JP2547010B2 - Method for producing copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention is excellent in heat resistance, chemical resistance, mechanical properties and moldability, and is compatible or compatible with various non-polar and polar materials. The present invention relates to a method for producing a good copolymer of

<Prior Art> Styrene-based resins or methyl methacrylate-based resins have excellent moldability and appearance.
Widely used as electric parts and office equipment parts.
However, these resins have the drawback of being inferior in heat resistance, and in recent years, for the purpose of improving their heat resistance, development of resins in which a maleimide monomer, a maleic anhydride or methacrylic acid or the like was introduced as a heat resistance-imparting component has been developed. It is being actively promoted.

Furthermore, for the purpose of improving the impact strength of the resin containing these heat resistance imparting components, for example, a composition of a styrene-maleimide copolymer and an ABS resin (Japanese Patent Publication No. 61-26936, Japanese Patent Publication No. 58-129043, etc.). ), A composition of a styrene-maleimide copolymer and a polycarbonate (JP-A-53-12924).
5), a composition comprising styrene and / or methyl methacrylate-acrylonitrile-maleimide copolymer, ABS resin and polycarbonate (Japanese Patent Publication No. 61-5097).
6), a composition of a styrene-maleimide copolymer or a styrene-acrylonitrile-maleimide copolymer and polyphenylene ether (JP-A-61-174249, JP-B-60-
58257) etc. have been proposed.

<Problems to be Solved by the Invention> However, since the resin obtained by introducing the maleimide-based monomer or the like as described above has a very large polarity, the compatibility with a non-polar or small-polarity material is poor. This tendency becomes more remarkable as the content of the heat resistance imparting component such as the maleimide-based monomer in the resin increases. As a result, it is difficult to obtain a resin composition having the characteristics that each resin originally has. For example, a composition of a styrene-maleimide copolymer and polyphenylene ether as disclosed in the above Japanese Patent Publication No. 60-58257 is poor in compatibility, so that it is difficult to obtain a composition having high heat resistance and impact strength.

<Means for Solving the Invention> The present inventors have solved the above-mentioned problems and have excellent heat resistance, chemical resistance, mechanical properties and molding processability, and other excellent weather resistance, color developability, and the like, and As a result of diligent studies to obtain a copolymer having very good compatibility or affinity with various non-polar and polar materials, a copolymer composed of a specific heat resistance-imparting component and having a specific composition distribution The manufacturing method was found and the present invention was achieved.

That is, in the present invention, in the presence or absence of a thermoplastic resin and / or a rubbery polymer, any of a maleimide-based monomer (A-1) and an unsaturated carboxylic acid-based monomer (A-2). Or one or two kinds of monomers (A) and an aromatic vinyl monomer (B-
1) and a monomer containing one or more monomers selected from unsaturated nitrile-based monomers (B-2) and unsaturated carboxylic acid ester-based monomers (B-3) A copolymer (B) and a monomer (C) copolymerizable therewith, and the average composition (excluding the thermoplastic resin and the rubbery polymer) represented by the formulas (1) and (2). In the method for producing a polymer, the monomer (B-2) and / or the monomer (B-1) is used.
Alternatively, by providing a step of stepwise or continuously changing the addition ratio of at least one monomer of (B-3) to perform copolymerization, the monomers (B-2) and (B-3) The heat resistance is characterized by having a composition distribution such that 1 to 90% by weight is present in a region having a total content of 10% by weight or less and 99 to 10% by weight in a region exceeding the content of 10% by weight. The present invention provides a method for producing a copolymer which is excellent in chemical resistance, mechanical strength and molding processability and has good compatibility or affinity with various nonpolar and polar materials.

Average composition The present invention will be described in detail below.

Copolymer Constituents Examples of thermoplastic resins and / or rubbery polymers that can be used in the production of the copolymer of the present invention include the following.

Polyethylene, polypropylene, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1
Copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, N-phenylmaleimide grafted polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer , Ethylene- (meth) acrylic acid and its metal salt copolymers, ethylene- (meth) acrylic acid ester copolymers such as methyl, ethyl, propyl, butyl, glycidyl and dimethylaminoethyl, ethylene- (meth) acrylate, ethylene-
(Meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid alkyl ester-maleic anhydride copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoro Ethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl butyral, polyvinyl chloride,
Butadiene rubber, styrene-butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer, acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyamideimide, polyether One or more of imide, polyether ester, polyether ester amide, polyether amide, polyether ether ketone, polyphenylene sulfide, polysulfone, polyether sulfone, polyphenylene ether, polyoxymethylene and the like. Especially glass transition temperature is 0 ℃
The following are preferred.

