JPS63258914A - Production of copolymer - Google Patents

Abstract

PURPOSE:To obtain a copolymer with excellent heat resistance, chemical resistance, high strength and good processability by polymerization of unsaturated carboxylic acids, aromatic vinyls, unsaturated nitriles, unsaturated esters and comonomers in the presence or absence of a thermoplastic resin under specific conditions. CONSTITUTION:A copolymer which has an average composition satisfying equations I and II where component A distributes 1-90wt.% in the region containing less than 10wt.% of components iv and v, while distributes 99-10wt.% in the region containing over 10wt.%, is obtained by copolymerization of (A) (i) a maleimide monomer, (ii) unsaturated carboxylic acid monomer, (B) (iii) aromatic vinyl monomers, (iv) unsaturated nitrile monomers, and (v) unsaturated ester monomers, and (C) other monomers copolymerizable with them, in the presence or absence of a thermoplastic resin or rubber polymer, so that copolymerization of is effected as varying the ratio of at least one of components A, iv and v to component iii followed by polymerization by addition of only monomers selected from components B and C.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has excellent heat resistance, chemical resistance, mechanical properties, and moldability, and has compatibility or affinity with various non-polar and polar materials. The present invention relates to a method for producing a good copolymer.

<Prior Art> Styrene resins or methyl methacrylate resins have excellent moldability and appearance, and are widely used as vehicle parts, electrical parts, office equipment parts, and the like. However, these resins have the disadvantage of poor heat resistance, and in recent years, in order to improve their heat resistance, resins have been developed that incorporate maleimide monomers, maleic anhydride, methacrylic acid, etc. as heat resistance imparting ingredients. It is being actively progressed.

Furthermore, in order to improve the impact strength of resins incorporating these heat resistance imparting components, for example, compositions of styrene-maleimide copolymers and ABS resins (Japanese Patent Publication No. 61-26
936, JP-A-Sho 58-12904.9, etc.) Compositions of styrene-maleimide copolymer and polycarbonate (JP-A 53-1
29245), styrene and/or methyl methacrylate-acrylonitrile-maleimide copolymer, AB
Compositions consisting of S resin and polycarbonate (Japanese Patent Publication No. 61-50976), compositions of styrene-maleimide copolymers, styrene-acrylonitrile-maleimide copolymers, and polyphenylene ether (Japanese Patent Publication No. 61-198)
74249, Japanese Patent Publication No. 6O-58257), etc. have been proposed.

<The problem that the invention is trying to solve> However,
Resins made by introducing maleimide monomers, etc., as mentioned above, have very high polarity and are therefore not compatible with small materials. This tendency becomes more pronounced as the content of heat resistance imparting components such as maleimide monomers in the resin increases. As a result, it is difficult to obtain a resin composition having the characteristics originally possessed by each resin. For example, a composition of a styrene-maleimide copolymer and polyphenylene ether as disclosed in the above-mentioned Japanese Patent Publication No. 60-58257 has poor compatibility, so it is difficult to obtain a composition with high heat resistance and impact strength.

<Means for Solving the Invention> The present inventors have solved the above-mentioned problems and improved heat resistance, etc.
We are working diligently to obtain a copolymer that has excellent chemical resistance, mechanical properties, moldability, processability, weather resistance, color development, etc., and has very good compatibility or affinity with various non-polar and polar materials. As a result of studies, a method for producing a copolymer comprising a specific heat resistance imparting component and having a specific composition distribution was discovered, leading to the present invention.

That is, the present invention provides the following methods: in the presence or absence of a thermoplastic resin and/or a rubbery polymer, the monomer formula of a maleimide monomer; Saturated nitrile monomer (B-2) and unsaturated carboxylic acid ester monomer (
B-3) consisting of one or more monomers (Bl) and a monomer copolymerizable with these (Q), whose average composition (thermoplastic resin and rubbery polymer) ) are represented by formulas (1) and (2), in which the following (j) or (i) and (
The copolymer obtained by providing the production process Il) has a total content of monomers (c), (B-2) and "B-3) in the range of 1 to 90% by weight. 9% by weight, in the area where the content exceeds 10% by weight
Excellent heat resistance, chemical resistance, mechanical strength, and moldability, characterized by having a composition distribution of 9 to IO weight %, and compatibility with various non-polar and polar materials. Alternatively, the present invention provides a method for producing a copolymer with good affinity.

Average composition Production process (i) Monomer (3) and (B-) relative to monomer (B-1)
2) A step of copolymerizing by changing the addition ratio of at least one monomer among (B-3) stepwise or continuously.

(ii) A step of adding and polymerizing only one or more monomers selected from monomers (B-1), (B-2), (B-3), and 0.

The present invention will be explained in detail below.

