JP2003226719A - (meth)acrylate type copolymer having vinyl ether group and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (meth)acrylate type copolymer having a vinyl ether group without causing gelation by a vinyl ether group. <P>SOLUTION: A (meth)acrylate type monomer having a vinyl ether group [monomer (A)], a (meth)acrylic acid type monomer [monomer (B)] and a monomer having a Q value range of 0.6-1.4 and an e value range of -0.4 to -1.2 [monomer (C)] are polymerized to give a (meth)acylate type copolymer having a vinyl ether group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a vinyl ether group-containing (meth) acrylic acid ester-based copolymer and a method for producing the same. More specifically, vinyl ether group-containing (meth) acrylic acid esters [monomer (A)], (meth) acrylic acid-based monomer [monomer (B)], and a Q value of 0.6 to 1 The present invention relates to a copolymer obtained by polymerizing a monomer [monomer (C)] having an e value in the range of 0.4 to 1.2 and a production method thereof. is there.

The vinyl ether group-containing (meth) acrylic acid ester-based copolymer obtained by the present invention is useful as a raw material for medicines and agricultural chemicals, synthetic intermediates, cross-linking agents, resins for powder coatings, and a wide range of polymerizable materials. It is a compound.

[0003]

2. Description of the Related Art As vinyl ether group-containing (meth) acrylic acid ester-based copolymers, binary copolymers of vinyl ether group-containing (meth) acrylic acid esters and (meth) acrylic acid esters are known. ing. As a method for producing this copolymer, there is known a method of selectively radically or anionically polymerizing vinyl ether group-containing (meth) acrylic acid esters and (meth) acryloyl groups of (meth) acrylic acid esters. However, anionic polymerization is not industrially advantageous because it is slightly affected by water. Further, in the case of radical polymerization, not only a (meth) acryloyl group but also a vinyl ether group may be polymerized to form a crosslinked gel polymer.

As a polymerization method in which such a crosslinking reaction is suppressed, Japanese Patent Laid-Open No. 6-100628 discloses a polymerization method at a low monomer concentration. In addition, JP-A-6-25
Japanese Patent No. 6426 discloses a polymerization method in the presence of a radical chain transfer agent.

However, the above-mentioned conventional methods have problems that the amount of the solvent used is large and the efficiency is low, the radical chain transfer agent is expensive, and the radical chain transfer agent affects the physical properties of the produced polymer. .

As a vinyl ether group-containing (meth) acrylic acid ester-based copolymer, a binary copolymer of vinyl ether group-containing (meth) acrylic acid esters and styrenes is known. However, it is difficult to control the physical properties of this binary copolymer and it cannot be used for various purposes.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and a vinyl ether group-containing (meth) acryl that can be developed into various applications without gelation due to crosslinking of the vinyl ether group. It is intended to provide an acid ester-based copolymer.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have found that when the monomer (A) and the monomer (B) are copolymerized, It was found that a novel copolymer can be obtained by adding the monomer (C) without gelation. The copolymer obtained by the present invention can be applied to various uses by changing the monomer (B).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The degree of polymerization of the vinyl ether group-containing (meth) acrylic acid ester-based copolymer according to the present invention is a number average molecular weight, and the lower limit is preferably 1,000.
Or more, more preferably 2,000 or more, particularly preferably 3,000 or more, and the upper limit value is preferably 20,0.
0,000 or less, more preferably 10,000,000
It is 0 or less, particularly preferably 5,000,000 or less.

Specific examples of the vinyl ether group-containing (meth) acrylic acid esters [monomer (A)] according to the present invention include 2-vinyloxyethyl (meth) acrylate,
1-Methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, (meth) acrylic acid 4 −
Vinyloxycyclohexyl, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, p- (meth) acrylate
Vinyloxymethylphenylmethyl, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, 2- [2- (2-vinyloxyethoxy) ethoxy] ethyl (meth) acrylate, 2- (meth) acrylic acid (2-Vinyloxypropoxy) propyl, 2- (2-) (meth) acrylic acid
Vinyloxyisopropoxy) isopropyl, polyethylene glycol monovinyl ether (meth) acrylate,
(Meth) acrylic acid polypropylene glycol monovinyl ether and the like can be mentioned.

The content of the above-mentioned monomer (A) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, particularly preferably 1% by weight, based on the total weight of the polymerizable monomers. % Or more, preferably 50% by weight or less, more preferably 30% by weight or less, further preferably 25% by weight or less, particularly preferably 15% by weight or less. The content ratio is preferable in terms of reaction efficiency and physical properties.