As the maleimide-based monomer (A-1), maleimide, N-methylmaleimide, N-ethylmaleimide, N
-Isopropyl maleimide, N-butyl maleimide, N
-Hexylmaleimide, N-octylmaleimide, N-
Lauryl maleimide, N-cyclohexyl maleimide,
N-phenylmaleimide, N-2,3 or 4-methylphenylmaleimide, N-2,3 or 4-ethylphenylmaleimide, N-2,3 or 4-butylphenylmaleimide, N-2,6-dimethylphenylmaleimide , N-2,3
-Or 4-chlorophenylmaleimide, N-2,3 or 4-bromophenylmaleimide, N-2,5-dichlorophenylmaleimide, N-3,4-dichlorophenylmaleimide, N-2,5-dibromophenylmaleimide, N-
3,4-dibromophenylmaleimide, N-2,4,6-trichlorophenylmaleimide, N-2,4,6-tribromophenylmaleimide, N-2,3 or 4-hydroxyphenylmaleimide, N-2,3 Or 4-methoxyphenylmaleimide, N-2,3 or 4-carboxyphenylmaleimide, N-4-nitrophenylmaleimide, N-4-
Diphenylmaleimide, N-1-naphthylphenylmaleimide, N-4-cyanophenylmaleimide, N-4-
Phenoxyphenylmaleide, N-4-benzylphenylmaleimide, N-2-methyl-5-chlorophenylmaleimide, N-2-methoxy-5-chlorophenylmaleimide and the like are exemplified, and one kind or two or more kinds can be used. Of these, N-aryl-substituted maleimides are particularly preferable.

Examples of the unsaturated carboxylic acid-based monomer (A-2) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and hymic acid anhydride. Of these, methacrylic acid and maleic anhydride are particularly preferable.

Any one type or two types of the above-mentioned maleimide type monomer (A-1) and unsaturated carboxylic acid type monomer (A-2) constitutes a copolymer as the monomer (A).

As the aromatic vinyl-based monomer (B-1), styrene, α-methylstyrene, α-chlorostyrene, p-t
-Butylstyrene, p-methylstyrene, o-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, p-bromostyrene, o
-Bromostyrene, 2,5-dibromostyrene, 3,4-dibromostyrene, cyanostyrene, 2-isopropenylnaphthalene and the like can be mentioned, and one or more kinds can be used. Of these, usually styrene or α-
Methylstyrene is preferred.

Examples of the unsaturated nitrile-based monomer (B-2) include acrylonitrile, methacrylonitrile, maleonitrile, fumaronitrile and the like, and one kind or two or more kinds can be used. Of these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid ester-based monomer (B-3) include (meth) acrylic acid methyl, ethyl, propyl,
(Meth) acrylic acid ester monomers such as butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl and dimethylaminoethyl, and mono- and unsaturated monocarboxylic acids such as maleic acid, itaconic acid, citraconic acid and hymic acid. Examples thereof include dialkyl ester. These may be used alone or in combination of two or more. Of these, methyl methacrylate is usually preferred.

One selected from the above aromatic vinyl-based monomer (B-1), unsaturated nitrile-based monomer (B-2) and unsaturated carboxylic acid ester-based monomer (B-3) Alternatively, two or more of them form a copolymer as the monomer (B).

Further, as is clear from the formula (1), a monomer copolymerizable with the above-mentioned monomers (A) and (B) can be used as the monomer (C).

Examples of the monomer (C) include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, butadiene and acrylamide. , Methacrylamide, vinyl acetate, vinylpyrrolidone, vinylpyridine,
Vinyl carbazole, vinyl ether, vinyl ketone,
Examples include coumarone, indene and acenaphthylene.

Average Composition The average composition of all polymers obtained by the method of the present invention is represented by the above formulas (1) and (2). Here, in the formula (1), when the amount of the monomer (A) is less than 1% by weight, a copolymer having high heat resistance cannot be obtained. On the other hand, when the amount exceeds 60% by weight, mechanical strength and processability are increased. Not only decreases, but also the affinity with non-polar or low-polarity materials decreases. Particularly preferable amount of the monomer (A) is 3 to 50.
% By weight. Further, in the formula (2), the monomer (C)
When the amount of the above exceeds 50% by weight, the original properties of the copolymer are lost. The preferable amount of the monomer (C) is 0 to 30.
% By weight.

Composition distribution The copolymer obtained by the method of the present invention has a total content of monomers (B-2) and (B-3) of 1 to 90% by weight in the region of 10% by weight or less, and the content of 10% by weight. The composition distribution is such that 99% to 10% by weight is contained in a region exceeding 100%.

When the total content of the monomers (B-2) and (B-3) is less than 1% by weight in the range where the copolymer is less than 1% by weight, the copolymer has poor affinity with a non-polar or small-polarity material, On the other hand, if the amount exceeds 90% by weight, the chemical resistance is poor. A particularly preferable range of the region where the total content of the monomers (B-2) and (B-3) is 10% by weight or less is 5 to 80% by weight.

Furthermore, in order to improve chemical resistance, color development, affinity with various organic materials, etc., the copolymer is a monomer (B-
It is desirable that the copolymer has a composition distribution such that the total content of 2) and (B-3) exceeds 2 to 80% by weight in a region exceeding 20% by weight.

Production of Copolymer In the production process of the present invention, copolymerization is performed by changing the addition ratio of the monomer (B-2) and / or (B-3) to the monomer (B-1) stepwise or continuously. It is a step of polymerizing. The following method may be mentioned as a specific method of the manufacturing process.

(A) Polymerization is started by increasing the addition ratio of the monomer (B-2) and / or (B-3) to the monomer (B-1), and polymerization is performed while gradually decreasing the addition ratio. Method.

(B) Polymerization is started by lowering the addition ratio of the monomer (B-2) and / or (B-3) to the monomer (B-1), and polymerization is performed while gradually increasing the addition ratio. Method.

(C) A method of polymerizing while optionally changing the addition ratio of the monomer (B-2) and / or (B-3) to the monomer (B-1).