0 Constituent Components of Copolymer Examples of the thermoplastic resin and/or rubbery polymer 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 Graft polyolefin, chlorinated polyolefin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid and its metal salt copolymer,
Ethylene-(meth)acrylic acid ester copolymers such as methyl (meth)acrylate, ethyl, propyl, butyl, glycidyl, and dimethylaminoethyl, ethylene-(meth)acrylic acid alkyl ester-(meth)acrylic acid copolymers , ethylene-(meth)acrylic acid alkyl ester-maleic anhydride copolymer, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer,
Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinyl butyral, polyvinyl chloride, butadiene rubber, styrene-butadiene random or block copolymer, hydrogen Styrene-butadiene random or block copolymer, acrylonitrile-butadiene rubber, isobutylene rubber, acrylic rubber, silicone resin, polycarbonate, polyester, polyamide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, polyetheramide , polyetheretherketone, polyphenylene sulfide, polysulfone, polyethersulfone, polyphenylene ether, polyoxymethylene, and the like. Particularly preferred are those having a glass transition temperature of 0°C or less.

As the maleimide monomer (A-1), maleimide,
N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-
Phenylmaleimide, N-2,8 or 4-methylphenylmaleimide, N-2,3t or 4-nitylphenylmaleimide, N-2,3 or 4-butylphenylmaleimide, N-2,6-dimethylphenylmaleimide enylmaleimide, N
-2,8 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-phenoxyphenylmaleimide, N-4-benzylphenylmaleimide,
N-2-methyl-5-chlorophenylmaleimide, N-
Examples include 2-methoxy-5-chlorophenylmaleimide, and one or more of them can be used. Among these, N-aryl-substituted maleimides are particularly preferred.

Examples of the unsaturated carboxylic acid monomer (A-2) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and himic anhydride. Among these, methacrylic acid and maleic anhydride are particularly preferred.

Any one or two of the above maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2) constitute a copolymer as the monomer (6).

As the aromatic vinyl monomer CB-1), styrene,
a-methylstyrene, α-chlorostyrene, pt-butylstyrene, p-methylstyrene, 0-chlorostyrene, p-chlorostyrene, 2,5-dichlorostyrene,
3.4-dichlorostyrene, p-bromostyrene, 〇-
Bromostyrene, 2,5-dipromostyrene, 3.4-
Examples include dipromostyrene, cyanostyrene, 2-isopropenylnaphthalene, etc., and one or more types can be used. Among these, styrene or α-methylstyrene is usually preferred.

Examples of the unsaturated nitrile monomer (B-2) include acrylonitrile, methacrylonitrile, maleonitrile, and fumaronitrile, and one or more of them can be used. Among these, acrylonitrile is usually preferred.

Examples of the unsaturated carboxylic acid ester 11-mer (13-3) include (meth)acrylates such as methyl, ethyl, propyl, butyl, lauryl, cyclohexyl, 2-hydroxyethyl, glycidyl, and dimethylaminoethyl; Examples include acrylic acid ester monomers, and mono- and dialkyl esters of unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, and hymic acid. One or more types of these can be used. Among these, methyl methacrylate is usually preferred.

One type selected from the above-mentioned aromatic vinyl monomer (B-1), unsaturated nitrile monomer (B-2), and unsaturated carboxylic acid ester monomer (B-3) Alternatively, two or more types constitute a copolymer with zero monomers.

Furthermore, as is clear from formula (1), the above monomer (
A monomer copolymerizable with (c) and (c) can be used as monomer (0).

101 units) include ethylene, propylene, butene-11pentene-1,4-methylpentyne-11 vinyl chloride, vinylidene chloride, tetrafluoroethylene, monochlorotrifluoroethylene, hexafluoropropylene, butadiene, acrylamide, methacrylamide,
Examples include vinyl acetate, vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinyl ether, vinyl ketone, coumaron, indene and acenaphthylene.

0 Average composition The average composition of all the polymers obtained by the method of the present invention is represented by the above formulas (1) and (2).

In formula (1), if the amount of the monomer formula is less than 1% by weight, a copolymer with high heat resistance cannot be obtained;
If it exceeds 0% by weight, not only mechanical strength and processability will decrease, but also compatibility with non-polar or less polar materials will decrease. A particularly preferred amount of monomer (c) is 3 to 50% by weight. In addition, in formula (2), if the amount of monomer (Q) exceeds 50% by weight, the original properties of the copolymer will be lost.The preferred amount of monomer 0 is 0.
~30% by weight.

0 Composition distribution The copolymer obtained by the method of the present invention has a composition distribution such that the content exceeds the ff11O weight% of 99 to 10% by weight.

If the amount is less than 1% by weight, the affinity with non-polar or less polar materials will be poor, while if the amount exceeds 90% by weight, the chemical resistance will be poor in the range of 5 to 80% by weight.

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

0 Production of copolymer In the present invention, the kudzu production step (i) comprises at least one of the monomers (monomers (6), (B-2) and (B-3) for B-H). This is a step of copolymerizing by changing the monomer addition ratio stepwise or continuously.Specific methods for manufacturing step (i) include the following methods.

(a) Monomer (c) and C for monomer (B-1)
A method in which polymerization is initiated by increasing the addition ratio of at least one of B-2> and (B-8), and polymerization is carried out while gradually decreasing the addition ratio.

(b) Monomer (c) for monomer (B-1), (
A method in which polymerization is started by lowering the addition ratio of at least one of B-2) and (B-3), and polymerization is carried out while gradually increasing the addition ratio.