The (meth) acrylic acid-based monomer [monomer (B)] according to the present invention is a (meth) acrylic-based monomer that is not the monomer (A). , Methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as isostearyl (meth) acrylate; aromatic group-containing (meth) acrylic acid esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; (meth) acrylic acid 2 -Hydroxyethyl, (meth) acrylic acid 2-
Hydroxyl group-containing (meth) acrylates such as hydroxypropyl, 3-hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate; trifluoroethyl (meth) acrylate, ( Halogen-containing (meth) acrylic acid esters such as tetrafluoroethyl (meth) acrylate; Epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate; ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Di (meth) acrylates such as acrylate, 1,4-butanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate; nitrogen atom-containing (such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate) (Meth) acrylic acid esters; (meth) acrylic acid such as (meth) acrylic acid, sodium (meth) acrylate, potassium (meth) acrylate, magnesium (meth) acrylate, calcium (meth) acrylate and salts thereof And the like. These (meth) acrylic acid-based monomers may be used alone or in combination of two or more kinds.

The content of the above-mentioned monomer (B) is preferably 10% by weight or more, more preferably 30% by weight or more, particularly preferably 50% by weight, based on the total weight of the polymerizable monomers.
It is above, preferably 98% by weight or less, more preferably 95% by weight or less, particularly preferably 90% by weight or less. The content ratio is preferable in terms of reaction efficiency and physical properties.

The Q value and the e value are constants represented by the Alfrey-Price equation, the Q value represents the resonance factor of the monomer, and the e value represents the polar factor of the monomer. .

A monomer having a Q value of 0.6 to 1.4 and an e value of -0.4 to -1.2 according to the present invention [monomer (C)]. Specifically, styrene,
p-methylstyrene, p-tert-butylstyrene, p-
Methoxystyrene, 3,4-dimethoxystyrene, α-
Acetoxystyrene, p-acetoxystyrene, p-chloromethylstyrene, o-vinylphenol, m-vinylphenol, 2-vinylpyridine, 5-vinyl-2-
Picoline, 2-isopropenylnaphthalene, 2- (o-
Examples include monomers such as methyl) -4-vinylcatechol and trimethyl (p-vinylphenylsilane).

Of these, styrene, α-acetoxystyrene, p-acetoxystyrene, m-vinylphenol and 2- (o-methyl) -4-vinylcatechol are preferable, and styrene is particularly preferable.

The content of the above-mentioned monomer (C) is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, particularly preferably 1% by weight, based on the total weight of the polymerizable monomers. % Or more, preferably 50% by weight or less, more preferably 30% by weight or less, further preferably 25% by weight or less, particularly preferably 15% by weight or less. The content ratio is preferable in terms of reaction efficiency and physical properties.

The structural unit (X) may be any of those represented by the above general formula (1), wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, and R ³ Represents a hydrogen atom or an organic residue.

The organic residue represented by R ² in the general formula (1) is, for example, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, an ether bond in the structure and / or
Or 2 to 2 carbon atoms having an oxygen atom through an ester bond
Examples thereof include an alkylene group having 20 carbon atoms and an optionally substituted aromatic group having 6 to 11 carbon atoms.

Of these, an alkylene group having 2 to 6 carbon atoms and an alkylene group having 2 to 9 carbon atoms having an oxygen atom in the structure through an ether bond are preferably used.

The organic residue represented by R ³ in the general formula (1) is, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a halogenated group having 1 to 5 carbon atoms. Examples thereof include a chlorinated, brominated or fluorinated alkyl group and an aromatic group having 6 to 11 carbon atoms. Of these, an alkyl group having 1 to 2 carbon atoms is preferably used.

The structural unit (X) is derived from the monomer (A).

The structural unit (Y) may be represented by the general formula (2), wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrogen atom, an organic residue or an alkali. (Earth) Represents a metal.

The organic residue represented by R ⁵ in the general formula (2) is, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, or a hydroxyalkyl having 2 to 20 carbon atoms. Group, C2-C20 alkoxyalkyl group, C2-C20 acetoxyalkyl group, C1-C8 halogenated (eg chlorinated, brominated or fluorinated) alkyl group, alkenyl group, C6 To 11 optionally substituted aromatic groups and the like.

The structural unit (Y) is derived from the monomer (B).

The structural unit (Z) may be any of those represented by the general formula (3), and R ^{6 in} the formula represents an optionally substituted aromatic group.

The structural unit (Z) is preferably derived from the monomer (C).

The method for producing the vinyl ether group-containing (meth) acrylic acid ester-based copolymer of the present invention includes:
The monomers (A), (B) and (C) may be copolymerized with a radical polymerization initiator, heat, electron beam, ultraviolet ray, radiation or the like. Of these, the method using a radical polymerization initiator is preferable.

