JPS63125503A - Radical-curable copolymer resin and its composition and preparation - Google Patents

Abstract

PURPOSE:To prepare a radical-curable copolymer resin which has various useful applications, by copolymerizing a styrene monomer with (meth)acrylic acid and subsequently causing the formed copolymer to react with glycidyl (meth) acrylate. CONSTITUTION:A styrene monomer of formula I is copolymerized with glycidyl methacrylate or glycidyl acrylate. The resulting copolymer resin is subsequently incorporated with methacrylic acid or acrylic acid which is equimolar to the epoxy group contained in said resin so as to cause a reaction of the carboxyl group with the epoxy group, whereby a copolymer resin consisting chiefly of a compound of formula II having an acryloyl or methacryloyl group at the side chain end is obtained, wherein X is phenyl, acrylphenyl or halogenated phenyl; R1, R2 and R3 are each a hydrogen atom or a methyl group; m and n are integers, indicating that the two monomers cause random copolymerization in the main chain.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a resin having a polymerizable acryloid group or a methacryloid group at the end of a side chain, which is useful for various weighing applications, and a composition thereof. and a manufacturing method.

BACKGROUND ART Conventionally, as radical curable resins, unsaturated polyester resins and vinyl ester resins are typical, and diallyl phthalate resins are also used for applications such as molding materials and decorative laminates. Each of these resins is utilized for various purposes by taking advantage of its characteristics and physical properties, and has become indispensable.

On the other hand, however, with rapid advances in technology, resins with even higher performance are often required, and it is often necessary to improve resins in response to these demands.

- For example, unsaturated polyester resin has excellent water resistance, heat resistance, and K4 quality, and is widely used in applications such as FRP and artificial surrogate stone. Especially in the field of artificial surrogate stone, etc. The resin's transparency and whiteness when used in combination with fillers are unsatisfactory, and its surface hardness is also insufficient, so it is actually used with an overcoat depending on the application.

Furthermore, vinyl ester resin has a drawback that it is difficult to use as a matrix resin for laminated materials unless other resins are used in combination because the vinyl ester resin has too good fluidity.

[Problem to be Solved by the Invention 1] The present invention aims to eliminate various drawbacks of existing radical curable resins, expand their uses, and provide a radical curable resin that can meet new performance requirements for curable resins. The present invention also aims to provide a composition and a method for producing the same.

[Means for Solving the Problems] The object of the present invention is to solve the problems by the general formula [wherein X represents any one of a phenyl group, an alkylphenyl group, and a halogenated phenyl group,
, R3 is hydrogen or a methyl group, and m and n are positive integers, indicating that both monomers are randomly copolymerized in the main chain]. base [hereinafter, both (meta)
fJI has shown that this is achieved by a radically curable copolymer resin having an acryloyl group, and that this copolymer resin can at least compensate for most of the drawbacks of unsaturated polyester resins and the like.

Furthermore, according to the present invention, the copolymer resin component represented by the above general formula has a diacrylyyl structure or dimethacryloyl structure represented by the general formula [wherein R1 and R2 represent hydrogen or a methyl group]. There is provided a radically curable copolymer resin component further comprising 50% by weight or less of a divinyl compound having η.

Furthermore, according to the present invention, a styrene monomer and glycidyl methacrylate or glycidyl acrylate are copolymerized, and then methacrylic acid or acrylic acid is added in an amount substantially equivalent to the epoxy group contained in this copolymer resin. General formula % formula % [wherein X represents any one of a phenyl group, an alkylphenyl group, and a halogenated phenyl group, R1, R2,
R3 is hydrogen or a methyl group, and m and n are positive integers, indicating that both monomers are randomly copolymerized in the main chain. Provided is a method for producing a radically curable copolymer resin containing a compound having the following as a main component.

Generally, according to the present invention, a styrenic monomer and methacrylic acid or acrylic acid are copolymerized, and then glycidyl methacrylate or glycidyl acrylate is added in a substantially equimolar amount to the carboxyl group contained in the copolymer resin. In addition, the general formula % formula % [wherein X represents any one of a phenyl group, an alkylphenyl group, and a halogenated phenyl group, and R, RR is hydrogen or a methyl group, m and n are positive integers, indicating that both monomers are randomly copolymerized in the main chain] At the end of the side chain ( A method for producing a radically curable copolymer resin containing a compound having a meth)acryloyl group as a main component is provided.

