), -OM group (M is an alkali (earth))
It represents a metal) or an _CH 2 ⁼ CR 1 COO- group. And a (meth) acrylic polymer having a structural unit represented by the following general formula (2): R ³ —CH ＝ CH— (OA) n—X (where R ³ is a hydrogen atom or an organic residue) A represents a —CHR ⁴ CHR ⁵ — group (R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue), and a plurality of A may be the same or different; When two oxyalkylene groups (OA) are composed of two or more oxyalkylene groups, the bonding form may be either block or random, n represents a positive number of 2 or more, and X represents an -OH group or halogen. Which represents an atom represented by the following general formula (3):

[0012]

Embedded image

(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or an organic residue, and A represents —C
Represents an HR ⁴ CHR ⁵ — group (R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue), a plurality of A may be the same or different, and a plurality of oxyalkylene groups (OA ) Is composed of two or more oxyalkylene groups, the bonding form may be either block or random. n represents a positive number of 2 or more. Having a vinyl ether group having a structural unit represented by) in the side chain (meth)
The present invention relates to a method for producing an acrylate polymer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A (meth) acrylic polymer, which is one of the raw materials of the present invention, may be a homopolymer as long as it has a structural unit represented by the general formula (1). The polymer is not particularly limited. R ¹ in the general formula (1) is a hydrogen atom or a methyl group, and Z is —OH
Group, a halogen atom, -OR ² group ^{(R 2} represents an organic residue), - OM group (M represents an alkali (representing earth) metal) or _CH 2 ⁼ CR 1 COO- group. The organic residue represented by R ² is a linear, branched alkyl group having 1 to 4 carbon atoms.

The range of the degree of polymerization of the (meth) acrylate polymer essentially containing the structural unit represented by the general formula (1) has a lower limit of the number average molecular weight, preferably 1,0.
00, more preferably 2000, particularly preferably 300
0, and the upper limit of the number average molecular weight is preferably 20,0
00,000, more preferably 10,000,000,
Particularly preferably, it is 5,000,000.

Typical examples of the structural unit represented by the general formula (1) are not particularly limited, but specific examples include (meth) acrylic acid, (meth) acrylic chloride, and (meth) acrylic acid. ) Acrylic acid bromide, (meth) acrylic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
Butyl acrylate, sodium (meth) acrylate,
Examples include structural units derived from monomers such as potassium (meth) acrylate, magnesium (meth) acrylate, and calcium (meth) acrylate.

Of these, (meth) acrylic acid, (meth) acrylic chloride, (meth) acrylic anhydride, methyl (meth) acrylate, ethyl (meth) acrylate, sodium (meth) acrylate, ( Structural units derived from a monomer of potassium (meth) acrylate are preferably used.

The structural units other than the structural unit represented by the general formula (1) constituting the (meth) acrylate polymer according to the present invention are not particularly limited. , Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-propyl (meth) acrylate , Isopropyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Isodecyl (meth) acrylate, tridecyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) (Meth) acrylates such as acrylate, isobornyl (meth) acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate and phenoxyethyl (meth) acrylate; 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, methyl (α-hydroxymethyl) acrylate, ethyl (α-hydroxymethyl) acrylate, caprolactone-modified hydroxy acrylate (Placcel F series, trade name, Daicel Chemical Industries, Ltd.)
), Caprolactone-modified hydroxy methacrylate (trade name: Placcel FM series, manufactured by Daicel Chemical Industries, Ltd.), hydroxyl group-containing (meth) acrylates such as 4-hydroxymethylcyclohexylmethyl (meth) acrylate; acrylic acid, methacrylic acid, maleic acid Acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, carboxyl-terminated caprolactone-modified acrylate (trade name: Placcel FA series, Daicel Chemical Industries, Ltd.)
), Carboxyl group-terminated caprolactone-modified methacrylate (trade name: Praxel FMA series, manufactured by Daicel Chemical Industries, Ltd.), sulfoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl Acid functional group-containing (meth) acrylates such as acid phosphate; styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl chloride,
Vinyl compounds such as vinylidene chloride; silicon-containing polymerizable compounds such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and trimethylsiloxyethyl methacrylate Monomers: trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, hexafluoro Halogen-containing polymerizable monomers such as propyl methacrylate and perfluorooctylethyl (meth) acrylate; (meth) acrylamide, N, N-dimethylaminopropylacrylamide , N-isopropylacrylamide, t-butylacrylamide, methylenebis (meth) acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, N-methylol (meth) acrylamide, N, N'-dimethylamino Ethyl (meth) acrylate, N, N'-diethylaminoethyl (meth) acrylate, N-methyl-N-vinylformamide, dimethylaminoethyl methacrylate sulfate, N
-Vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinylpyrrolidone, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diacetoneacrylamide, N
-Nitrogen atom-containing polymerizable monomers such as -phenylmaleimide, N-cyclohexylmaleimide, and 2-isopropenyl-2-oxazoline; ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol diacrylate, polyethylene glycol # 200 di (meth) acrylate,
Polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) acrylate, polyethylene glycol # 1000 diacrylate, 1,3-butylene glycol diacrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, 1,9
-Nonanediol diacrylate, neopentyl glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, EO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris Acryloyloxyethyl phosphate,
Glycerin dimethacrylate, 2-hydroxy-1,3
-Dimethacryloxypropane diacrylate, 2,2-
Polyfunctional polymerizable monomers such as bis [4- (methacryloxyethoxy) phenyl] propane diacrylate and 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane diacrylate; vinyl methyl ether, Vinyl ethyl ether, vinyl isopropyl ether, vinyl-n-propyl ether, vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-2-ethylhexyl ether, vinyl-n-octadecyl ether, Biano such as cyanomethyl vinyl ether, 2,2-dimethylaminoethyl vinyl ether, 2-chloroethyl vinyl ether, β-difluoromethyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, divinyl ether, etc. Ethers; glycidyl (meth)
Acrylate, α-methylglycidyl acrylate,
3,4-epoxycyclohexylmethyl acrylate (trade name CYCLOMERA200, manufactured by Daicel Chemical Industries, Ltd.), α-methylglycidyl methacrylate (trade name M-GMA, manufactured by Daicel Chemical Industries, Ltd.), 3,4
-Epoxy group-containing polymerizable monomers such as epoxycyclohexylmethyl methacrylate (trade name CYCLOMER M100, manufactured by Daicel Chemical Industries, Ltd.); 2-methacryloyloxyethyl isocyanate (trade name Karens MOI, Showa Denko KK) , Methacryloyl isocyanate (trade name: MAI, Nippon Paint Co., Ltd.), m-isopropenyl-α, α-dimethylbenzyl isocyanate (trade name: m-TMI, Takeda Pharmaceutical Co., Ltd.) 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2
6,6-pentamethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2
6,6-pentamethylpiperidine, 4-cyano-4-
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,
6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-
(Meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-
(Meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-
UV-stable polymerizable monomers such as 2,2,6,6-tetramethylpiperidine; and structural units derived from such monomers. These structural units may be used alone or in combination of two or more.