Specific examples of the above radical polymerization initiator include 2,2'-azobis- (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,
2'-azobis (2,4-dimethylvaleronitrile),
2.2'-azobis-2-methyl methyl propionate,
Dimethyl 2,2'-azobisisobutyrate, 2,2'azobis-2-methylvaleronitrile, 1,1'-azobis-
1-cycloheptanenitrile, 1,1'-azobis-1
-Azo initiators such as phenylethane and phenylazotriphenylmethane; benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauroyl peroxide, tert-butyl peracetate, tert-perbenzoate Butyl, tert-butyl hydroperoxide, tert-butyl peroxypivalate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t
-Peroxide initiators such as -butylperoxy-2-ethylhexanoate; and the like. Among these, azo initiators are particularly preferable.

The amount of the radical polymerization initiator used is preferably 0.001% by weight based on the total weight of the polymerizable monomers.
Or more, more preferably 0.01% by weight or more, further preferably 0.05% by weight or more, particularly preferably 0.1% by weight or more, preferably 30% by weight or less, more preferably 20% by weight or less, It is preferably 15% by weight or less, particularly preferably 10% by weight or less. The amount of the radical polymerization initiator used is preferable in terms of yield and economy.

In the method for producing a vinyl ether group-containing (meth) acrylic acid ester-based copolymer according to the present invention, it is not necessary to use a solvent, but it is preferable to use a solvent in order to prevent gelation. Solvents that can be used include aromatic solvents such as benzene, toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; isopropyl alcohol, n-butanol and the like. Aliphatic alcohol solvents such as; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether and other alkylene glycol monoalkyl ether solvents; diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and other ether solvents; To be

The amount of the organic solvent or water used is such that the total weight of the polymerizable monomers is preferably 10% by weight or more, more preferably 20% by weight, based on the total amount of (solvent + polymerizable monomers). % Or more, preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 50% by weight or less.

If necessary, a chain transfer agent, an emulsifier, and other additives may be added appropriately.

The reaction temperature for the polymerization is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, particularly preferably 40 ° C. or higher, preferably 150 ° C. or lower, more preferably 120 ° C. or lower, particularly preferably Is 100 ° C. or lower.

In order to prevent the gelation of the vinyl ether group-containing (meth) acrylic acid ester-based copolymer of the present invention and stably produce it, at least a part of the monomer composition and / or radical polymerization is used. It is preferable to add at least a part of the initiator composition to the reaction system.

The monomer composition means the monomer (A),
As long as it contains 0.1% by weight or more of any one of the monomers (B) and (C), a combination of these monomers may be used, and a solvent, a radical chain transfer agent, etc. may be contained. Good. Of these, the monomer (A) or (C)
It is preferable to include the monomer, and it is particularly preferable to include the monomers (A) and (C).

Further, the radical polymerization initiator composition may be any composition containing a radical polymerization initiator in an amount of 0.1% by weight or more, and has a polymerizability other than the monomers (A), (B) and (C). It may contain a monomer, a solvent, a radical chain transfer agent, and the like.

As a method of adding the monomer composition and / or the radical polymerization initiator composition to the reaction system,
Examples include (a) a method of adding the whole amount to the reaction system, and (b) a method of previously charging a part of the reaction system and adding the rest to the reaction system. When both the monomer composition and the radical polymerization initiator composition are added to the reaction system, they may be added separately or may be mixed in advance and added.

At least part of the monomer composition, and / or
Alternatively, the time for adding at least a part of the radical polymerization initiator composition to the reaction system is preferably 5% or more, more preferably 10% or more, particularly preferably 20% or more, with respect to the total reaction time. It may be added continuously or intermittently.

From the viewpoint of preventing gelation, it is preferable that the dissolved oxygen concentration in the reaction solution and the dropping solution be 20 ppm or less.

The dissolved oxygen concentration in the reaction solution and the dropping solution is preferably 20 ppm or less, more preferably 10 ppm or less, further preferably 5 ppm or less, and particularly preferably 3 ppm or less.

As a method of reducing the dissolved oxygen concentration to 20 ppm or less, a method of sufficiently bubbling an inert gas such as nitrogen, a method of sufficiently repeating decompression and replacement with an inert gas,
Examples include a method in which pressurization with an inert gas and opening pressure are sufficiently repeated. These methods may be carried out alone,
You may implement in combination.

The vinyl ether group-containing (meth) acrylic acid ester-based copolymer produced according to the present invention is
It can be obtained by purifying the reaction solution. As the above-mentioned purification means, re-precipitation in a poor solvent of the produced vinyl ether group-containing (meth) acrylic acid ester-based copolymer, a method of drying under reduced pressure after filtration, a method of evaporating unreacted monomers and a solvent, and Examples thereof include a method using GPC fractionation. You may implement these methods in combination.

