JP2508192B2 - Process for producing N-arylmaleimide copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an N-arylmaleimide copolymer useful for a thermoplastic resin.

(Prior Art) Rubber-modified thermoplastic resins obtained by graft-polymerizing acrylonitrile and styrene on rubber include so-called ABS resin, AA
There is one known as S resin. These resins are widely used today because of their excellent workability, mechanical strength, surface gloss and chemical resistance. However, it is hard to say that it has sufficient heat resistance depending on the field of use. As a method of improving the heat resistance, it is generally known that a part or all of styrene is replaced with α-methylstyrene for use. However, even with this method, there is a limit to the improvement of heat resistance, and it is not always satisfactory in the field requiring heat resistance such as parts of automobiles and light electric equipment.

On the other hand, copolymers of vinyl monomers such as styrene and N-substituted maleimides have high heat distortion temperature and thermal decomposition temperature (Polymer Thesis, Vol. 36, No. 7, p. 447). , 1979
, Published by The Society of Polymer Science, Japan, inferior in mechanical properties such as impact resistance [Journal of Polymer Science (J.
Polymer Sci.) Vol. 36, p. 241, published 1959].

Therefore, it has been proposed to obtain a copolymer having excellent impact resistance and heat resistance by reacting N-substituted maleimide, olefinic unsaturated nitrile and aromatic vinyl in the presence of a rubber component. (British Patent No. 3,721,724). However, carrying out the polymerization reaction of maleimide or the like in the presence of the rubber component induces a marked decrease in the polymerization rate. In addition, the amount of the copolymer that does not bond with the rubber component increases. Furthermore, the molecular weight tends to be low. Therefore, it was difficult to achieve both heat resistance and impact resistance.

Further, a thermoplastic resin composition prepared by blending a copolymer containing an N-substituted maleimide and a graft copolymer based on a rubber-like polymer has been proposed (Japanese Patent Publication No. 46-3410).
No. 3 bulletin. See JP-A-53-117050). The thermoplastic resin composition proposed here exhibits excellent thermal shock resistance and heat resistance, but it cannot be said to be sufficient.

(Problems to be Solved by the Invention) The present invention solves the above problems. That is,
A method for producing an N-arylmaleimide copolymer useful for a thermoplastic resin composition containing a graft copolymer based on a rubbery polymer, which is significantly improved in impact resistance and heat resistance at the same time. It is provided.

(Means for Solving the Problems) The present invention relates to an aqueous solution prepared by adding a chain transfer agent and an emulsifier in advance and adding 10 to 60% by weight of N-arylmaleimide, 16 to 65% by weight of an aromatic vinyl compound and a vinyl cyanide compound. ，
A N-arylmaleimide system characterized by carrying out a copolymerization reaction by adding a monomer containing 60 to 15% by weight of at least one compound selected from the group consisting of acrylic acid ester and methacrylic acid ester and a polymerization initiator. The present invention relates to a method for producing a copolymer. The N-arylmaleimide-based copolymer produced by this method is particularly useful when used as the following composition. That is, (A) an N-arylmaleimide copolymer produced by the above method, (B) in the presence of 1 to 15 parts by weight of a rubber-like polymer, 50 to 85% by weight of an aromatic vinyl compound and a vinyl cyanide compound. 15
A graft copolymer obtained by polymerizing 85 to 99 parts by weight of a monomer mixture containing 50 to 50% by weight, and (C) an aromatic vinyl compound 60 to 80 in the presence of 30 to 80 parts by weight of a rubber-like polymer. Wt% and vinyl cyanide compound 20
Containing a graft copolymer obtained by polymerizing 70 to 20 parts by weight of a monomer mixture containing 40 to 40% by weight, the component (A) being 10 to 80% by weight, the component (B) and the component (C). The total of the components is 90 to 20% by weight. (B)
A heat-resistant impact-resistant thermoplastic resin composition prepared by blending the component / (C) component in a weight ratio of 1/99 to 99/1 is particularly useful.

First, a method for producing an N-arylmaleimide copolymer and the obtained copolymer [that is, the copolymer of the component (A) (hereinafter, referred to as "copolymer (A)")] will be described.