The structural unit represented by the general formula (1) in the (meth) acrylic acid ester-based polymer accounts for 1 to 100% by weight, more preferably 3 to 10% by weight in the polymer.
0% by weight, more preferably 10 to 100% by weight
As long as it is contained at a ratio of The content ratio is preferable in terms of reaction efficiency and physical properties.

The vinyl ethers as one of the raw materials of the present invention are not particularly limited as long as they are compounds represented by the above general formula (2), wherein R ³ is a hydrogen atom or an organic residue, A represents a —CHR ⁴ CHR ⁵ — group, R ⁴ and R ⁵ are each independently a hydrogen atom or an organic residue, n is a positive number of 2 or more, and X is an —OH group or a halogen atom. is there. However, when Z in the structural unit represented by the general formula (1) is a halogen atom, X is not a halogen atom.

The organic residue represented by R ³ in the general formula (2) is, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a halogen having 1 to 5 carbon atoms. (For example, chlorinated, brominated or fluorinated) alkyl groups and aromatic groups having 6 to 11 carbon atoms.

Of these, alkyl groups having 1 to 2 carbon atoms are preferably used.

The organic residue represented by R ⁴ and R ⁵ contained in the group represented by A in the above general formula (2) may be, for example, a linear, branched or branched C 1-10 carbon atom. Cyclic alkyl group, hydroxyalkyl group having 1 to 5 carbon atoms, 1 to 5 carbon atoms
And a halogenated (for example, chlorinated, brominated or fluorinated) alkyl group of 5 and an aromatic group having 6 to 11 carbon atoms.

Of these, alkyl groups having 1 to 2 carbon atoms, halogenated alkyl groups having 1 to 2 carbon atoms,
8 aromatic groups are preferably used.