(C) Monomer (6) for monomer (B-1), (
A method of polymerizing while arbitrarily changing the addition ratio of at least one of B-2) and (B-3>).

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

In addition, in the production step (ii) of the present invention, monomers (B-1), (B-2) are , (B-3) and (
This is a step in which only one or more monomers selected from Q are added and polymerized.

In particular, it is possible to polymerize so that the amount of monomer (B-1) alone or the monomer containing monomer (B-1) as the main component gradually increases from the start of addition to the end of addition. It is preferable to obtain a polymer having good affinity with polar materials.

Here, the arbitrary timing of the above-mentioned copolymerization step means any one before the copolymerization, during the copolymerization, and after the copolymerization in the manufacturing step (i).

In addition, the monomer (B-1
), (B-2), (B-3) and (2), there is no particular restriction on the total amount of all monomers (C), (Bl and (Q)).
~90% by weight is preferred.

In order to produce a copolymer having a specific compositional distribution as the object of the present invention, the above step (i) is essential in the entire production process. Further, step (i) and step (It) may be combined, and further, known polymerization steps such as batch addition of mixed monomers, continuous addition polymerization, etc. may be combined as necessary.

Moreover, there are no restrictions on the polymerization method, and any method such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, or a combination thereof can be used. In this case, known polymerization initiators, chain transfer agents, solvents, suspension stabilizers, emulsifiers, pH adjusters, etc. can be used alone or in combination.

The copolymer is produced in the presence or absence of a thermoplastic resin and/or rubbery polymer. When the polymerization is carried out in the presence of the copolymer, the upper limit of the amount of the thermoplastic resin and/or rubbery polymer in the copolymer is preferably 80% by weight or less. Here, especially when the above-mentioned monomers are polymerized in the presence of a rubbery polymer, a graft copolymer having high impact strength can be obtained. The structure of this graft copolymer is not particularly limited, but the weight average particle diameter of the graft copolymer is 0.05.
~IOμm1 Grafting ratio is preferably 10 to 200% by weight. In addition, the intrinsic viscosity of the copolymer is usually 0.2~
1.5d6/g is preferred. Here, when the above-mentioned monomers are graft-polymerized in the presence of a thermoplastic resin and/or rubbery polymer, generally all the monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer, and monomers are not graft-polymerized to the thermoplastic resin or rubbery polymer. Some of the polymers form free copolymers. Therefore, the intrinsic viscosity of the copolymer in this case means the intrinsic viscosity of the free copolymer. Note that the intrinsic viscosity is a value measured in a dimethylformamide solution at 30°C.

In addition, the copolymer containing a maleimide monomer component in the present invention is not only a copolymer produced by directly copolymerizing a maleimide monomer and another monomer, but also a copolymer containing maleic anhydride. A copolymer containing methacrylic acid or methyl methacrylate may be imidized by reacting with ammonia, a primary amine, an isocyanate, etc. The copolymer 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.

Furthermore, for the copolymer obtained by the method of the present invention,
Antioxidants, heat stabilizers, light stabilizers, lubricants, as necessary.
Plasticizers, antistatic agents, inorganic and organic colorants, blowing agents, inorganic and organic fillers, flame retardants, surface gloss improvers,
A matting agent etc. can be added.

These various additives can be added during the copolymer manufacturing process or in the subsequent processing process.

In addition, copolymerized glass fibers, metal m-fibers, carbon fibers or powders thereof, low melting point alloys, calcium carbonate, talc, gypsum, alumina, silica, mica, boron nitride, zirconia, silicon carbide, obtained by the method of the present invention, Can be used as a composite material such as potassium titanate.

Furthermore, polystyrene, rubber-modified polystyrene, maleic anhydride-styrene copolymer, maleic anhydride-acrylonitrile-styrene copolymer, acrylonitrile-
Styrene copolymer, acrylonitrile-a-methylstyrene copolymer, methacrylonitrile-styrene copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate-acrylonitrile-styrene copolymer, methacryl Methyl acid-methacrylic acid copolymer, methyl methacrylate-maleic anhydride copolymer, maleimide monomer and aromatic vinyl monomer, unsaturated carboxylic acid, unsaturated carboxylic acid ester, unsaturated nitrile monomer copolymer with one or more types of other copolymerizable monomers, methyl methacrylate-glutaric anhydride copolymer, methyl methacrylate-styrene-glutaric anhydride copolymer, methacrylic acid Methyl-glutarimide copolymer, styrene-acrylonitrile-methacrylic acid copolymer, ABS resin, AES resin, MBS resin,
AC5 resin, AAS resin, polyethylene, polypropylene, polybutene-11 ethylene-butene-1 copolymer,
Propylene-butene-1 copolymer, propylene-ethylene block copolymer, ethylene-propylene rubber, maleic anhydride graft polyolefin, maleimide monomer graft 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, (meth)acrylic ester copolymers such as dimethylamine ethyl, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic ester-(meth)acrylic acid copolymers, etrafluoroethylene, ethylene- Tetrafluoroethylene copolymer, tetrafluoroethylene-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, polyimide, polyamideimide, polyetherimide, polyetherester, polyetheresteramide, polyetheramide, polyetheretherketone, polyphenylene sulfide, polysulfone, polyethersulfone, polyphenylene ether, styrene-rubber modified polyphenylene ether , vehicle parts, ship parts, etc. as one or more resin compositions or laminates with polyoxymethylene, etc.
It can be widely used in many fields such as aircraft parts, electrical and electronic parts, building materials, office equipment, power tools, agricultural machinery parts, household goods, sports and leisure goods, etc.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Note that all parts and percentages shown in the examples are based on weight.