[Function] In the present invention, the molar fraction in the copolymer resin of the repeating unit having a (meth)acryloyl group at the end of the side chain is 1 to 1.
90%, preferably 5 to 50%. Although it depends on the application, if the content of repeating units having an acryloyl group or methacryloyl group at the end of the side chain is less than 1%, the radical polymerization rate described below will be slow and the physical properties after curing will be insufficient. On the other hand, if it exceeds 90 mol%, the cured product will be hard and even brittle.

In the present invention, some of the styrenic monomers forming the main chain are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, It is also possible to improve the physical properties by substitution with monomers such as lauryl methacrylate, acrylonitrile, vinyl acetate, nylidene chloride, vinyl chloride, dibdel maleate, dioctyl maleate, and vinyl propionate.

Copolymerization can also be carried out by solution polymerization, pearl polymerization, etc., but in the case of solution polymerization, it is used as it is for the reaction in the next step. In the case of pearl polymerization, the resulting copolymer is dissolved in a solvent or monomer before being used in the next reaction step.

Copolymerization of styrenic monomer and glycidyl monomer,
Alternatively, when copolymerizing styrenic monomers with methacrylic acid or acrylic acid, known radical polymerization catalysts,
For example, it can be easily carried out by using specific peroxides, azo compounds, etc. and by selecting an appropriate polymerization temperature.

In the present invention, the polymerization rate in the copolymerization step does not necessarily have to be 100%; for example, it is stopped at 80%.
One of the advantages of the present invention is that it can proceed to the next step while containing residual monomers.

That is, in the next step, the glycidyl monomer as an unreacted monomer is reacted with methacrylic acid or acrylic acid, or the unreacted monomer methacrylic acid or acrylic acid is reacted with glycidyl methacrylate-1- or chrycidyl acrylate. Through the reaction, a divinyl compound having a cyacryloyl structure or dimethacryloyl groove represented by the general formula [wherein R and R represent hydrogen or a methyl group] is produced, but up to a certain amount of this divinyl compound The coexistence of these does not impair the physical properties of the copolymer resin in the present invention after polymerization.

Furthermore, it is obvious that the residual styrene monomer does not pose any problem in the present invention as will be described later.

In the reaction of the second step in the present invention, it is preferable to use a suitable polymerization inhibitor, such as hydroquinone, in order to prevent polymerization of the residual styrene monomer and crosslinking reaction between the copolymer resins.

The number of epoxy groups or carboxyl groups added and reacted per 1 carboxyl group or epoxy group contained in the reaction of the second step in the present invention is 0.9 to 1.
．． 1 equivalent, preferably 0.95 to 1.05 equivalent.

The radically curable copolymer resin according to the present invention can be cured by co-merging with a monomer as a heptamer solution, or crosslinking can be carried out by polymerizing the unsaturated bonds of the polymer without using a heptamer together. It is also possible.

The above monomers include styrene, vinyltoluene, chlorostyrene, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
Examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, benzyl methacrylate, dibutyl maleate, dioctyl maleate, vinyl acetate, vinyl propionate, etc.
A mixture of more than one species may be used.

The curable resin and composition of the present invention may contain reinforcing agents, fillers, colorants, mold release agents, curing agents, accelerators, stabilizers, etc., as necessary, to produce FRP, adhesives, paints, and molding materials. It can be widely used for etc.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples unless it departs from the gist of the present invention.

Further, throughout this specification, all temperatures are in degrees Celsius, and parts and percentages are on a suspended basis unless otherwise specified.

[Production of styrene/glycidyl methacrylate copolymer] In a separable flask (1000 ml) equipped with a stirrer, a thermometer with a gas inlet tube, a reflux condenser, and a dropping funnel, add methane (199C) as a solvent. Then, styrene (52, Oo, 0.5 mol), glycidyl methacrylate (14,2Q, 0.1 mol), benzoyl peroxide (0,52 o), and dodecyl mercaptan (0,52 g) were charged. When the reaction was carried out at ℃ for 5 hours under nitrogen blowing, the polymerization rate of styrene was 62%.
The polymerization rate of glycidyl methacrylate was 73%. The solvent and unreacted monomers were removed using a rotary evaporator to obtain a white polymer.