 Of the above methods, the method (a) is usually preferred.

Further, the polymerization method is not limited at all, and it can be produced by any method such as a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and a combination thereof. In this case, a polymerization initiator, a chain transfer agent, a solvent, a suspension stabilizer,
Known emulsifiers, pH adjusters and the like can be used alone or in combination.

The copolymer is produced in the presence or absence of a thermoplastic resin and / or a rubbery polymer. When the polymerization is carried out in the presence, the upper limit of the amount of the thermoplastic resin and / or the rubbery polymer in the copolymer is preferably 80% by weight or less. Here, when the above-mentioned monomer is polymerized particularly in the presence of a rubbery polymer, a graft copolymer having high impact strength can be obtained. There are no particular restrictions on the production of this graft copolymer, but the weight average particle size of the graft copolymer is from 0.05 to 10
It is preferable that the thickness is 10 μm and the graft ratio is 10 to 200% by weight.
The intrinsic viscosity of the copolymer is usually preferably 0.2 to 1.5 dl / g. Here, when the above-mentioned monomers are graft-polymerized in the presence of the thermoplastic resin and / or the rubber-like polymer, generally, all the monomers do not graft-polymerize with the thermoplastic resin or the rubber-like polymer, Some of the monomers form free copolymers. Therefore, the intrinsic viscosity of the copolymer in this case means the intrinsic viscosity of the free copolymer. The intrinsic viscosity is a value measured at 30 ° C. in a dimethylformamide solution.

Incidentally, the copolymer containing a maleimide-based monomer component in the present invention, as well as those produced by directly copolymerizing a maleimide-based monomer and other monomers, maleic anhydride The copolymer contained therein may be imidized by reacting with ammonia, primary amine, isocyanic acid ester or the like. Further, the copolymer containing methacrylic acid or methyl methacrylate may be converted into ammonia or primary amine. And the like, and may be converted into a copolymer containing a glutaric anhydride group or a glutarimide group by heat treatment in the presence or absence of the like.

Further, for the copolymer obtained by the method of the present invention, if necessary, an antioxidant, a heat stabilizer, a light stabilizer, a lubricant, a plasticizer, an antistatic agent, an inorganic and organic colorant, a foaming agent, Inorganic and organic fillers, flame retardants, surface gloss improvers, matting agents and the like can be added.

These various additives can be added during the process of producing the copolymer or in the subsequent process.

Incidentally, the copolymer obtained by the method of the present invention can be used alone, and since it has a very good affinity with various polar materials, glass fiber, metal fiber, carbon fiber or these It can be used as a composite material of powder, low melting point alloy, calcium carbonate, talc, gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, potassium titanate and the like.

Furthermore, polystyrene, rubber-modified polystyrene, maleic anhydride-styrene copolymer, maleic anhydride-acrylonitrile-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, methacrylonitrile- Styrene copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate-acrylonitrile-styrene copolymer, methyl methacrylate-methacrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer , Maleimide-based monomers and aromatic vinyl-based monomers,
Unsaturated carboxylic acid, unsaturated carboxylic acid ester, unsaturated nitrile-based monomer, copolymer with one or more other copolymerizable monomers, methyl methacrylate-glutaric anhydride copolymer , Methyl methacrylate-styrene-glutaric anhydride copolymer, methyl methacrylate-glutarimide copolymer, styrene-acrylonitrile-methacrylic acid copolymer, ABS resin, AES resin, MBS resin, ACS resin, AAS resin, polyethylene , Polypropylene, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride grafted polyolefin, maleimide monomer Grafted polyolefin, chlorinated polyolefin, ethylene-
Vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid and its metal salt copolymer, ethylene-methyl (meth) acrylate, ethyl, propyl, butyl, glycidyl, dimethylaminoethyl, etc. (Meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, ethylene-methacrylic acid ester-maleic anhydride Copolymer, ethylene-maleimide (N-aryl substituted maleimide) copolymer, ethylene- (meth) acrylic acid ester-maleimide (N-aryl substituted maleimide)
Copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl butyral, poly Vinyl chloride, butadiene rubber, styrene-
Butadiene random or block copolymer, hydrogenated styrene-butadiene random or block copolymer,
Acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyimide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, polyetheramide, polyetheretherketone, polyphenylene sulfide, Vehicle parts, ship parts, aircraft parts, electric / electronic parts as one or more resin compositions or laminates with polysulfone, polyether sulfone, polyphenylene ether, styrene-rubber modified polyphenylene ether, polyoxymethylene, etc. It can be widely used in many fields such as parts, building materials, office equipment, power tools, agricultural machine parts, household products, sports and leisure products.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. All parts and percentages shown in the examples are based on weight.

Example 1 Pure water in 20 reactors equipped with stirrer and plate baffle
After 70 parts, 0.1 part of sodium dodecylbenzenesulfonate and 0.05 part of potassium persulfate were charged and the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 75 ° C. with stirring.

A solution consisting of 30 parts of N-phenylmaleimide, 10 parts of acrylonitrile and 30 parts of styrene ((1) solution)
Was continuously added over 6 hours. Simultaneously with the start of the addition of this monomer solution, an aqueous solution containing 50 parts of pure water, 0.3 part of potassium persulfate and 1.2 parts of sodium dodecylbenzenesulfonate was continuously added over 7 hours.