Example 1 (Copolymer 1-(1)) 70 parts of pure water, 0.1 part of potassium persulfate, and 0.4 part of sodium lauryl sulfate were charged into a 201 reactor equipped with a stirrer and a plate pan, and the reactor was heated. After replacing the inside with nitrogen gas, the temperature was raised to 70''C while stirring.

It was added continuously over time. Simultaneously with the start of addition of this monomer solution, the following emulsifier and polymerization initiator aqueous solutions were continuously added over 8 hours. Thereafter, the temperature was raised to 80''C and maintained for 3 hours to obtain latex with a polymerization rate of 99.1%.

A calcium chloride aqueous solution was added to the obtained polymer latex to coagulate it, and the copolymer was recovered. Table 1 shows the analysis results during the polymerization process.

0 Monomer solution N-phenylmaleimide C) 4020101 Acrylonitrile (%) 15 20 10 2 Styrene) 45608097 Total amount added (parts) 30 20 Emulsifier-polymerization initiator solution Pure water 50 parts Sodium lauryl sulfate 1 Part Potassium persulfate o, Part a Example 2 (Copolymer 1-(2)) Into the reactor used in Example 1 were added 70 parts of pure water, 0.1 part of potassium persulfate, and 0.2 part of potassium alkenylsuccinate. 1 part, and 0.05 part of sodium lauryl sulfate, and the p of the aqueous phase was adjusted with a potassium dihydrogen phosphate-disodium hydrogen phosphate aqueous solution.
H was adjusted to 6 or 7. Next, the inside of the reactor was purged with nitrogen gas, and then the temperature was raised to 70'C while stirring.

To this, a mixed solution consisting of 12 parts of N-phenylmaleimide and 8 parts of acrylonitrile and 80 parts of styrene were used, and the addition ratio of N-phenylmaleimide-acrylonitrile mixed solution/styrene at the start and end of addition was 40%/60, respectively. % and 0%/100% over 5 hours.

Note that t-dodecyl mercaptan was used as a chain transfer agent.

In addition, at the same time as starting addition of this monomer, potassium persulfate
．． 2 parts, 0.8 parts of the above potassium alkenyl succinate,
An aqueous solution consisting of 0.4 parts of sodium lauryl sulfate and 50 parts of pure water was continuously added over 5 hours. After that, 75
The mixture was heated to 0.degree. C. and maintained for 3 hours to obtain latex with a polymerization rate of 98.5%. Note that during the polymerization, the pH of the aqueous phase is 6.5 to 6.5.
The pfi was adjusted by adding a potassium dihydrogen phosphate-disodium hydrogen phosphate aqueous solution so that the pfi was 9.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 2 shows the analysis results during the polymerization process.

Example 3 (Copolymer 1-(3)) 60 parts of pure water, 0.1 part of potassium persulfate, and 0.2 part of sodium dodecylbenzenesulfonate were charged into the reactor used in the production of Example 1, and the reaction was carried out. After purging the inside of the vessel with nitrogen gas, the temperature was raised to 70''C while stirring.

Using 20 parts of methacrylic acid and 80 parts of styrene, the addition ratio of methacrylic acid/styrene at the start and end of addition was 40%/60% and 0%71, respectively.
It was continuously added over 6 hours so that the concentration was 0.00%. In addition,
T-dodecyl mercaptan was used as a chain transfer agent.

Additionally, at the same time as the addition of monomers started, 0.3% of potassium persulfate was added.
1.2 parts of sodium dodecylbenzenesulfonate and 60 parts of pure water were continuously added over 6 hours. Thereafter, the temperature was raised to 75°C and maintained for 3 hours to obtain latex with a polymerization rate of 99.2%.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 3 shows the analysis results during the polymerization process.

Example 4 (Copolymer 1-(4)) 80 parts of pure water, 0.05 part of potassium persulfate, and 1 part of sodium dodecylbenzenesulfonate were charged into the reactor used in Example 1, and the inside of the reactor was heated. After purging with nitrogen gas, the temperature was raised to 65° C. with stirring.

First, 7 parts of a solution consisting of 14 parts of N-phenylmaleimide, 11 parts of acrylonitrile, 45 parts of α-methylstyrene, and 0.1 part of pentaerythritol tetrakis(thioglycolate) were added to the mixture, and the temperature was raised to 70°C. To this, the remaining monomer solution (63 parts) and an aqueous solution consisting of 5 parts of sodium dodecylbenzenesulfonate, 063 parts of potassium persulfate, and 50 parts of pure water were continuously added over 5 hours.