Representative examples of vinyl ethers having the oligoalkylene glycol represented by the general formula (2) as a spacer are not particularly limited, but specific examples thereof include 2- (vinyloxyethoxy) ethanol. , 2
-(Vinyloxyisopropoxy) ethanol, 2- (vinyloxyethoxy) propanol, 2- (vinyloxyisopropoxy) propanol, 2- (vinyloxyethoxy) isopropanol, 2- (vinyloxyisopropoxy) isopropanol, 2- ( Vinyloxyethoxyethoxy) ethanol, 2- (vinyloxyethoxyisopropoxy) ethanol, 2- (vinyloxyisopropoxyethoxy) ethanol, 2- (vinyloxyethoxyethoxy) propanol, 2- (vinyloxyethoxyisopropoxy) propanol, 2- (vinyloxyisopropoxyethoxy) propanol, 2- (vinyloxyethoxyethoxy) isopropanol, 2- (vinyloxyethoxyisopropoxy) isopropanol, 2- (vinyloxyisopropoxy) Ethoxy) isopropanol, 2-
(Vinyloxyethoxyethoxyethoxy) ethanol,
2- (vinyloxyethoxyethoxyethoxyethoxy)
Ethanol, 2- (isopropenoxyethoxyethoxy) ethanol, 2- (isopropenoxyethoxyethoxyethoxy) ethanol, 2- (isopropenoxyethoxyethoxyethoxy) ethanol, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethanol, polyethylene glycol Hydroxyl group-containing vinyl ethers such as monovinyl ether and polypropylene glycol monovinyl ether; 1-chloro-2- (vinyloxyethoxy) ethane;
1-chloro-2- (vinyloxyisopropoxy) ethane, 1-chloro-2- (vinyloxyethoxy) propane, 1-chloro-2- (vinyloxyisopropoxy) propane, 1-chloro-2- (vinyloxy Ethoxy) isopropane, 1-chloro-2- (vinyloxyisopropoxy) isopropane, 1-chloro-2- (vinyloxyethoxyethoxy) ethane, 1-chloro-2- (vinyloxyethoxyisopropoxy) ethane, 1 -Chloro-2-
(Vinyloxyisopropoxyethoxy) ethane, 1-chloro-2- (vinyloxyisopropoxyisopropoxy) ethane, 1-chloro-2- (vinyloxyethoxyethoxy) propane, 1-chloro-2- (vinyloxyethoxyiso) Propoxy) propane, 1-chloro-2- (vinyloxyisopropoxyethoxy) propane, 1-chloro-2- (vinyloxyisopropoxyisopropoxy)
Propane, 1-chloro-2- (vinyloxyethoxyethoxy) isopropane, 1-chloro-2- (vinyloxyethoxyisopropoxyiso) propane, 1-chloro-2
-(Vinyloxyisopropoxyethoxy) isopropane, 1-chloro-2- (vinyloxyisopropoxyisopropoxy) isopropane, 1-chloro-2- (vinyloxyethoxyethoxyethoxy) ethane, 1-chloro-
2- (vinyloxyethoxyethoxyethoxyethoxy)
Ethane, 1-chloro-2- (isopropenoxyethoxyethoxy) ethane, 1-chloro-2- (isopropenoxyethoxyethoxy) ethane, 1-chloro-2- (isopropenoxyethoxyethoxyethoxy) ethane, 1-chloro -2- (isopropenoxyethoxyethoxyethoxyethoxy) ethane, 1-chloro-2- (vinyloxypolyethoxy) ethane, 1-chloro-2- (vinyloxypolyisopropoxy) ethane, 1-bromo-2- ( Vinyloxyethoxy) ethane, 1-bromo-2- (vinyloxyisopropoxy) ethane, 1-bromo-2- (vinyloxyethoxy) propane, 1-bromo-2- (vinyloxyisopropoxy) propane, 1-bromo -2- (vinyloxyethoxy) isopropane, 1-bromo-2- (vinyloxyisopropoxy) Sopuropan, 1-bromo-2-
(Vinyloxyethoxyethoxy) ethane, 1-bromo-
2- (vinyloxyethoxyisopropoxy) ethane, 1
-Bromo-2- (vinyloxyisopropoxyethoxy)
Ethane, 1-bromo-2- (vinyloxyisopropoxyisopropoxy) ethane, 1-bromo-2- (vinyloxyethoxyethoxy) propane, 1-bromo-2- (vinyloxyethoxyisopropoxy) propane, 1-bromo -2- (vinyloxyisopropoxyethoxy) propane, 1-bromo-2- (vinyloxyisopropoxyisopropoxy) propane, 1-bromo-2- (vinyloxyethoxyethoxy) isopropane, 1-bromo-2-
(Vinyloxyethoxyisopropoxyiso) propane,
1-bromo-2- (vinyloxyisopropoxyethoxy) isopropane, 1-bromo-2- (vinyloxyisopropoxyisopropoxy) isopropane, 1-bromo-2- (vinyloxyethoxyethoxyethoxy) ethane, 1-bromo-2- (vinyloxyisopropoxyethoxy) isopropane Bromo-2- (vinyloxyethoxyethoxyethoxyethoxy) ethane, 1-bromo-2- (isopropenoxyethoxy) ethane, 1-bromo-2- (isopropenoxyethoxyethoxy) ethane, 1-bromo-2
-(Isopropenoxyethoxyethoxyethoxy) ethane, 1-bromo-2- (isopropenoxyethoxyethoxyethoxyethoxy) ethane, 1-bromo-2- (vinyloxypolyethoxy) ethane, 1-bromo-2- (vinyl Roxypolyisopropoxy) ethane, 1-iodo-2
-(Vinyloxyethoxy) ethane, 1-iodo-2-
(Vinyloxyisopropoxy) ethane, 1-iodo-2
-(Vinyloxyethoxy) propane, 1-iodo-2-
(Vinyloxyisopropoxy) propane, 1-iodo-
2- (vinyloxyethoxy) isopropane, 1-iodo-2- (vinyloxyisopropoxy) isopropane, 1
-Iodo-2- (vinyloxyethoxyethoxy) ethane, 1-iodo-2- (vinyloxyethoxyisopropoxy) ethane, 1-iodo-2- (vinyloxyisopropoxyethoxy) ethane, 1-iodo-2- ( Vinyloxyisopropoxyisopropoxy) ethane, 1-iodo-2- (vinyloxyethoxyethoxy) propane, 1-
Iodo-2- (vinyloxyethoxypropoxy) propane, 1-iodo-2- (vinyloxyisopropoxyethoxy) propane, 1-iodo-2- (vinyloxyisopropoxyisopropoxy) propane, 1-iodo-
2- (vinyloxyethoxyethoxy) isopropane, 1
-Iodo-2- (vinyloxyethoxyisopropoxyiso) propane, 1-iodo-2- (vinyloxyisopropoxyethoxy) isopropane, 1-iodo-2- (vinyloxyisopropoxyisopropoxy) isopropane, 1- Iodo-2- (vinyloxyethoxyethoxyethoxy) ethane, 1-iodo-2- (vinyloxyethoxyethoxyethoxyethoxy) ethane, 1-iodo-2
-(Isopropenoxyethoxy) ethane, 1-iodo-
2- (isopropenoxyethoxyethoxy) ethane, 1
-Iodo-2- (isopropenoxyethoxyethoxyethoxy) ethane, 1-iodo-2- (isopropenoxyethoxyethoxyethoxyethoxy) ethane, 1-iodo-2- (vinyloxypolyethoxy) ethane, 1-iodo- Halogen-containing vinyl ethers such as 2- (vinyloxypolyisopropoxy) ethane are exemplified.

Of these, 2- (vinyloxyethoxy)
Ethanol, 2- (vinyloxyethoxyethoxy) ethanol, 2- (vinyloxyethoxyethoxyethoxy)
Ethanol, 1-chloro-2- (vinyloxyethoxy)
Ethane, 1-chloro-2- (vinyloxyethoxyethoxy) ethane and 1-chloro-2- (vinyloxyethoxyethoxyethoxy) ethane are preferably used.