After the addition of the above monomer solution, the following monomer solutions (2) to (6) were successively added over 20 minutes each. Then add 0.2 parts of potassium persulfate and add 2 parts of styrene.
It was added continuously over time.

Then, it hold | maintained at 75 degreeC for 2 hours. In addition, t-dodecyl mercaptan was used as a chain transfer agent. The obtained latex was coagulated with an aqueous solution of calcium chloride to recover a copolymer. Table 1 shows the analysis results in the polymerization process.

Monomer solution (2) (3) (4) (5) (6) Acrylonitrile (%) 40 30 20 10 3 Styrene (%) 60 70 80 90 97 Addition quantity 2 2 2 2 2 Example 2 The reactor used in Example 1 was charged with 50 parts of pure water and potassium persulfate.
0.1 part and sodium dodecylbenzene sulfonate 0.1
Then, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70 ° C. with stirring.

This was mixed with 24 parts of N-phenylmaleimide, 9 parts of acrylonitrile, 27 parts of styrene and t-dodecyl mercaptan.
A solution consisting of 0.2 parts was continuously added over 5 hours. At the same time when the addition of this monomer solution was started, potassium persulfate was added.
An aqueous solution consisting of 0.3 part, 1.2 parts of sodium dodecylbenzenesulfonate and 70 parts of pure water was continuously added over 7 hours.

After the addition of the above monomer solution, 6 parts of acrylonitrile and 14 parts of styrene were continuously used, and the addition ratios of acrylonitrile / styrene at the start of addition and at the end of addition were 40% / 60% and 0% / 100%, respectively. The ratio was changed so that Then, 0.2 part of potassium persulfate was added, and then 20 parts of styrene was continuously added over 2 hours.

Then, it heated up at 75 degreeC and hold | maintained for 2 hours. An aqueous magnesium sulfate solution was added to the obtained latex for coagulation treatment, and the copolymer was recovered. Table 2 shows the analytical results in the polymerization process.

Example 3 The reactor used in Example 1 was charged with an aqueous solution consisting of 0.1 part of potassium persulfate, 0.2 part of sodium lauryl sulfate and 60 parts of pure water, the inside of the reactor was replaced with nitrogen gas, and then the temperature was raised to 50 ° C. with stirring. The temperature was raised.

A solution consisting of 21 parts of N-phenylmaleimide, 49 parts of methyl methacrylate and 0.2 part of t-dodecyl mercaptan was first charged in 3 parts and heated to 70 ° C. Then, the remaining monomer solution (67 parts) was continuously added over 6 hours. Simultaneously with the start of the addition of this monomer solution, an aqueous solution containing 0.3 part of potassium persulfate, 1.5 parts of sodium lauryl sulfate and 60 parts of pure water was continuously added over 8 hours.

After the above monomer solution was added, 10 parts of methyl methacrylate and 10 parts of paramethylstyrene were continuously used, and the addition ratio of methyl methacrylate / paramethylstyrene at the start of addition and at the end of addition was 100% / 0, respectively. % And 0% / 10
The ratio was changed so as to be 0%, and continuous addition was performed over 2 hours. Then, 0.1 part of potassium persulfate was added, and then 10 parts of paramethylstyrene was continuously added over 1 hour.

Then, it heated up at 75 degreeC and hold | maintained for 3 hours. The obtained latex was coagulated with an aqueous solution of calcium chloride to recover a copolymer. Table 3 shows the analysis results in the polymerization process.

Example 4 70 parts of pure water and potassium persulfate were used in the reactor used in Example 1.
0.2 parts and sodium dodecylbenzene sulfonate 0.3
Of the solution consisting of 25 parts of N-cyclohexylmaleimide, 21 parts of methyl methacrylate and 14 parts of styrene were added with stirring, and then the temperature was raised to 70 ° C. Warmed.

The remaining monomer solution (57 parts) was continuously added thereto over 5 hours. An aqueous solution containing 50 parts of pure water, 0.2 part of potassium persulfate and 1.1 parts of sodium dodecylbenzenesulfonate was continuously added over 8 hours. After the above monomer solution was added, a solution of 9.5 parts of methyl methacrylate and 0.5 part of methyl acrylate was added over 1 hour, and subsequently 6 parts of methyl methacrylate and 14 parts of styrene were used.
The addition ratios of methyl methacrylate / styrene at the start of addition and at the end of addition are 60% / 40% and 0% / 100, respectively.
The ratio was changed so that it became%, and the mixture was added over 2 hours. Then 10 parts of styrene and 1% aqueous solution of potassium persulfate 10
Parts were added continuously over 1 hour.

Then, it hold | maintained at 70 degreeC for 2 hours. In addition, t-dodecyl mercaptan was used as a chain transfer agent. The obtained latex was coagulated with an aqueous solution of calcium chloride to recover a copolymer. Table 4 shows the analysis results in the polymerization process.

Example 5 70 parts of pure water, 0.2 part of sodium dodecylbenzenesulfonate and 0.1 part of potassium persulfate were added to the reactor used in Example 1.
And nitrogen gas was substituted in the reactor, 20 parts of N-phenylmaleimide and 14 parts of acrylonitrile were stirred under stirring.
Parts, 43 parts of styrene, and 3 parts of a mixed solution consisting of 3 parts of methacrylic acid were added, and the temperature was raised to 70 ° C. The balance (77
Part) and 0.3 parts of potassium persulfate, 0.8 parts of sodium dodecylbenzenesulfonate and 50 parts of pure water.
Part aqueous solution was added continuously over 6 hours.