The copolymerization component N-arylmaleimide is used in an amount of 10 to 60% by weight, preferably 12 to 55% by weight. When N-arylmaleimide is less than 10% by weight, the heat resistance of the thermoplastic resin composition (hereinafter, simply referred to as a resin composition) obtained by blending the copolymer (A) is lowered, and 60% by weight is added. When it exceeds, the fluidity and impact resistance of the resin composition are deteriorated. Aromatic vinyl compound is 16 to 65% by weight, preferably 18 to 60% by weight
used. If the amount of the aromatic vinyl compound is less than 16% by weight, the impact resistance of the resin composition will decrease, and if it exceeds 65% by weight, the heat resistance will decrease. At least one compound selected from the group consisting of vinyl cyanide compounds, acrylic acid esters and methacrylic acid esters 60 to 15% by weight, preferably
Used from 55 to 18% by weight. If the amount of these monomers is less than 15% by weight, the fluidity and impact resistance of the resin composition will decrease.
When it exceeds 0% by weight, the heat resistance of the resin composition is lowered. 30% by weight of other copolymerizable monomers
You may use below. 100% by weight of the above monomers in total
It is adjusted to become.

 The copolymer (A) is obtained by emulsion polymerization.

A chain transfer agent is added to adjust the molecular weight of the copolymer (A) and improve moldability. Chain transfer agent,
It is generally used by dissolving in a monomer. However, in the present invention, the chain transfer agent is present together with the emulsifier in advance to prepare an emulsified aqueous solution, and then the monomer and the polymerization initiator are added to carry out the copolymerization reaction. By this,
Improves heat resistance and impact resistance. This is because the monomer moves to the emulsifier micelle incorporating the chain transfer agent and the polymerization proceeds, so the concentration of the chain transfer agent with respect to the monomer changes and the molecular weight distribution becomes broader, making it compatible with the graft copolymer. Is improved. For this reason, other polymerization methods such as solution polymerization, suspension polymerization and bulk polymerization cannot be used in the present invention.

Examples of chain transfer agents include n-dodecyl mercaptan, t-dodecyl mercaptan, xanthogen disulfide, terpene and tetrahydronaphthalene. The chain transfer agent is preferably used in an amount of 0.01 to 3% by weight based on the monomer.

Anionic, cationic or nonionic surfactants can be used as the emulsifier. Anionic surfactants are particularly preferable, and specific examples thereof include sodium lauryl sulfate, potassium oleate, disproportionated potassium rosinate, sodium dioctylsulfosuccinate, and sodium dodecylbenzenesulfonate. These are 0.5 ~
Preference is given to using 7% by weight. In addition, in order to improve the emulsion stability, sulfates, chlorides, carbonates and the like of alkali metals such as sodium and potassium may be used.

As the polymerization initiator used in the polymerization, persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, water-soluble peroxides such as queumen hydroperoxide and the like, and compounds forming a redox system with them. There is a combination with. These are usually used in an amount of 0.05 to 5% by weight based on the monomers.

As the aryl group of the N-arylmaleimide,
Phenyl group, 4-diphenyl group, 1-naphthyl group, mono- or dimethylphenyl group, 2,6-diethylphenyl group, mono- or dihalogenated phenyl group, 2,4,6-trichlorophenyl group, 2,4 , 6-tribromophenyl group, 4-n-butylphenyl group, 2-methyl-4-n-butylphenyl group, 4-benzylphenyl group, 2,3- or 4-methoxyphenyl group, 2-methoxy- 5-chlorophenyl group, 2-methoxy-5-bromophenyl group, 2,5-dimethoxy-4-chlorophenyl group, 2,3- or 4-ethoxyphenyl group, 2,5-diethoxyphenyl group, 4-phenyl group Enoxyphenyl group, 4-methoxycarbonylphenyl group, 4-cyanophenyl group, 2,3- or 4-
And a nitrophenyl group, 2,3-, 2,4-, 2,5- or 4,3-methylchlorophenyl group. Particularly, those having a phenyl group or an o-methylphenyl group are preferable.

Examples of the aromatic vinyl compound used for producing the copolymer (A) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, dichlorostyrene and bromostyrene. , Dibromostyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene, vinylnaphthalene and the like. Of these, styrene and α-methylstyrene are preferred.

The vinyl cyanide compound used for producing the copolymer (A) includes acrylonitrile, methacrylonitrile, and the like, and acrylic acid ester and methacrylic acid ester include acrylic acid or methacrylic acid methyl ester, ethyl ester, There are butyl ester, hexyl ester, etc., and methyl acrylate and methyl methacrylate are particularly preferable.

The weight average molecular weight of the copolymer (A) is preferably in the range of 50,000 to 300,000. If it is less than 50,000, the impact resistance tends to decrease, and if it exceeds 300,000, the fluidity tends to decrease.

The weight average molecular weight in the present invention is a value measured by gel permeation chromatography and calculated in terms of standard polystyrene.