(Meth) having a vinyl ether group in the side chain
The method for producing the acrylate polymer is, for example, a method using a (meth) acrylic acid polymer and a hydroxyl group-containing vinyl ether (method I); Method using hydroxyl group-containing vinyl ethers (Production method II); Method using (meth) acrylic anhydride-based polymer and hydroxyl group-containing vinyl ethers (Production method III); Method using (meth) alkyl acrylate-based polymer and hydroxyl group-containing vinyl ethers (Production method IV); Method using (meth) acrylic acid polymer and halogen-containing vinyl ethers (Production method V); Method using alkali (earth) metal (meth) acrylate-based polymer and halogen-containing vinyl ethers (Production method V)
I); Hereinafter, each production method will be described.

(Production Method I) In the production method using a (meth) acrylic acid-based polymer and a hydroxyl group-containing vinyl ether, the reaction is preferably carried out in the presence of an acid catalyst. Further, it is preferable to remove water generated by the reaction out of the reaction system.

The ratio of the (meth) acrylic acid-based polymer to the hydroxyl group-containing vinyl ether in the initial stage of the reaction is not particularly limited, but specifically, the general formula contained in the (meth) acrylic acid-based polymer For one hydroxyl group in the structural unit represented by (1), the hydroxyl group-containing vinyl ether is preferably in the range of 0.1 to 20 molecules, more preferably in the range of 0.5 to 10 molecules, and more preferably in the range of 0.8 to 10. A range of 6 molecules is more preferred. The above range of the ratio is preferable in terms of yield and economy.

The acid catalyst is not particularly limited, but specifically, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid,
Mineral acids such as boric acid and partially neutralized salts thereof; tungstic acid, molybdic acid, tangstosilicic acid, molybdosilicic acid, tungstophosphoric acid, molybdophosphoric acid and other heteropolyacids and partially neutralized salts thereof; methanesulfonic acid, paratoluenesulfonic acid Lewis acids such as boron fluoride, boron chloride, aluminum chloride, tin dichloride, and tin tetrachloride; acidic ion exchange resins having at least one ion exchanger of sulfonic acid groups and alkylsulfonic acid groups; mordenite Type, X type, Y type, β type, ZSM
Acidic zeolite such as -5 type; These acid catalysts may be used alone or in combination of two or more.

The amount of the acid catalyst used is not particularly limited, but specifically, 0.001 to 30% by weight, preferably 0.1 to 30% by weight, based on the hydroxyl group-containing vinyl ethers.
005-20% by weight, more preferably 0.01-15%
%, Particularly preferably in the range of 0.02 to 10% by weight. The above range of the amount of the catalyst is preferable in terms of yield and economy.

As a method for removing the produced water, for example,
Examples of the method include performing the reaction under reduced pressure, performing the reaction using an azeotropic solvent, and performing the reaction in the presence of a drying agent. Of these, a method of performing the reaction under reduced pressure and a method of performing the reaction using an azeotropic solvent are preferable.

The azeotropic solvent is not particularly limited as long as it does not hinder the reaction. Specifically, diethyl ether, diisopropyl ether, dibutyl ether, benzene, toluene, xylene, pentane, hexane, heptane, cyclohexane , Chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene and the like. These azeotropic solvents may be used alone or
More than one type may be used in combination.

The amount of the azeotropic solvent to be used is not particularly limited. Specifically, the azeotropic solvent is used in an amount of 0 to 30 based on the total weight of the (meth) acrylic acid polymer and the hydroxyl group-containing vinyl ether.
It may be used in an amount of 0% by weight, preferably 0 to 200% by weight, more preferably 0 to 150% by weight, particularly preferably 0 to 100% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

The reaction temperature of the above reaction is not particularly limited, but is preferably in the range of 0 ° C. to 150 ° C.
The temperature is more preferably in the range of 0 ° C to 130 ° C, and more preferably 40 ° C to 1 ° C.
A temperature in the range of 20 ° C is particularly preferred. The reaction pressure is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure. The reaction time may be appropriately set so that the above reaction is completed.

(Production Method II) In the production method using a (meth) acrylic acid halide polymer and a hydroxyl group-containing vinyl ether, the reaction is preferably carried out in the presence of a base catalyst.

The ratio of the (meth) acrylic acid halide polymer to the hydroxyl group-containing vinyl ether in the initial stage of the reaction is not particularly limited, but specifically, the ratio is based on the (meth) acrylic acid halide polymer. For one halogen atom in the structural unit represented by the general formula (1) included, the hydroxyl group-containing vinyl ether is preferably in the range of 0.1 to 20 molecules, more preferably in the range of 0.5 to 10 molecules. , 0.8 to 6 molecules. The above range of the ratio is preferable in terms of yield and economy.

The base catalyst is not particularly limited, but specific examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trimethylamine, triethylamine, tolbutylamine, pyridine and the like. These base catalysts may be used alone or in combination of two or more.

The amount of the base catalyst used is not particularly limited, but specifically, 0.5 to 3 mol, preferably 0.6 to 1 mol of the hydroxyl group-containing vinyl ether.
It may be used so as to fall within the range of 2 to 2 mol, more preferably 0.7 to 1.5 mol, particularly preferably 0.8 to 1.3 mol. The above range of the amount of the catalyst is preferable in terms of yield and economy.

Further, since the reaction has a large heat of reaction, it is necessary to prevent runaway of the reaction. To prevent the reaction,
There is a method in which a reaction is performed using a heat removal apparatus, or a method in which one of the raw materials is continuously or intermittently added to react. These methods may be used alone or in combination.