Thereafter, the temperature was raised to 75°C and held for 2 hours.

Then, 4 parts of a solution consisting of 60% N-phenylmaleimide and 40% acrylonitrile and 16% styrene were added.
and 0.2 parts of t-dodecylmercaptan, and the addition ratios of N-phenylmaleimide-acrylonitrile solution/styrene at the start and end of addition were 40%/60% and O%/100%, respectively. The addition ratio was changed so that the addition ratio was changed, and the addition was continued over a period of 2 hours.

Thereafter, 0.1 part of potassium persulfate was added to obtain a latex with a polymerization rate of 99.2%.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 4 shows the analysis results during the polymerization process.

Example 5 (Copolymer 1-5) 70 parts of pure water, 1 part of sodium dodecylbenzenesulfonate, and 0.1 part of potassium persulfate were charged into the reactor used in Example 1, and the inside of the reactor was flushed with nitrogen. After purging with gas, 5 parts of a solution consisting of 21 parts of N-cyclohexylmaleimide, 10 parts of acrylonitrile, 32 parts of methyl methacrylate, and 7 parts of styrene were charged with stirring to 70"
The temperature was raised to C. Add the remaining monomer solution (65 parts) to this
It was added continuously over time.

Next, using 1.5 parts of a solution consisting of 60% N-cyclohexylmaleimide, 1096 acrylonitrile and 30% methyl methacrylate, and 8.5 parts of styrene, N-cyclohexylmaleimide-acrylonitrile was prepared at the beginning and end of the addition. - Addition ratio of methyl methacrylate solution/styrene is 30%/70% and O% respectively
/100% over 1 hour.

Then, after adding 0.2 parts of potassium persulfate, 20 parts of styrene was continuously added over 2 hours. After that, 75
At the same time as the addition of the monomers started, an aqueous solution consisting of 50 parts of pure water, 0.6 parts of sodium dodecylbenzenesulfonate, and 0.2 parts of potassium persulfate was added for 7 hours. It was added continuously.

Note that t-dodecyl mercaptan was used as a chain transfer agent.

The obtained latex was coagulated with an aqueous magnesium sulfate solution, and the copolymer was recovered. Table 5 shows the analysis results during the polymerization process.

Example 6 (Copolymer 1-(6)) The reactor used in Example 1 was charged with 60 parts of pure water, 0.5 part of sodium dodecylbenzenesulfonate, and 0.1 part of potassium persulfate. Next, the inside of the reactor was purged with nitrogen gas, and then the temperature was raised to 75°C while stirring.

A solution consisting of 24 parts of N-phenylmaleimide, 2 parts of methacrylic acid, 10 parts of acrylonitrile and 24 parts of paramethylstyrene was continuously added to this over 6 hours.

Next, using 4 parts of a solution consisting of 60% N-phenylmaleimide and 40% acrylonitrile and 16 parts of styrene, the addition ratio of N-phenylmaleimide-acrylonide 1-nor solution/p-methylstyrene at the start and end of addition was 50%, respectively. %150% and θ%/10
The ratio was changed to 0%, and the addition was continued over 2 hours.

Next, 0.2 parts of potassium persulfate was added, and then 20 parts of paramethylstyrene was continuously added over 2 hours. Thereafter, it was held at 75°C for 2 hours. Simultaneously with the start of monomer addition, an aqueous solution consisting of 50 parts of pure water, 0.5 parts of sodium dodecylbenzenesulfonate, and 0.2 parts of potassium persulfate was continuously added over 8 hours.

Note that t-dodecyl mercaptan was used as a chain transfer agent.

The obtained latex was coagulated with an aqueous calcium chloride solution, and the copolymer was recovered. Table 6 shows the analysis results during the polymerization process.

Example 7 (Copolymer 1-(7)) + 50 parts of styrene, 0.15 parts of lauroyl peroxide and 0.5 parts of t-dodecyl mercaptan were charged into the reactor used in Example 1, and the inside of the reactor was heated. After purging with nitrogen gas, the temperature was raised to 70° C. while stirring.

When the polymerization rate of styrene reached 5%, the following monomer solutions (1) and (2) were successively added over 1 hour each. Next, the following monomer solution III! (3) was continuously added over 3 hours.

After adding 8 parts of acrylonitrile to this, 200 parts of pure water
A solution consisting of 2 parts of an aqueous solution of 0.1 part of partially saponified polyvinyl alcohol and 0.1 part of hydroxypropylmethyl cellulose was added, and the solution was heated to 2 parts at 70°C.
Polymerization was carried out at 90"C for 2 hours and then at 115C for 2 hours.

After polymerization, unreacted monomers were recovered by steam distillation, and polymer beads containing 0.1% residual styrene were recovered. Table 7 shows the analysis results during the polymerization process.