Then, using 4 parts of acrylonitrile and 16 parts of styrene, the addition ratio of acrylonitrile / styrene at the start and end of the addition was 40% / 60% and 0% /
The ratio was changed so as to be 100%, and the addition was continued for 2 hours.

After that, the temperature was raised to 75 ° C. and kept for 3 hours. In addition, t-dodecyl mercaptan was used as a chain transfer agent. The obtained latex was coagulated with magnesium sulfate to recover the copolymer. Table 5 shows the analysis results in the polymerization process.

Example 6 60 parts of pure water and potassium persulfate were used in the reactor used in Example 1.
0.1 part and 0.1 part of sodium lauryl sulfate were charged, the inside of the reactor was replaced with nitrogen gas, and then, with stirring, 20 parts of N-2-chlorophenylmaleimide, 10 parts of acrylonitrile,
Of a solution consisting of 32 parts of methyl methacrylate, 8 parts of styrene, and 0.3 parts of t-dodecyl mercaptan, 3 parts were initially charged and the temperature was raised to 70 ° C. To this, the remaining monomer solution (67 parts) and an aqueous solution consisting of 60 parts of pure water, 0.2 parts of potassium persulfate and 1.2 parts of sodium lauryl sulfate were continuously added over 5 hours.

Then, using 6 parts of a solution consisting of 25% acrylonitrile and 75% methyl methacrylate and 12 parts styrene,
The addition ratio of acrylonitrile-methyl methacrylate solution / styrene at the start of addition and at the end of addition is 60 each.
Change the ratio so that it becomes% / 40% and 0% / 100%. 2
It was added continuously over time. Then potassium persulfate 0.1
After adding 1 part, 10 parts of styrene was continuously added over 1 hour.

After that, the temperature was raised to 75 ° C. and kept for 2 hours. The obtained latex was coagulated with an aqueous magnesium sulfate solution to recover a copolymer. Table 6 shows the analysis results in the polymerization process.

Example 7 70 parts of pure water, 0.2 part of sodium dodecylbenzene sulfonate and 0.2 part of potassium persulfate were used in the reactor used in Example 1.
Then, 5 parts of a solution consisting of 14 parts of methacrylic acid and 56 parts of styrene was charged and the temperature was raised to 70 ° C. The remaining monomer solution (65 parts) was continuously added to this over 6 hours. Simultaneously with the start of the addition of this monomer solution, an aqueous solution containing 50 parts of pure water, 1.5 parts of sodium dodecylbenzenesulfonate and 0.3 parts of potassium persulfate was continuously added over 8 hours.

After the above monomer solution was added, 3 parts of acrylonitrile and 17 parts of styrene were used, and the addition ratio of acrylonitrile / styrene was 30% at the start of addition and after the end of addition.
/ 70% and 0% / 100% were added over 2 hours.

Then, 0.1 part of potassium persulfate was added, and then 10 parts of styrene was continuously added over 1 hour. After that, the temperature was raised to 75 ° C. and kept for 2 hours. The obtained latex was coagulated with an aqueous solution of calcium chloride to recover a copolymer. In addition, t-dodecyl mercaptan was used as a chain transfer agent. Table 7 shows the analysis results in the polymerization process.

Example 8 70 parts of pure water and potassium persulfate were used in the reactor used in Example 1.
0.1 part, sodium lauryl sulfate 0.2 part and potassium alkenyl succinate 0.2 part were charged, and the pH of the aqueous phase was adjusted to 6.8 with a potassium dihydrogen phosphate-disodium hydrogen phosphate aqueous solution. Next, after replacing the inside of the reactor with nitrogen gas, the temperature was raised to 65 ° C. with stirring. To this, a solution consisting of 5 parts of acrylonitrile and 15 parts of α-methylstyrene was charged,
The temperature was raised to 75 ° C over 1 hour. Then, a solution consisting of 15 parts of N-phenylmaleimide, 6 parts of acrylonitrile and 24 parts of α-methylstyrene was continuously added over 5 hours, and then a solution of 0.5 parts of N-phenylmaleimide and 4.5 parts of acrylonitrile was added over 30 minutes. Added continuously. Then, it hold | maintained at 75 degreeC for 2 hours. (First step) Further, simultaneously with the start of the continuous addition of the above-mentioned monomer solution, an aqueous solution consisting of 0.2 part of potassium persulfate, 0.7 part of sodium lauryl sulfate, 0.7 part of potassium alkenylsuccinate and 70 parts of pure water was added over 6 hours. Added continuously.

Then, using 3 parts of acrylonitrile and 12 parts of styrene, acrylonitrile /
Addition ratio of styrene is 40% / 60% and 0% / 10 respectively
It was added over 2 hours so as to be 0%. (Second stage) Next, 15 parts of styrene was continuously added over 1 hour.
Then, it was kept at 75 ° C. for 2 hours. (3 steps) In addition, pentaerythritol tetrakis (thioglycolate) was used as a chain transfer agent. An aqueous solution containing 10 parts of pure water, 0.2 part of sodium lauryl sulfate and 0.2 part of potassium persulfate was added over 3 hours from the start of the second stage polymerization.

The obtained latex was coagulated with an aqueous solution of calcium chloride to recover a copolymer. Table 8 shows the analysis results in the polymerization process.