Next, the heat resistant and impact resistant thermoplastic resin composition (hereinafter, simply referred to as a resin composition) containing the copolymer (A) as one component will be described in detail.

The graft copolymer (hereinafter referred to as "graft copolymer (B)"), which is the component (B) of the resin composition, will be described.

The graft copolymer (B) is a graft copolymer obtained by polymerizing a monomer in the presence of a small amount of a rubber-like polymer. ) And a graft copolymer of component (C) described below in a specific amount to facilitate compatibility with each other and improve impact resistance without lowering heat resistance of the resin composition. it can.

The rubber-like polymer used for producing the graft copolymer (B) is used in an amount of 1 to 15% by weight, preferably 3 to 10% by weight. The monomer to be graft-polymerized is used in an amount of 99 to 85% by weight, preferably 97 to 90% by weight. If the rubber-like polymer is less than 1% by weight, the impact resistance of the resin composition will decrease,
If it exceeds 5% by weight, the ability of the copolymer (A) and the graft copolymer of the component (C) to be compatible with each other decreases, and the heat resistance of the resin composition decreases.

The monomer to be graft-polymerized is an aromatic vinyl compound 50
.About.85% by weight, preferably 65 to 75% by weight and vinyl cyanide compound 50 to 15% by weight, preferably 35 to 25% by weight. If necessary, other copolymerizable monomers such as methacrylic acid ester, acrylic acid ester, vinyl acetate, etc. are preferably contained in an amount of not more than 30% by weight, particularly preferably not more than 25% by weight, based on all monomers. You can leave. The above monomers are adjusted to 100% by weight in total. If the amount of the aromatic vinyl compound is too small or the amount of the vinyl cyanide compound is too large, the fluidity tends to decrease. If there are too many aromatic vinyl compounds or too few vinyl cyanide compounds, the impact resistance tends to decrease. Further, if the amount of other copolymerizable monomer is too much, the impact resistance tends to be lowered.

Examples of the rubber-like polymer include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polyisoprene, poly-2,3-dimethylbutadiene, polypiperylene, polychloroprene, ethylene-propylene-diene copolymer and the like. The diene-based copolymer, ethylene-propylene rubber, acrylic rubber, and composite rubber obtained by synthesizing acrylic rubber in the presence of the diene-based copolymer.

The acrylic rubber is a polyfunctional monomer and has 1 to 13 carbon atoms.
It can be obtained by copolymerizing the acrylate ester having an alkyl group of 1) and, if necessary, another monomer copolymerizable therewith.

Polyfunctional monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol diacrylate, divinylbenzene,
Examples thereof include polyvalent vinyl compounds such as diallyl phthalate, dicyclopentadiene acrylate, and dicyclopentadiene methacrylate, and polyvalent allyl compounds such as triallyl cyanurate, triallyl isocyanurate, and diallyl phthalate. Nurate and triallyl cyanurate are particularly preferred. The polyfunctional monomer is preferably 0.
It is used in the range of 1 to 20% by weight, particularly preferably 0.5 to 10% by weight. If it is less than 0.1% by weight, the degree of crosslinking is insufficient and the impact resistance and the appearance of the molded product tend to be poor. If it exceeds 20% by weight, the degree of crosslinking is excessive and the impact resistance tends to decrease. Examples of the acrylic acid ester having an alkyl group having 1 to 13 carbon atoms include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. Of these, butyl acrylate is particularly preferable. The acrylic ester is preferably used in an amount of 50 to 99.9% by weight, particularly preferably 65 to 99.5% by weight, based on all monomers. If it is less than 50% by weight, impact resistance tends to decrease. Other monomers that can be copolymerized with acrylic acid ester include styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, methacrylic acid alkyl ester (methyl ester, butyl ester, etc.). It is used in the range of 0 to 30% by weight, preferably 0 to 25% by weight. If it exceeds 30% by weight, sufficient impact resistance cannot be obtained.

The composite rubber is a polyfunctional monomer in the presence of the diene-based polymer rubber, an acrylate ester having an alkyl group having 1 to 13 carbon atoms, and optionally copolymerizable with them. It is obtained by copolymerizing a polymerizable monomer obtained by blending the above monomer. The diene polymer and the polymerizable monomer are used in a weight ratio of the former / the latter of preferably 5/95 to 40/60, and more preferably 20/80 to 35/65. If this ratio is less than 5/95, the impact resistance and the appearance of the molded product tend to be poor, and if it exceeds 40/60, the weather resistance tends to be poor. The composite rubber preferably has a polymerization rate of the polymerizable monomer of 50 to 93.
It is particularly preferable that the rubber-like resin composition is obtained by stopping the polymerization in the range of 55% by weight, particularly 55-75% by weight. It is preferable to use a graft copolymer obtained by using such a rubber-like resin composition from the viewpoint of impact resistance and heat resistance. That is, when the polymerization rate exceeds 93% by weight, the impact resistance improving effect tends to decrease, and when it is less than 50% by weight, the heat resistance tends to decrease. The composition of the polymerizable monomer used for producing the composite rubber is the same as that for producing the acrylic rubber.