0 Monomer solution Maleic anhydride (parts) 0.5 2 8 Acrylonitrile (parts) 0 1.5 4 Styrene (parts) 9.5 6.5 18 Example 8 (
Copolymer 1-(8)) To the reactor used in Example 1, 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate, and 0.3 parts of dextrose were added. Then, 60 parts (solid content equivalent) of polybutadiene latex (rubber weight average particle size 0.42 μm, 1 gel content 78%, solid content 40%, emulsifier sodium dodecylbenzenesulfonate, pH 6.5) was charged. The inside of the reactor was purged with nitrogen gas, and the temperature was raised to 70''C while stirring.

Add to this a mixed solution of 30% N-phenylmaleimide and 70% acrylonitrile and 3 styrene.
Using 2 parts, the addition ratio of N-phenylmaleimide-acrylonitrile mixed solution/styrene at the start and end of addition was 40%/60% and O%/100, respectively.
% over 4 hours. Note that t-dodecyl mercaptan was used as a chain transfer agent. Simultaneously with the start of monomer addition, an aqueous solution consisting of 0.2 parts of cumene hydroperoxide, 0.7 parts of sodium dodecylbenzenesulfonate, and 20 parts of pure water was continuously added over 4 hours. Thereafter, the temperature was raised to 75''C and maintained for 2 hours to obtain a latex with a grafting rate of 35% and a polymerization rate of 99.1%.

This latex was coagulated with an aqueous magnesium sulfate solution, and the copolymer was recovered. Table 8 shows the analysis results during the polymerization process.

Example 9 (Copolymer 1-(9)) In the reactor used in Example 1, 20 parts of pure water, o, t parts of sodium dodecylbenzenesulfonate, 0.002 parts of ferrous sulfate heptahydrate, and pyrroline were added. 0.1 part of sodium chloride and 0.3 part of dextrose were added, and then polybutyl acrylate rubber latex (rubber weight average particle size 0.21
After charging 50 parts (in terms of solid content) of 76% gel content (μm1, 43% solid content), the inside of the reactor was replaced with nitrogen gas, and 8 parts of styrene and 12 parts of methyl methacrylate were charged with stirring for 1 hour. The temperature was raised to 75°C. An aqueous solution consisting of 0.3 parts of t-butyl hydroperoxide and 10 parts of pure water was continuously added to this over 2 hours.

Next, using 6 parts of a solution consisting of 60% N-2-chlorophenylmaleimide and 40% acrylonitrile and 24 parts of styrene, N-
The addition ratio of 2-chlorophenylmaleimide-acrylonitrile solution/styrene was changed to 40%/100% and O%/100%, respectively, and the addition was continued over a period of 3 hours.

Note that ethylene glycol dithioglycolate was used as a chain transfer agent. Simultaneously with the start of the addition of these monomers, an aqueous solution consisting of 0.3 parts of [-butyl hydroperoxide, 0.5 parts of sodium dodecylbenzenesulfonate, and 30 parts of pure water] was continuously added over a period of 3 hours.

Thereafter, it was kept at 75°C for 2 hours.

The obtained latex was coagulated with magnesium sulfate,
A copolymer with a graft ratio of 51% was recovered. Table 9 shows the analysis results during the polymerization process.

Example 10 (Copolymer 1-(10)) In the reactor used in Example 1, 70 parts of pure water, 0.02 part of potassium persulfate,
0.05 parts of sodium lauryl sulfate and 0.0 parts of potassium alkenylsuccinate (alkyl group has 16 to 18 carbon atoms).
After charging an aqueous solution consisting of 0.05 parts, the pH of the aqueous phase was adjusted to 6.9 with a potassium dihydrogen phosphate-disodium hydrogen phosphate aqueous solution (buffer solution). Next, the inside of the reactor was purged with nitrogen gas, and then the temperature was raised to 75°C while stirring. A solution consisting of 20 parts of N-phenylmaleimide, 10 parts of acrylonitrile, 30 parts of styrene and 0.2 parts of t-dodecylmercaptan was continuously added to this over 4 hours.

In addition, at the same time as the addition of this monomer solution started, an aqueous solution consisting of 0.25 parts of potassium persulfate, 0.8 parts of sodium lauryl sulfate, 0.8 parts of potassium alkenyl succinate, and 50 parts of pure water was added continuously over 6 hours. Added.

Next, after adding the above monomer solution, a solution 3 consisting of 60% N-phenylmaleimide and 40% acrylonitrile was added.
and 17 parts of styrene over 2 hours so that the addition ratio of N-phenylmaleimide-acrylonitrile solution/styrene at the start and end of addition was 30%/70% and 0%/100%, respectively. Added. Thereafter, 0.2 parts of potassium persulfate was added, followed by continuous addition of 20 parts of styrene over 2 hours, and 75"
It was held at C for 2 hours. Note that during the polymerization, the pH of the aqueous phase is 6-6.
7 using the above buffer solution. Note that 1-dodecylmercaptan was used as a chain transfer agent.

The obtained latex was coagulated with an aqueous magnesium sulfate solution, and the copolymer was recovered. Table 10 shows the analysis results during the polymerization process.

A copolymer was obtained by the method of Example 1 except that # was used for polymerization. The results are shown in Table 11.

Polymerization was carried out according to the method of Example 3 to obtain the copolymers shown in Table 11.