Example 9 To the reactor used in Example 1, 30 parts of pure water, 0.002 part of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.2 part of lactose were added, followed by butyl acrylate rubber latex (weight average particle size). 0.4 μm, gel content 77%, solid content 40
%, The emulsifier sodium lauryl sulfate, pH 6.1 (50 parts by weight) (solid content equivalent) was charged, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70 ° C. with stirring.

A solution containing 3 parts of N-phenylmaleimide, 6 parts of acrylonitrile, 16 parts of α-methylstyrene and 0.2 part of ethylene glycol thiodiglycolate, and 0.5 part of sodium lauryl sulfate, 0.3 part of cumene hydroperoxide and pure water. An aqueous solution consisting of 20 parts was continuously added over 5 hours.

Next, using 2 parts of acrylonitrile and 8 parts of styrene, the addition ratio of acrylonitrile / styrene at the start and end of the addition was 40% / 60% and 0% / 100, respectively.
% Was continuously added over 1 hour, and then 15 parts of styrene was continuously added over 2 hours. Then 75
The temperature was raised to ℃ and kept for 2 hours. Simultaneously with the start of the addition of acrylonitrile and styrene, an aqueous solution containing 0.1 part of potassium persulfate, 0.1 part of sodium lauryl sulfate and 10 parts of pure water was continuously added over 3 hours.

The obtained latex was coagulated with an aqueous calcium chloride solution to obtain a copolymer having a graft ratio of 47%. Table 9 shows the analysis results in the polymerization process.

Example 10 The reactor used in Example 1 was charged with 30 parts of pure water and potassium persulfate.
0.1 part and sodium lauryl sulfate 0.1 part and polybutadiene latex (weight average particle diameter of rubber 0.45μ
m, gel content 77%, solid content 41%) 25 parts (as solid content) and styrene-butadiene copolymer latex (weight average particle diameter of rubber 0.21 μm, styrene content 24%, gel content 81)
%, Solid content 45%) After charging 25 parts (solid content conversion),
The inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 75 ° C. with stirring.

A solution of 9 parts of N-phenylmaleimide, 6 parts of acrylonitrile and 15 parts of styrene and 20 parts of pure water.
Parts, 0.2 parts of potassium persulfate and 0.5 parts of sodium lauryl sulphate were added continuously over a period of 4 hours (first stage). Subsequently, a solution of 1.5 parts of acrylonitrile and 3.5 parts of styrene was added over 30 minutes. (Second stage) Next, a solution of 0.5 part of acrylonitrile and 4.5 parts of styrene was added over 30 minutes. (Third stage) Next, 0.2 part of potassium persulfate was added, and then 10 parts of styrene was added over 1 hour. Then, it hold | maintained at 75 degreeC for 2 hours. (Fourth stage) In addition, terpinolene was used as a chain transfer agent. The obtained latex was coagulated with magnesium sulfate to recover a copolymer having a graft ratio of 57%. Table 10 shows the analysis results in the polymerization process.

Comparative Example 1 70 parts of pure water, 0.1 part of sodium dodecylbenzenesulfonate and 0.1 part of potassium persulfate were used in the reactor used in Example 1.
After a portion was charged and the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 70 ° C. with stirring.

20 parts of N-phenylmaleimide, 20 parts of acrylonitrile, 60 parts of styrene and t-dodecyl mercaptan
Solution consisting of 0.3 parts and pure water 50 parts, sodium dodecylbenzenesulfonate 0.8 parts and potassium persulfate 0.2
Part aqueous solution was added continuously over 5 hours.

Then, it was kept at 70 ° C. for 2 hours. The obtained latex was coagulated with an aqueous calcium chloride solution to recover the copolymers shown in Table 11.

Comparative Example 2 50 parts of pure water and potassium persulfate were used in the reactor used in Example 1.
0.1 part and sodium dodecylbenzene sulfonate 0.1
Then, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70 ° C. with stirring.

This was mixed with 24 parts of N-phenylmaleimide, 9 parts of acrylonitrile, 27 parts of styrene and t-dodecyl mercaptan.
A solution consisting of 0.2 parts was continuously added over 3 hours. At the same time when the addition of this monomer solution was started, potassium persulfate was added.
An aqueous solution consisting of 0.2 part, 1.2 parts of sodium dodecylbenzenesulfonate and 70 parts of pure water was continuously added over 5 hours.

After adding the above monomer solution, continue to acrylonitrile
12 parts, styrene 28 parts and t-dodecyl mercaptan 0.
A solution of 2 parts was added continuously over a period of 2 hours. Then, it heated up at 75 degreeC and hold | maintained for 2 hours. The obtained latex was coagulated with an aqueous magnesium sulfate solution to recover the copolymers shown in Table 11.

Comparative Example 3 70 parts of pure water, 0.5 part of sodium dodecylbenzenesulfonate and 0.2 parts of potassium persulfate were added to the reactor used in Example 1.
After charging 1 part of the reactor and replacing the inside of the reactor with nitrogen gas, 5 parts of a solution consisting of 1 part of methacrylic acid, 3 parts of acrylonitrile, 94 parts of styrene and 0.3 part of t-dodecyl mercaptan was charged with stirring and the temperature was raised to 70 ° C. Warmed.