[0044]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

The dissolved oxygen concentration was measured using a dissolved oxygen meter (UC-12-SOL type manufactured by Central Science Co., Ltd.).

Example 1 2,2'-azobisisobutyronitrile (hereinafter referred to as "AIBN") was placed in a four-necked flask equipped with a stirrer, a thermometer, a cooling device, a dropping device and a nitrogen gas introducing tube.
1.2 g and 43.2 g of benzene were charged, and nitrogen gas was sufficiently bubbled while stirring (dissolved oxygen concentration
3.8 ppm). After the temperature was raised to 60 ° C and the temperature became constant, methacrylic acid 2 was thoroughly bubbled with nitrogen gas.
-(Vinyloxyethoxy) ethyl (hereinafter "VEEM")
4.0 g, methyl methacrylate (hereinafter referred to as "MM
A.) 18.2 g, styrene (Q = 1, e =-
0.8) 1.0 g and benzene 24.0 g (dissolved oxygen concentration 3.2 ppm) was added dropwise over 5 hours. Then, the mixture was further stirred at the same temperature for 3 hours to obtain a polymer. This was reprecipitated using 1 L of hexane, filtered and dried under reduced pressure for purification. The yield of the obtained substance is 16.3.
It was g.

The substance obtained as described above was used as HLC-81.
Type 20 gel permeation chromatography (manufactured by Tosoh Corporation, eluent tetrahydrofuran; hereinafter referred to as "G"
PC ") and 400MHz UNITY-PL
Analysis was performed using a US nuclear magnetic resonance apparatus (manufactured by Varian, solvent deuterated chloroform; hereinafter referred to as "NMR"). As a result, the obtained polymer was VEEM, styrene and MM.
It was confirmed that the copolymer was A (copolymer composition ratio (calculated from NMR of copolymer): VEEM / styrene / MMA = 9.8 / 6.8 / 83.4 (mol%)) .
The number average molecular weight (calculated from GPC, converted to polystyrene) of the obtained copolymer was 4000. The NMR chart of the copolymer is shown in FIG.

Example 2 A device similar to that of Example 1 was charged with 1.1 g of AIBN and 36.9 g of benzene, and nitrogen gas was sufficiently bubbled (dissolved oxygen concentration 3.3 ppm). After the temperature was raised to 60 ° C. and the temperature became constant, a mixed solution of 4.2 g of VEEM sufficiently bubbled with nitrogen gas, 17.5 g of MMA, 1.5 g of styrene, and 10.4 g of benzene (dissolved oxygen concentration 3. 0 ppm), and AIBN 1.1 g and benzene 23.9 g with sufficient bubbling of nitrogen gas.
Of the mixed solution (dissolved oxygen concentration of 2.8 ppm) was added dropwise over 6 hours. Then, the mixture was stirred at the same temperature for 2 hours to obtain a polymer. This was reprecipitated using 1 L of hexane, filtered and dried under reduced pressure for purification. The yield of the obtained polymer was 16.6 g.

Further, the obtained copolymer was treated with GPC and
As a result of analysis by NMR, the number average molecular weight was 4100,
The copolymer composition ratio is VEEM / styrene / MMA = 10.
It was 2 / 9.5 / 80.3 (mol%).

Further, the infrared absorption spectrum of the obtained copolymer was measured. Infrared absorption spectrum is shown in FIG.

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, a vinyl ether group-containing (meth) acrylic acid ester-based copolymer which can be used in various applications can be produced without gelling with a vinyl ether group.

[Brief description of drawings]

1 is an NMR chart of the copolymer obtained in Example 1. FIG.

2 is an infrared absorption spectrum of the copolymer obtained in Example 2. FIG.

Claims (3)

[Claims] 1. A vinyl ether group-containing (meth) acrylic acid ester-based copolymer, which is not a vinyl ether group-containing (meth) acrylic acid ester [monomer (A)] or a monomer (A) ( (Meth) acrylic acid-based monomer [monomer (B)], and Q value in the range of 0.6 to 1.4, and e value in the range of -0.4 to -1.2 A copolymer obtained by polymerizing a monomer [monomer (C)]. 2. A vinyl ether group-containing (meth) acrylic acid ester-based copolymer having the following general formula (1): (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic residue, and R ³ represents a hydrogen atom or an organic residue.); Formula (2): (In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrogen atom, an organic residue, or an alkaline (earth) metal), and a structural unit (Y) represented by the following general formula ( 3): (In the formula, R ⁶ represents an aromatic group which may be substituted.) A copolymer having a structural unit (Z). 3. A method for producing a vinyl ether group-containing (meth) acrylic acid ester-based copolymer, wherein the monomers (A), (B) and (C) are polymerized. Manufacturing method.