In this reaction, it is not necessary to use a solvent, but any solvent may be used as long as it does not inhibit the reaction. The solvent is not particularly limited, and specifically, diethyl ether, diisopropyl ether, dibutyl ether,
Tetrahydrofuran, benzene, toluene, xylene,
Examples thereof include pentane, hexane, heptane, cyclohexane, chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and acetonitrile. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is not particularly limited. Specifically, the amount of the solvent is 0% of the total weight of the (meth) acrylic halide polymer and the hydroxyl group-containing vinyl ether.
To 300% by weight, preferably 0 to 200% by weight, more preferably 0 to 150% by weight, particularly preferably 0 to 10% by weight.
It may be used so as to be within the range of 0% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

The reaction temperature of the above reaction is not particularly limited, but is preferably in the range of 0 ° C. to 100 ° C.
The temperature is more preferably in the range of 0 ° C to 80 ° C, and 15 ° C to 60 ° C.
Particularly preferred is in the range of ° C. The reaction pressure is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure. The reaction time may be appropriately set so that the above reaction is completed.

(Production Method III) In the production method using a (meth) acrylic anhydride polymer and a hydroxyl group-containing vinyl ether, the reaction is preferably carried out without a catalyst or in the presence of a base catalyst.

The ratio of the (meth) acrylic anhydride polymer to the hydroxyl group-containing vinyl ether in the initial stage of the reaction is not particularly limited, but is specifically included in the (meth) acrylic anhydride polymer. With respect to one (meth) acrylic anhydride in the structural unit represented by the general formula (1):
The hydroxyl group-containing vinyl ethers are preferably in the range of 0.1 to 20 molecules, more preferably in the range of 0.5 to 10 molecules,
A range of 0.8 to 6 molecules is more preferred. The above range of the ratio is preferable in terms of yield and economy.

The base catalyst is not particularly limited, but specific examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, trimethylamine, triethylamine, tributylamine, and the like. Pyridine and the like. These base catalysts may be used alone or in combination of two or more.

The amount of the base catalyst to be used is not particularly limited, but specifically, 0 to 1 mol, preferably 0.005 mol, per 1 mol of the hydroxyl group-containing vinyl ether.
It may be used so as to fall within the range of 0.5 to 0.5 mol, more preferably 0.01 to 0.3 mol, particularly preferably 0.05 to 0.2 mol. The above range of the amount of the catalyst is preferable in terms of yield and economy.

In this reaction, it is not necessary to use a solvent, but any solvent may be used as long as it does not inhibit the reaction. The solvent is not particularly limited, and specifically, diethyl ether, diisopropyl ether, dibutyl ether,
Tetrahydrofuran, benzene, toluene, xylene,
Examples thereof include pentane, hexane, heptane, cyclohexane, chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and acetonitrile. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is not particularly limited. Specifically, the amount of the solvent is from 0 to 30 based on the total weight of the (meth) acrylic anhydride polymer and the hydroxyl group-containing vinyl ether.
It may be used in an amount of 0% by weight, preferably 0 to 200% by weight, more preferably 0 to 150% by weight, particularly preferably 0 to 100% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

The reaction temperature of the above reaction is not particularly limited, but is preferably in the range of 0 ° C. to 150 ° C.
The temperature is more preferably in the range of 0 ° C to 130 ° C, and more preferably 40 ° C to 1 ° C.
A temperature in the range of 20 ° C is particularly preferred. The reaction pressure is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure. The reaction time may be appropriately set so that the above reaction is completed.

(Production Method IV) In the production method using a (meth) acrylic acid alkyl ester polymer and a hydroxyl group-containing vinyl ether, the reaction is preferably carried out in the presence of a transesterification catalyst. Further, it is preferable to remove the alkyl alcohol generated by the reaction out of the reaction system.

The ratio of the (meth) acrylic acid alkyl ester polymer to the hydroxyl group-containing vinyl ether in the initial stage of the reaction is not particularly limited, but is specifically included in the (meth) acrylic acid alkyl ester polymer. The ratio of hydroxyl group-containing vinyl ethers to one alkyl (meth) acrylate in the structural unit represented by the general formula (1) is preferably in the range of 0.1 to 20 molecules, and 0.5
The range of 10 to 10 molecules is more preferred, and the range of 0.8 to 6 molecules is even more preferred. The above range of the ratio is preferable in terms of yield and economy.

The transesterification catalyst is not particularly limited, but specific examples include calcium oxide,
Oxides such as barium oxide, lead oxide, zinc oxide and zirconium oxide; hydroxides such as calcium hydroxide, thallium hydroxide, tin hydroxide, lead hydroxide and nickel hydroxide; lithium chloride, calcium chloride, tin chloride; Halides such as lead chloride, zirconium chloride and nickel chloride; carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, lead carbonate, zinc carbonate and nickel carbonate; hydrogen carbonate such as potassium hydrogen carbonate, rubidium hydrogen carbonate and cesium hydrogen carbonate Salts: sodium phosphate, potassium phosphate, rubidium phosphate,
Phosphates such as lead phosphate, zinc phosphate and nickel phosphate;
Nitrates such as lead nitrate, zinc nitrate and nickel nitrate; lead acetate;
Carboxylates such as zinc acetate and nickel acetate; alkoxy compounds such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, calcium methoxide, calcium ethoxide, barium methoxide, barium ethoxide, and tetraethoxytitanium ;
Acetylacetonate complexes such as lithium acetylacetonate, zinc acetylacetonate, and zirconia acetylacetonate; dibutyltin oxide, dioctyltin oxide and the like; These transesterification catalysts may be used alone or in combination of two or more.

The amount of the transesterification catalyst used is not particularly limited, but specifically, 0.001 to 30% by weight, preferably 0.005 to 20% by weight of the hydroxyl group-containing vinyl ether. Preferably 0.01 to
It may be used in an amount of 15% by weight, particularly preferably 0.02 to 10% by weight. The above range of the amount of the catalyst is preferable in terms of yield and economy.

Examples of the method for removing the produced alkyl alcohol include a method of performing the reaction under reduced pressure, a method of performing the reaction using an azeotropic solvent, and a method of performing the reaction in the presence of an adsorbent. Of these, a method of performing the reaction under reduced pressure and a method of performing the reaction using an azeotropic solvent are preferable.