The polymerization for producing the acrylic rubber and the composite rubber can be performed by a known emulsion polymerization method. In this emulsion polymerization, as a polymerization initiator, potassium persulfate,
Persulfates such as sodium persulfate and ammonium persulfate, water-soluble peroxides such as Kyumen hydroperoxide, and combinations of these with compounds that form a redox system are used. Anionic and cationic emulsifiers are used. , Or a nonionic surfactant can be used, and an anionic surfactant is particularly preferable.

The aromatic vinyl compound used in the production of the graft copolymer (B) is the same as that used in the production of the copolymer (A), and the vinyl cyanide compound is acrylonitrile or methacrylic acid. Ronitrile, etc.
Among the other copolymerizable monomers used as necessary, the same methacrylic acid ester and acrylic acid ester as those used in the production of the copolymer (A) can be used.

Next, the graft copolymer of component (C) (hereinafter referred to as "graft copolymer (C)") will be described.

The graft copolymer (C) has a larger ratio of a rubbery polymer than the graft copolymer (B), and is used for improving the impact resistance of the heat resistant thermoplastic resin composition according to the present invention.

The rubber-like polymer used in the production of the graft copolymer (C) and the monomer to be graft-polymerized are respectively 30 to 80% by weight, preferably 40 to 70% by weight and 70 to 20% by weight, preferably Used from 60 to 30% by weight. 30% by weight of rubbery polymer
If it is less than 80%, the impact resistance decreases, and if it exceeds 80% by weight, the heat resistance decreases.

The monomer to be graft-polymerized is an aromatic vinyl compound 60
% To 80% by weight, preferably 65 to 78% by weight, and 20 to 40% by weight, preferably 20 to 35% by weight of a vinyl cyanide compound, if necessary, other than methacrylic acid ester, acrylic acid ester, vinyl acetate, etc. The copolymerizable monomer of is preferably 30% by weight or less based on all monomers, and particularly preferably
It may be contained up to 25% by weight. The above monomers are adjusted so that the total amount becomes 100% by weight. If the amount of the aromatic vinyl compound is too small or the amount of the vinyl cyanide compound is too large, the fluidity tends to decrease. If the amount of the aromatic vinyl compound is too large or the amount of the vinyl cyanide compound is too small, the impact resistance tends to decrease.

The rubber-like polymer, aromatic vinyl compound, vinyl cyanide compound and other copolymerizable monomers used are the same as those in the graft copolymer (B), and are preferable. The same can be used as.

It is preferable that both of the graft copolymers (B) and (C) have a weight average molecular weight of their acetone-soluble components of 50,000 to 300,000. If the weight-average molecular weight of the acetone-soluble component of these graft copolymers is too small, impact resistance tends to decrease, and if it is too large, molding processability tends to decrease.

The above-mentioned copolymer (A), graft copolymer (B) and graft copolymer (C) are 10 to 80% by weight, preferably 20 to 70% by weight of the copolymer (A) and the graft copolymer. 90 to 20% by weight of the total of (B) and the graft copolymer (C),
It is preferably 80 to 30% by weight, and the ratio of graft copolymer (B) / graft copolymer (C) is 1/99 to
The heat-resistant, impact-resistant thermoplastic resin composition according to the present invention can be obtained by blending so as to be 99/1, preferably 10/90 to 95/5. If the content of the copolymer (A) is less than 10% by weight, the heat resistance will decrease, and if it exceeds 80% by weight, the fluidity and impact resistance will decrease. If the ratio of graft copolymer (B) / graft copolymer (C) is less than 1/99 by weight, heat resistance tends to decrease, and if it exceeds 99/1, impact resistance tends to decrease. Become.

(Example) Hereinafter, the present invention will be described more specifically with reference to examples.