The remaining monomer solution and an aqueous solution consisting of 50 parts of pure water, 1.5 parts of sodium dodecylbenzenesulfonate and 0.8 parts of potassium persulfate were continuously added thereto over 8 hours.

Then, it heated up at 75 degreeC and hold | maintained for 2 hours. The obtained latex was coagulated with an aqueous calcium chloride solution to recover the copolymers shown in Table 11.

The analysis results of the copolymers obtained in Examples 1 to 10 and Comparative Examples 1 to 3 are summarized in Table 11 below. The first
The abbreviations shown in Tables to Table 11 represent the following. The composition of the copolymer was determined from elemental analysis of carbon, hydrogen, nitrogen and oxygen, and the mass balance in the manufacturing process of the copolymer.

NPMI: N-Phenylmaleimide CHMI: N-Cyclohexylmaleimide CPMI: N-2-Chlorophenylmaleimide MAA: Methacrylic acid AN: Acrylonitrile MMA: Methyl methacrylate MA: Methyl acrylate S: Styrene AMS: α-Methylstyrene PMS: Paramethyl Styrene SBR: Styrene-butadiene copolymer rubber BR: Polybutadiene rubber BAR: Polybutyl acrylate rubber [η]: Dimethylamide solution, intrinsic viscosity measured at 30 ° C. Unit dl / g Next, produced in each Example and Comparative Example. The following tests were conducted as test examples in order to investigate the properties of the copolymers.
The thermoplastic resins and rubbery polymers for blending used in the test are the following polymers A to M.

Polymer A (ABS) To the reactor used in Example 1 was added 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 parts of sodium pyrophosphate and 0.3 parts of dextrose, and then polybutadiene latex (weight of rubber). Average particle size 0.47μm, gel content 79%, solid content
42%) 60 parts (solid content conversion) was charged, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70 ° C. with stirring.

To this, a mixed solution of 15 parts of acrylonitrile, 35 parts of styrene and 0.3 part of t-dodecyl mercaptan and an aqueous solution of 1.2 parts of potassium alkenylsuccinate, 0.3 part of t-butylhydroperoxide and 30 parts of pure water were applied over 3 hours. Added continuously. Then, the mixture was kept at 75 ° C. for 2 hours to obtain a latex having a polymerization rate of 99.1%. The obtained latex was coagulated with magnesium sulfate to recover a polymer having a graft ratio of 42% and an ungrafted copolymer having an intrinsic viscosity of 0.47 dl / g.

Polymer B (AAS) Butyl acrylate rubber latex (weight average particle size 0.3
μm, gel content 79%, solid content 42%) 50 parts (as solid content) was used as a rubber component, and 36 parts of styrene and 14 parts of acrylonitrile were used. Polymerization was performed to obtain a polymer having a polymerization rate of 98.9%, a graft rate of 47%, and an ungrafted copolymer having an intrinsic viscosity of 0.52 dl / g.

Polymer C (ABSM) 30 parts of pure water, 0.002 part of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.3 part of dextrose were added to the reactor used in Example 1, and then acrylonitrile-butadiene rubber latex ( Weight average particle diameter of rubber 0.31μ
m, gel content 77%, acrylonitrile content 30%, solid content
41%) 60 parts (solid content conversion) was charged, the inside of the reactor was replaced with nitrogen gas, and the temperature was raised to 70 ° C. with stirring. to this,
The following monomer solution containing t-dodecyl mercaptan was continuously added over 4 hours for polymerization. On the other hand, simultaneously with the start of addition of the monomer solution, the following aqueous solution of emulsifier-polymerization initiator was continuously added over 4 hours. Then, the mixture was kept at 75 ° C. for 2 hours to obtain a latex having a polymerization rate of 98.9%. The obtained polymer latex was coagulated with calcium chloride to recover a polymer having a graft ratio of 41% and an ungrafted copolymer having an intrinsic viscosity of 0.51 dl / g.

Monomer solution (part) Acrylonitrile …… 5 Methyl methacrylate …… 23 Styrene …… 12 Emulsifier-polymerization initiator aqueous solution (part) Pure water …… 30 Sodium dehydroabietate 1.5 Cumene hydroperoxide 0.3 Polymer D (MBS) ) To the reactor used in Example 1 was added 30 parts of pure water, 0.002 part of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.3 part of dextrose, and then styrene-butadiene rubber latex (weight average particle of rubber). Diameter 0.47μm, gel content
77%, styrene content 25%, solid content 41%) 50 parts (solid content conversion) was charged, and then the inside of the reactor was replaced with nitrogen gas,
The temperature was raised to 70 ° C. with stirring. The following monomer solution containing t-dodecyl mercaptan was continuously added thereto for 4 hours for polymerization. On the other hand, simultaneously with the start of addition of the monomer solution, the following aqueous solution of emulsifier-polymerization initiator was continuously added over 4 hours. Then, the temperature was maintained at 75 ° C for 2 hours, and the polymerization rate was 98.9
% Latex was obtained. The obtained polymer latex was coagulated with calcium chloride to recover a polymer having a graft ratio of 45% and an ungrafted copolymer of 0.49 dl / g.