The azeotropic solvent is not particularly limited as long as it does not inhibit the reaction. Specifically, diethyl ether, diisopropyl ether, dibutyl ether, benzene, toluene, xylene, pentane, hexane, heptane, cyclohexane , Chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene and the like. These azeotropic solvents may be used alone or
More than one type may be used in combination.

The amount of the azeotropic solvent to be used is not particularly limited. Specifically, the amount of the azeotropic solvent is preferably 0 to 300% by weight of the total weight of the alkyl (meth) acrylate polymer and the hydroxyl group-containing vinyl ether. May be used in the range of 0 to 200% by weight, more preferably 0 to 150% by weight, particularly preferably 0 to 100% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

The reaction temperature of the above reaction is not particularly limited, but is preferably not lower than the temperature of the alkyl alcohol to be formed or the azeotropic temperature.
It is preferably in the range of 40 ° C to 180 ° C, and 50 ° C to 170 ° C.
C is more preferable, and a range of 60C to 160C is particularly preferable. The reaction pressure is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure.
The reaction time may be appropriately set so that the above reaction is completed.

(Production Method V) In the production method using a (meth) acrylic acid-based polymer and a halogen-containing vinyl ether, the reaction is preferably carried out in the presence of a base catalyst.

The ratio of the (meth) acrylic acid polymer and the halogen-containing vinyl ether in the initial stage of the reaction is not particularly limited, but specifically, the general formula (I) contained in the (meth) acrylic acid polymer For one (meth) acrylic acid in the structural unit represented by 1), the content of the halogen-containing vinyl ether is preferably in the range of 0.1 to 20, more preferably 0.5 to 0.5.
The range of 10 to 10 is more preferable, and the range of 0.8 to 6 is still more preferable. The above range of the ratio is preferable in terms of yield and economy.

The base catalyst is not particularly limited, but specific examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trimethylamine, triethylamine, tolbutylamine, pyridine, picoline, lutidine, and the like. Examples include quinoline, isoquinoline, collidine, and strongly basic ion exchange resins. These base catalysts may be used alone or in combination of two or more.

The amount of the base catalyst to be used is not particularly limited, but specifically, 0.5 to 6 moles, preferably 0.1 to 6 moles, per mole of the halogen-containing vinyl ether.
It may be used in an amount of 6 to 5 mol, more preferably 0.7 to 4 mol, particularly preferably 1 to 3 mol. The above range of the amount of the catalyst is preferable in terms of yield and economy.

In this reaction, it is not necessary to use a solvent, but any solvent may be used as long as it does not inhibit the reaction. The solvent is not particularly limited, and specifically, diethyl ether, diisopropyl ether, dibutyl ether,
Tetrahydrofuran, benzene, toluene, xylene,
Examples thereof include pentane, hexane, heptane, cyclohexane, chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and acetonitrile. Further, pyridine, picoline, lutidine, quinoline, isoquinoline, collidine and the like, which are also used as a catalyst, can be used as a solvent. These solvents may be used alone or in combination of two or more.

The amount of the solvent to be used is not particularly limited. Specifically, the solvent is used in an amount of 0 to 300% by weight, preferably 0 to 200% by weight, based on the total weight of the (meth) acrylic acid polymer and the halogen-containing vinyl ethers. % By weight, more preferably 0 to 150% by weight, particularly preferably 0 to 100% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

The reaction temperature of the above reaction is not particularly limited, but is preferably in the range of 0 ° C. to 100 ° C.
The temperature is more preferably in the range of 0 ° C to 80 ° C, and 15 ° C to 60 ° C.
Particularly preferred is in the range of ° C. The reaction pressure is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure. The reaction time may be appropriately set so that the above reaction is completed.

(Production Method VI) In the production method using an alkali (earth) metal salt polymer (meth) acrylate and a halogen-containing vinyl ether, the reaction is preferably carried out in the presence of a phase transfer catalyst.

The ratio of the alkali (earth) metal (meth) acrylate polymer and the halogen-containing vinyl ether in the initial stage of the reaction is not particularly limited, but specifically, the alkali (meth) acrylate ( With respect to one alkali (earth) metal (meth) acrylate in the structural unit represented by the general formula (1) contained in the (earth) metal salt-based polymer,
The halogen-containing vinyl ether is preferably in the range of 0.1 to 30 molecules, more preferably in the range of 0.5 to 20 molecules, and still more preferably in the range of 0.8 to 10. The above molar ratio range is preferable in terms of yield and economy.

The phase transfer catalyst is not particularly limited, but specific examples include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium. Iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, trimethylethylammonium chloride, trimethylethylammonium bromide, trimethylethylammonium iodide, triethylmethylammonium chloride, triethylmethylammonium bromide, triethylmethylammonium iodide Etc. Quaternary Ammo Um salts halides. These phase transfer catalysts may be used alone or in combination of two or more.

The amount of the phase transfer catalyst to be used is not particularly limited, but specifically, 0.0001 to 0.5 mol per 1 mol of the halogen-containing vinyl ether.
It is preferably 0.0005 to 0.1 mol, more preferably 0.001 to 0.05 mol, and particularly preferably 0.00
What is necessary is just to use it so that it may be in the range of 1-0.01 mol. The above range of the amount of the catalyst is preferable in terms of yield and economy.

In this reaction, it is not necessary to use a solvent, but any solvent may be used as long as it does not inhibit the reaction. The solvent is not particularly limited, and specifically, diethyl ether, diisopropyl ether, dibutyl ether,
Tetrahydrofuran, benzene, toluene, xylene,
Examples thereof include pentane, hexane, heptane, cyclohexane, chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, and acetonitrile. Further, a halogen-containing vinyl ether as a reaction substrate may be used in excess and used as a solvent.
These solvents may be used alone or in combination of two or more.