Comparative Example 3 (Copolymer 2-(3)) 30 parts of acrylonitrile and 70 parts of styrene were copolymerized by a known suspension polymerization method (according to Japanese Patent Publication No. 49-37590) to produce the copolymer shown in Table 11. Obtained union.

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

NPMI: N-phenylmaleimide CHMI: N-cyclohexylmaleimide CPMI: N
-2-chlorophenylmaleimide MAA: methacrylic acid MAH: maleic anhydride 8N: acrylonitrile MMA: methyl methacrylate S: styrene AMS: a-methylstyrene PMS: paramethylstyrene BR: polybutadiene rubber BAR: polybutyl acrylate rubber [ η] Intrinsic viscosity measured at 30"C in dimethylamide solution, unit: dl/F/Next, in order to investigate the characteristics of the copolymers produced in each example and comparative example, the following test was conducted as a test example. .The thermoplastic resin and rubbery polymer for blending used in the test are the following polymers A to B.

Polymer A (ABS) 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrrolyte phosphate, and dextro -mo.
) After charging 60 parts (solid content equivalent), the inside of the reactor was
The atmosphere was replaced with nitrogen gas, and the temperature was raised to 70°C while stirring.

To this, a mixed solution consisting of 15 parts of acrylonitrile, 35 parts of styrene, and 0.3 parts of t-dodecylmercaptan, and 1.2 parts of potassium alkenylsuccinate, t-
Butyl hydroperoxide 0.3 parts and pure water 30 parts
of the aqueous solution was added continuously over a period of 3 hours. Thereafter, it was held at 75"C for 2 hours to obtain a latex with a polymerization rate of 99.1%. The obtained latex was coagulated with magnesium sulfate, resulting in a grafting rate of 42% and an intrinsic viscosity of the ungrafted copolymer of 0. .47 dll'J polymer was recovered.

Polymer B (AAS) Butyl acrylate rubber latex (weight average particle size 0.3
The above copolymer 2-
Polymerization was carried out according to the production method of (5), and the polymerization rate was 98.9%.
Grafting rate 47%, intrinsic viscosity of ungrafted copolymer 0,
52 dl/'l of polymer was obtained.

Polymer C (ABSM) 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate and 0.3 parts of dextrose were added to the reactor used in Example 1, Next, after charging 60 parts (in terms of solid content) of acrylonitrile-butadiene rubber latex (rubber weight average particle size 0.31 μm, gel content 77%, acrylonitrile content 30%, solid content 41%), the inside of the reactor was flushed with nitrogen. Replace with gas and stir for 70 minutes.
The temperature was raised to °C. 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 emulsifier-polymerization initiator aqueous solution was continuously added over 4 hours. After that, it was kept 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, and a polymer having a graft ratio of 41% and an intrinsic viscosity of the ungrafted copolymer of 0.51 dl/da was recovered.

0 Monomer solution (part) Acrylonitrile・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 5 Methyl methacrylate・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・23 Styrene ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・120 emulsifier-polymerization initiator aqueous solution (part) pure
water ················
・・・・・・・・・・・・・・・・・・・・・ 30 Sodium dehydroabietate・・・・・・・・・・・・
・・・・・・・・・ 1.5 Kiyumene Hydroperoxide・・・・・・・・・・・・・・・・・・・・・
0.3 Polymer D (MBS) 30 parts of pure water, 0.002 parts of ferrous sulfate heptahydrate, 0.1 part of sodium pyrophosphate, and 0.3 parts of dextrose were added to the reactor used in Example 1. Then, styrene-butadiene rubber latex (rubber weight average particle size 0.4
After charging 50 parts (in terms of solid content) (7 μm 1 gel content: 77%, styrene content: 25%, solid content: 41%), the inside of the reactor was purged with nitrogen gas, and the temperature was raised to 70°C while 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 emulsifier-polymerization initiator aqueous solution was continuously added over 4 hours. After that, 75
The mixture was kept at °C for 2 hours to obtain a latex with a polymerization rate of 9869%. The obtained polymer latex was coagulated with calcium chloride, resulting in a grafting rate of 45% and an ungrafted copolymer of 0.
．． 49 dl/I of polymer was recovered.

0 Monomer solution (part) Methyl methacrylate 30 Styrene
200 emulsifier-polymerization initiator aqueous solution (part) pure water
30 Sodium dehydroabietate 1.5 t-Butyl hydroperoxide 0.8 Polymer E (AES) Into the reactor used in Example 1, block type polyether dispersant (Pluronic F68 manufactured by Asahi Denka Co., Ltd.) 0.5 550 parts of pure water dissolved in 550 parts of pure water, and ethylene-propylene-ethylidene norbornene ternary copolymer rubber chopped into 4 to 6 meshes (Iodine number: 21.1. Mooney viscosity at 100°C: 76, propylene content: 46.0 100 parts (% by weight) were added and stirred to suspend. Next, a monomer mixture of 40 parts of acrylonitrile and 75 parts of styrene containing 3 parts of t-butylperoxypivalate and 0.05 part of p-quinone was added as a polymerization initiator, and steam was immediately blown into the jacket of the autoclave to raise the temperature. Start heating. 2
The temperature reached 100°C after 0 minutes, and the temperature was kept at 100°C for 1 hour.
The polymerization reaction was carried out while maintaining the temperature at 0°C. As a result, the grafting rate was 71%, and the intrinsic viscosity Q of the ungrafted copolymer was 57.
A polymer of dl/I was obtained.