Monomer solution (part) Methyl methacrylate 30 Styrene 20 Emulsifier-polymerization initiator aqueous solution (part) Pure water 30 Sodium dehydroabietate 1.5 t-butyl hydroperoxide 0.3 Polymer E (AES) Reaction used in Example 1 In a container, 550 parts of pure water in which 0.5 part of block type polyether dispersant (Pluronic F68 manufactured by Asahi Denka Co., Ltd.) was dissolved, and ethylene-propylene-ethylidene norbornene terpolymer rubber chopped into 4 to 6 mesh (iodine A value of 21.1, Mooney viscosity at 100 ° C of 79, and propylene content of 46.0% by weight) (100 parts) were charged and suspended. Then, as a polymerization initiator, a monomer mixture of 40 parts of acrylonitrile containing 3 parts of t-butylperoxypivalate and 0.05 part of p-quinone and 75 parts of styrene was added,
Immediately start steaming by blowing steam into the jacket of the autoclave. After 20 minutes, the temperature reached 100 ° C and remained at 1
The temperature was kept at 100 ° C. for the polymerization reaction. As a result, the graft ratio was 71% and the intrinsic viscosity of the ungrafted copolymer was 0.
57 dl / g of polymer was obtained.

Polymer F Polystyrene (Nippon polystyrene, Esbrite 4) Polymer G Impact-resistant polystyrene (Nippon polystyrene, Esbright, 500SB) Polymer H Polycarbonate (Teijin Kasei, Panlite L-1250) Polymer I Polyamide (Mitsubishi Kasei, Novamid 1015G30) Polymer J Ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical, Bondfast 2B) Polymer K Polyester (Toyobo, Perprene P40H) Polymer L Styrene-butadiene block copolymer (Shell Chemical, Kraton) 1652) Polymer M Acrylonitrile-styrene copolymer (Nippon Steel Chemicals, styrene AS-30) Test Examples 1-12, Comparative Test Examples 1-7 Each of the copolymers obtained in Examples and Comparative Examples or with them Other thermoplastics were blended in the proportions shown in Table 12 and 100 parts of these blends were blended. Ri tri Ellen glycol as a stabilizer - bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate] 0.
1 part, dilauryl-3,3'-thiodipropionate 0.1 part and (2,4-di-t-butylphenyl) pentaerythritol diphosphite 0.2 part and ethylenebisstearamide 0.2 part as a lubricant were added, and vented. While devolatilizing with an axial extruder, the mixture was kneaded at 250 to 300 ° C and pelletized. The total amount of residual monomers in these pellets was 0.2% or less.

Mold the pellets at 250-320 ° C with an injection molding machine,
A test piece was prepared and its physical properties were measured. The results are shown in Table 12.

 The physical properties were measured by the following methods.

Notched Izod impact strength (abbreviated as NI): 1/4 inch thickness test piece, measured value at 23 ° C.

Heat distortion temperature (abbreviated as HDT): Measured under 1/4 inch thickness test piece, 264 psi load, and without annealing.

Solvent resistance: The test piece was immersed in gasoline at 30 ° C. for 24 hours, and then the surface roughness and the like were visually observed.

Test Examples 13 to 26 and Comparative Test Examples 8 to 16 Each of the copolymers obtained in Examples and Comparative Examples or each of them and other thermoplastic resin or rubbery polymer were blended in the ratios shown in Table 13. In each of the compositions, the following compounding agent (addition amount was 100 parts of the resin composition) was added and mixed in a Henschel mixer, and then the above-mentioned Test Example 1 was used.
The pellets were pelletized by the method described in 1 above, and a test piece was prepared to measure the physical properties. The results are shown in Table 13.

Compounding agent 1) 2-t-butyl-6- (3'-t-butyl-5 '
-Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate: 0.2 parts 2) Trisnonylphenyl phosphite: 0.2 parts 3) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) 0.3 parts 4) Ethylene bis stearamide 0.2 parts 5) Calcium stearate 0.3 parts <Effects of the Invention> As is clear from the results of Tables 12 and 13, the copolymer produced by the method of the present invention has good compatibility or affinity with various nonpolar and polar materials, Excellent heat resistance, mechanical strength and solvent resistance (chemical resistance)
Indicates.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08F 291/00 MRB C08F 291/00 MRB

Claims (2)

(57) [Claims] 1. A maleimide-based monomer (A-) in the presence or absence of a thermoplastic resin and / or a rubbery polymer.
1) and any one or two kinds of unsaturated carboxylic acid type monomer (A-2) (A), aromatic vinyl type monomer (B-1) and unsaturated nitrile type Monomer (B-2)
And a monomer (B) consisting of one or more monomers selected from unsaturated carboxylic acid ester-based monomers (B-3) and a monomer (B) copolymerizable therewith ( C)
In the method for producing a copolymer represented by the formulas (1) and (2), the average composition (excluding the thermoplastic resin and the rubbery polymer) of the monomer (B-1) By providing a step of stepwise or continuously changing the addition ratio of the monomers (B-2) and / or (B-3) to perform copolymerization, the monomers (B-2) and (B-3) 1 to 90% by weight in the region where the total content of 10% by weight or less, and 99 to 10% by weight in the region where the content exceeds 10% by weight. Manufacturing method of coalescence. 2. The copolymer comprises monomers (B-2) and (B
-3) 5 to 80% by weight in the region where the total content is 10% by weight or less, 95 to 20% by weight in the region in which the content exceeds 10% by weight, and 2 to 2 in the region in which the content exceeds 20% by weight. The method for producing a copolymer according to claim 1, which has a composition distribution such that the content is 80% by weight.