The amount of the solvent used is not particularly limited. Specifically, the solvent is used in an amount of from 0 to 300% by weight of the total weight of the alkali (earth) metal (meth) acrylate polymer and the halogen-containing vinyl ether. %, Preferably 0 to 200% by weight, more preferably 0 to 150% by weight, particularly preferably 0 to 100% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

The reaction temperature of the above reaction is not particularly limited, but is preferably in the range of 0 ° C. to 150 ° C.
The temperature is more preferably in the range of 0 ° C to 120 ° C, and preferably in the range of 20 ° C to 1 ° C.
A temperature in the range of 00 ° C is particularly preferred. The reaction pressure is not particularly limited, and may be any of normal pressure, increased pressure, and reduced pressure. The reaction time may be appropriately set so that the above reaction is completed.

Of the above-mentioned production methods I to VI, production methods II and VI are preferred in terms of the introduction ratio of vinyl ether groups, and production methods I and IV are preferred in terms of economical production.

The (meth) acrylate polymer having a vinyl ether group in the side chain produced by the present invention is represented by the above general formula (3), wherein R ¹ , R ³ , and A are The definitions are the same as in the general formulas (1) and (2), respectively.

The (meth) acrylate polymer having a vinyl ether group in the side chain produced according to the present invention can be obtained by purifying the reaction solution. The purification means is not particularly limited,
It can be separated and purified by a method of reprecipitating the produced (meth) acrylate polymer in a poor solvent, a method of evaporating unreacted vinyl ethers or a solvent, a method of GPC fractionation, or the like. These methods may be implemented in combination.

[0076]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The vinyl ether group introduction ratio indicates the ratio of the structural unit represented by the general formula (1) in the (meth) acrylic polymer converted to a vinyl ether group. ¹ H-NMR was used to calculate the vinyl ether group introduction rate.

Reference Example 1 (Production of acrylic acid / butyl acrylate copolymer) Acrylic acid was placed in a four-necked flask equipped with a stirrer, a thermometer, a cooling device, a dropping device, and a nitrogen gas inlet tube.
1 g, butyl acrylate 384.5 g, AIBN 4.
6 g and 1 L of benzene were charged, and 55 ° C. under a nitrogen gas stream.
And kept at the same temperature for 6 hours to obtain a polymer.

The solvent, benzene, was distilled off under reduced pressure, and the residue was purified by reprecipitation using 1 L of hexane. The purification yield of the polymer was 88 mol%.

Further, HLC-8020 type gel permeation chromatography (manufactured by Tosoh Corporation;
The number average molecular weight (in terms of polystyrene) of the polymer measured by PC was 9,800.

Reference Example 2 (Production of Acrylic Chloride / Ethyl Acrylate Copolymer)
5 g, ethyl acrylate 300.4 g, AIBN
9 g and benzene (1 L) were charged at 55 ° C. under a nitrogen gas stream.
And kept at the same temperature for 6 hours to obtain a polymer.

The solvent, benzene, was distilled off under reduced pressure, and the residue was purified by reprecipitation using 1 L of hexane. The purification yield of the polymer was 83 mol%, and the number average molecular weight (in terms of polystyrene) of the polymer measured by GPC was 89%.
00.

Reference Example 3 (Production of Methacrylic Anhydride / Methyl Methacrylate Copolymer) In the same apparatus as in Reference Example 1, methacrylic anhydride 77.1 was used.
g, 250.3 g of methyl methacrylate, AIBN
3 g, 2 L of benzene, and 55 ° C. under a nitrogen gas stream
And kept at the same temperature for 6 hours to obtain a polymer.

The solvent, benzene, was distilled off under reduced pressure and purified by reprecipitation using 2 L of hexane. The purification yield of the polymer was 72 mol%, and the number average molecular weight (in terms of polystyrene) of the polymer measured by GPC was 91 mol%.
00.

Example 1 (Production of Polymer Having Structural Unit Represented by General Formula (3) by Production Method I) A 500-ml four-necked flask equipped with a stirrer, a thermometer and a Dean-Stark trap was charged with 2- 66.1 g of (vinyloxyethoxy) ethanol, acrylic acid / butyl acrylate copolymer (copolymerization molar ratio; acrylic acid / butyl acrylate = 1/3) manufactured in Reference Example 1 11
4.1 g, p-toluenesulfonic acid monohydrate 0.33
g and 100 ml of toluene as an azeotropic solvent were added, and the mixture was heated to reflux while stirring and mixing. The reaction solution was kept stirring under reflux conditions for 5 hours. The solvent, toluene, was distilled off under reduced pressure, and the residue was purified by reprecipitation using 500 ml of hexane. The vinyl ether group introduction rate was 5 mol%.

Example 2 (General Formula (3) by Production Method II)
Production of Polymer Having Structural Unit Represented by Formula) Acrylic chloride / ethyl acrylate copolymer produced in Reference Example 2 was placed in a 500 ml four-necked flask equipped with a stirrer, a cooling device, a thermometer, and a dropping device. (Copolymer molar ratio: acrylic acid chloride / ethyl acrylate = 1)
/ 3) 97.7 g, 50.6 g of triethylamine and 70 ml of methylene chloride as a solvent were added, and the mixture was stirred and mixed at room temperature. 30 m of a methylene chloride solution of 66.1 g of 2- (vinyloxyethoxy) ethanol in the reaction solution.
After dropwise adding 1 over 1 hour at room temperature, stirring was further continued for 2 hours. The solvent methylene chloride was distilled off under reduced pressure, and the residue was purified by reprecipitation using 500 ml of hexane. The vinyl ether group introduction rate was 26 mol%.