[Synthesis of resin having (meth)acryloyl group in side chain] A 45% styrene solution of all the above copolymers was placed in the same apparatus as described above, and then methacrylic 1112
(6.4 g) and hydroquinone (0.040 g) were charged and reacted at 100°C for 5 hours. The reaction rate of methacrylic acid was 94%.

This resin liquid was pale yellow in color and had a viscosity of 5.6 poise at 25°C.

Room-temperature gelation test was performed by adding Percure SAJ (trade name, manufactured by NOF Corporation, peroxide catalyst, 1 part) and cobalt naphthenate (6% Go, 0.5 part) to 100 parts of the above resin solution. As a result, the gelation time was 13 minutes, the shortest curing time was 15.3 minutes, and the maximum exothermic temperature was 149°C.

Furthermore, the cured resin had the following physical properties and was excellent in transparency.

Tensile strength 6.5 ko/mm2 Bending strength
12.8 kg/mm2 Bending elastic modulus 31
4 kQ/mm2 Heat distortion temperature 120 °C [Production of styrene-methacrylic acid copolymer] Using the same equipment as in Example 1, methyl ethyl ketone (1
99G) and then styrene (52.0o, 0.5
mol), methacrylic acid (17.2 g, 0.2 mol), benzoyl peroxide (0.52 G), and dodecyl mercaptan (0.52 g), and reacted at 105 to 110°C for 4 hours under nitrogen blowing conditions. The polymerization rate of styrene was 65%, and the polymerization rate of methacrylic acid was 68%. Styrene was further added to this, and only methyl ethyl ketone was removed using a rotary evaporator to obtain a copolymer resin composition (45% copolymer-containing chains).

[Synthesis of resin having (meth)acryloyl group in side chain] The above-mentioned copolymer resin composition was placed in the same apparatus as in Example 1, and then glycidyl methacrylate (28.4a, 0.4a,
2 mol), hydroquinone (0.05 CI>),
When the reaction was carried out at 110 to 120°C for 3 hours, the reaction rate of glycidyl methacrylate was 88%.

Claims (5)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group,
2. R_3 is hydrogen or a methyl group, m and n are positive integers, and this indicates that both monomers are randomly copolymerized in the main chain. A radically curable copolymer resin having an acryloyl group or a methacryloyl group. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group,
2. R_3 is hydrogen or a methyl group, m and n are positive integers, and this indicates that both monomers are randomly copolymerized in the main chain. In a radically curable copolymer resin having an acryloyl group or a methacryloyl group, a part of the styrene monomer units constituting the main chain is substituted with a vinyl monomer unit other than the styrenic monomer unit. copolymer resin. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group,
2, R_3 is hydrogen or a methyl group, m and n are positive integers, indicating that both monomers are randomly copolymerized in the main chain]. For radically curable copolymer resin components having acryloyl groups, there are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 represent hydrogen or methyl groups] Diacryloyl represented by A radically curable copolymer resin composition further comprising 50% by weight or less of a divinyl compound having a structure or a dimethacryloyl structure. (4) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group, and R_3 is hydrogen or a methyl group] Copolymerizing the shown styrenic monomer with glycidyl methacrylate or glycidyl acrylate,
Then, methacrylic acid or acrylic acid is added in a substantially equimolar amount to the epoxy group contained in this copolymer resin to cause a reaction between the carboxyl group and the epoxy group. , chemical formulas, tables, etc.▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group, and R_1, R_
2, R_3 is hydrogen or a methyl group, m and n are positive integers, indicating that both monomers are randomly copolymerized in the main chain]. A method for producing a radically curable copolymer resin whose main component is a compound having an acryloyl group. (5) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group, and R_3 is hydrogen or a methyl group] The indicated styrene monomer and methacrylic acid or acrylic acid are copolymerized, and then glycidyl methacrylate or glycidyl acrylate is added in a substantially equimolar amount to the carboxyl groups contained in this copolymer resin to form carboxyl groups and epoxy There are general formulas▲mathematical formulas, chemical formulas, tables, etc. that are characterized by the reaction with groups▼ [In the formula, X represents either a phenyl group, an alkylphenyl group, or a halogenated phenyl group, and R_1 , R_
2, R_3 is hydrogen or a methyl group, m and n are positive integers, indicating that both monomers are randomly copolymerized in the main chain]. A method for producing a radically curable copolymer resin whose main component is a compound having an acryloyl group.