Polymer F Polystyrene (Japan Polystyrene, Nisbright 4) Polymer G High impact polystyrene (Japan Polystyrene,
Nisbright 5005B) Polymer ■1 Polycarbonate (Teijin Kasei, Panlite L-1250) Polymer I Polyamide (Mitsubishi Kasei, Tsubamitsudo 1015
G30) Polymer J Ethylene-glycidyl methacrylate copolymer (Sumiho Chemical, Bond First 2B) Polymer K Polyester (Toyobo, Pelprene P4oH
) Polymer L Styrene-butadiene block copolymer (Shell Chemical Co., Ltd., Kraton Test Examples 1 to 11, Comparative Test Examples 1 to 6 Each copolymer obtained in the Examples and Comparative Examples or their and other thermoplastic resins were blended in the proportions shown in Table 12, and triethylene glycol-bis[3-(3-t-butyl-
10.1 parts of 5-methyl-4-hydroxyphenyl)propionate, 0.1 part of dilauryl-3,3'-thiodipionate and 0.2 parts of (2°4-t-butylphenyl)pentaerythritol diphosphite. In addition, 0.2 part of ethylene bis stearamide was added as a lubricant, and the mixture was heated to 250~
The mixture was kneaded at 300°C and pelletized.

The total amount t of residual monomers in these pellets was all 0.2% or less.

This pellet was molded at 250 to 320'C using an injection molding machine to prepare a test piece, and its physical properties were measured. The results are shown in Table 12.

In addition, the physical properties were measured by the following method.

Zero Notched Izot Impact Strength (abbreviated as NI): Measured on 8 inch thick specimen at 23°C.

0 Heat Deformation Zone (abbreviated as HDT): Value measured on inch thick specimen, 264 psi load, without annealing.

0 Solvent Resistance: After the test piece was immersed in 30''C gasoline for 24 hours, the state of surface roughness etc. was observed with the naked eye.

Test Examples 12 to 25 and Comparative Test Examples 7 to 15 Each copolymer obtained in the Examples and Comparative Examples or them and another thermoplastic resin or rubbery polymer were blended in the proportions shown in Table 13. In addition, each composition was mixed with the following compounding agents (the amount added is the number of parts per 100 parts of the resin composition) using a Henschel mixer, and then pelletized by the method of Test Example 1 above to create a test piece. The physical properties were measured. The results are shown in Table 13.

O compounding agent 1) 2-t-butyl-6-(3'-t-butyl-5'-
Methyl-guhydroxybenzyl)-4-methylphenylacrylate・・・・・・・・・・・・・・・・・・
...0.2 part 2) Trisnonylphenyl phosphite ...0.2 part 3) 2-(3,5-
di-t-butyl-4-hydroxybenzyl)-2-n-
Butylmalonate bis(1,2,2゜6.6-bentamethyl-4-piperidyl) 0.3 parts 4) Ethylene bisstearamide 0. 2
Part 5) Calcium stearate...
...0.3 part〈Effect of the invention〉

Claims (1)

[Claims] 1. Maleimide monomer (A-1) and unsaturated carboxylic acid monomer (A-2) in the presence or absence of a thermoplastic resin and/or rubbery polymer. Any one or two monomers (A) and an aromatic vinyl monomer (B-1)
, 1 selected from unsaturated nitrile monomer (B-2) and unsaturated carboxylic acid ester monomer (B-3)
It consists of a species or two or more monomers (B) and a monomer (C) copolymerizable with these, and its average composition (excluding thermoplastic resins and rubbery polymers) is expressed by formula (1) and In the method for producing the copolymer represented by (2), the copolymer obtained by providing the following production steps (i) or (i) and (ii) contains monomers (A), (B-
2) and (B-3) has a composition distribution such that 1 to 90% by weight is in the region where the total content is 10% by weight or less, and 99 to 10% by weight in the region where the content exceeds 10% by weight. A method for producing a copolymer, characterized in that: Average composition {(A)/[(A)+(B)+(C)]}×100=1
~60% by weight (1) {(C)/[(A)+(B)+(C
) ] x 100 = 0 to 50% by weight (2) Production process (i) Monomer (A), (B-
2) A step of copolymerizing by changing the addition ratio of at least one monomer among (B-3) stepwise or continuously. (ii) Polymerization by adding only one or more monomers selected from monomers (B-1), (B-2), (B-3) and (C) Process. 2. The copolymer contains monomers (A), (B-2) and (B
-3) 5 to 80% by weight in the area where the total content is 10% by weight or less, 95 to 20% by weight in the area where the content exceeds 10% by weight, and 2 to 80% by weight in the area where the content exceeds 20% by weight. 8
The method for producing a copolymer according to claim 1, characterized in that the copolymer has a composition distribution such that the copolymer has a composition distribution of 0% by weight.