Example 3 (Production of Polymer Having Structural Unit of General Formula (3) by Production Method III) In a 500 ml four-necked flask equipped with a stirrer, a cooling device, a thermometer, and a dropping device, The produced methacrylic anhydride / methyl methacrylate copolymer (copolymer molar ratio; methacrylic anhydride / methyl methacrylate = 1)
/ 5) 163.7 g and toluene 150 m as solvent
and heated to 70 ° C. with stirring. 2- in the solution
66.1 g of (vinyloxyethoxy) ethanol was added dropwise over 2 hours. The temperature of the reaction solution was raised to 95 ° C., and stirring was continued at this temperature for 2 hours. The solvent, toluene, was distilled off under reduced pressure, and the residue was purified by reprecipitation using 500 ml of hexane. The vinyl ether group introduction rate was 13 mol%.

Example 4 (General Formula (3) by Production Method IV)
Production of a polymer having a structural formula represented by the following formula) In a device similar to that in Example 1, 2- (vinyloxyethoxy)
132.2 g of ethanol, 50.2 g of polyethyl acrylate having a number average molecular weight of 10300, 1.32 g of dibutyltin oxide, and 100 ml of toluene as a solvent
Was added thereto, and the mixture was heated to reflux conditions with stirring and mixing. The reaction solution was kept stirring under reflux for 6 hours. The solvent, toluene, was distilled off under reduced pressure, and the residue was purified by reprecipitation using 500 ml of hexane. The vinyl ether group introduction ratio was 17 mol%.

Example 5 (General Formula (3) by Production Method IV)
Production of Polymer Having Structural Unit Represented by) The same operation as in Example 4 was performed except that polyethyl acrylate was changed to 50.2 g of polymethyl methacrylate having a number average molecular weight of 9,900. The vinyl ether group introduction rate was 19 mol%.

Example 6 (Production of Polymer Having Structural Unit Represented by General Formula (3) by Production Method V) A 500 ml four-necked flask equipped with a stirrer, a cooling device, a thermometer, and a dropping device was prepared as a reference. 114.1 g of an acrylic acid / butyl acrylate copolymer (copolymerization molar ratio; acrylic acid / butyl acrylate = 1/3) produced in Example 1;
121.1 g of γ-collidine was added and mixed with stirring at room temperature. After 75.3 g of 1-chloro-2- (vinyloxyethoxy) ethane was added dropwise to the reaction solution over 1 hour at room temperature, stirring was further continued for 6 hours. Hexane 2
Purified by reprecipitation using L. The vinyl ether group introduction rate was 15 mol%.

Example 7 (General formula (3) according to production method VI)
Production of Polymer Having Structural Unit 1) In a 300 ml four-necked flask equipped with a stirrer, a cooling device, a thermometer and a dropping device, 225.9 g of 1-chloro-2- (vinyloxyethoxy) ethane, number average molecular weight 47.0 g of 8500 sodium polyacrylate and 0.42 g of tetrabutylammonium chloride were added, and the mixture was heated to reflux while stirring and mixing. The reaction solution was kept stirring under reflux for 6 hours. The reaction solution was purified by reprecipitation using 2 L of hexane. The vinyl ether group introduction ratio was 22 mol%.

[0091]

According to the present invention, a (meth) acrylate polymer having a vinyl ether group in the side chain can be produced with good yield, and the polymerization of the vinyl ether group in the side chain can be sufficiently improved. Can demonstrate.

The (meth) acrylate polymer having a vinyl ether group in the side chain obtained by the present invention is:
Pharmaceutical and agricultural chemical raw materials, synthetic intermediates, cross-linking agents, resins for powder coatings, as well as polymerizable materials such as adhesives, adhesives, biomaterials, dental materials, optical components, information recording materials, optical fiber materials,
Resist material, insulator, sealing material, printing ink, paint, casting material, decorative board, WPC, coating material, lining material, civil engineering building material, putty, repair material, flooring material, pavement material gel coat, overcoat, hand Lay-up, spray-up, pultrusion, filament winding, SMC, BMC
It is a useful compound that is widely used for molding materials such as, for example, sheets and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4J031 AA19 AA53 AC03 AC04 AC05 AE11 AF03 AF10 AF12 AF13 AF17 AF28 4J100 AE09Q AE10Q AJ02P AK13P AK31P AK38P AL03P BA03Q BA04Q BA06Q BA08Q BA15H BB01Q11 JA51 JA67

Claims (1)

[Claims] 1. The following general formula (1):(Where R¹Represents a hydrogen atom or a methyl group, and Z represents-
OH group, halogen atom, -OR²Group (R²Represents an organic residue
OM group (M represents an alkali (earth) metal)
Or CH₂= CR¹Represents a COO- group)
(Meth) acrylic polymer having a structural unit and the following general
Formula (2): R³-CH = CH- (OA) nx (wherein R³Represents a hydrogen atom or an organic residue, and A represents-
CHR^FourCHR^Five-Group (R ⁴And R⁵Are independent
Represents a hydrogen atom or an organic residue);
May be the same or different.
The len group (OA) is composed of two or more oxyalkylene groups
If the connection type is block or random
It may be. n represents a positive number of 2 or more, and X represents an -OH group.
Or a halogen atom. Vinyl ether represented by)
With the following general formula (3):(Where R¹Represents a hydrogen atom or a methyl group;³Is
A represents a hydrogen atom or an organic residue, and A represents -CHR^FourCHR^Five
-Group (R⁴And R⁵Are each independently a hydrogen atom or
Represents an organic residue), and two or more A
A plurality of oxyalkylene groups (OA)
When two or more oxyalkylene groups are
The combination format may be either block or random. n
Represents a positive number of 2 or more. Having a structural unit represented by)
(Meth) acrylic acid having a vinyl ether group in the side chain
A method for producing a stell-based polymer.