[Production of Copolymer (A)]

Production Example 1 (Synthesis of Copolymer (A-1)) 200 parts by weight of ion-exchanged water was charged into a reactor, and after replacement with nitrogen, 6
After heating to 0 ℃, 2 parts by weight of sodium lauryl sulfate, t
0.4 parts by weight of -dodecyl mercaptan was charged and stirred for 10 minutes to emulsify t-dodecyl mercaptan. Next, 0.15 parts by weight of potassium persulfate and 0.015 parts by weight of sodium sulfite were charged, and 100 parts by weight of a monomer consisting of 20% by weight of N-phenylmaleimide, 60% by weight of α-methylstyrene and 20% by weight of acrylonitrile was added for 3 hours. After the dropping was completed, the mixture was polymerized at 60 ° C. for 1 hour and at 80 ° C. for 2 hours. After completion of the polymerization, the degree of polymerization was determined by gas chromatography and found to be 9
It was 8%. In addition, the weight average molecular weight (M
Abbreviated as w. The gel permeation chromatography measurement, converted to standard polystyrene (the same applies below) was 120,000. This latex is referred to as a copolymer (A-1).

Production Example 2 (Synthesis of Copolymer (A-2)) 200 parts by weight of ion-exchanged water was charged in a reactor and after substitution with nitrogen, 6
After heating to 0 ℃, 2 parts by weight of sodium lauryl sulfate, t
0.5 parts by weight of -dodecyl mercaptan was charged and stirred for 10 minutes to emulsify t-dodecyl mercaptan. Next, 0.14 parts by weight of potassium persulfate and 0.028 parts by weight of sodium sulfite were charged, and 41% by weight of N-phenylmaleimide, 28% by weight of α-methylstyrene and 31% by weight of methyl methacrylate.
100 parts by weight of the monomer was continuously added dropwise over 3 hours, and after completion of the addition, polymerization was carried out at 60 ° C. for 1 hour and at 80 ° C. for 2 hours. The copolymer obtained has an Mw of 120,000 and a polymerization rate of 98%.
It was. This latex is referred to as a copolymer (A-2).

Production Example 3 (Synthesis of Copolymer (A-3)) A copolymer (A-3) was obtained in the same manner as in Production Example 2 except that methyl acrylate was used instead of methyl methacrylate. The copolymer obtained had an Mw of 120,000 and a polymerization rate of 98%.

Production Example 4 (Synthesis of Copolymer (A-4)) N-phenylmaleimide 41% by weight to 29% by weight, α-
A copolymer (A-4) was obtained in the same manner as in Production Example 2 except that 28% by weight of methylstyrene was changed to 20% by weight and 31% by weight of methylmethacrylate was changed to 51% by weight. The copolymer obtained had an Mw of 120,000 and a polymerization rate of 98%.

Production Example 5 (Synthesis of Copolymer (A-5)) The procedure of Production Example 2 was repeated except that t-dodecyl mercaptan was dissolved in the monomer and added dropwise, and the copolymer (A-
5) was obtained. The copolymer obtained has an Mw of 120,000 and a polymerization rate of 9
It was 8%.

Production Example 6 (Synthesis of Copolymer (A-6)) N-phenylmaleimide 41% by weight to 50% by weight, α-
A copolymer (A-6) was obtained in the same manner as in Production Example 2 except that 28% by weight of methylstyrene was changed to 40% by weight and 31% by weight of methyl methacrylate was changed to 10% by weight. The copolymer obtained had an Mw of 130,000 and a polymerization rate of 99%.

Production Example 7 (Synthesis of Copolymer (A-7)) N-phenylmaleimide 41% by weight to 30% by weight, α-
A copolymer (A-7) was obtained in the same manner as in Production Example 2 except that 28% by weight of methylstyrene was changed to 10% by weight and 31% by weight of methyl methacrylate was changed to 60% by weight. The polymerization rate was 96%.

[Manufacture of rubber latex]

Production Example 8 240 parts by weight of ion-exchanged water, 1.0 part by weight of potassium oleate, and polybutadiene latex 3 were placed in a reactor substituted with nitrogen.
0 parts by weight (solid content), butyl acrylate 70 parts by weight, triallyl isocyanurate 1.4 parts by weight, potassium persulfate 0.0
4 parts by weight and 0.004 parts by weight of sodium sulfite were added, and after nitrogen substitution, the temperature was raised, polymerization was carried out at 60 to 65 ° C. for 4 hours and then cooled to stop the polymerization. At this time, the polymerization rate determined from the solid content of the latex was 67%. This is designated as rubber latex (D).

[Production of Graft Copolymer (B)]

Production Example 9 (Synthesis of Graft Copolymer (B-1)) 200 parts by weight of ion-exchanged water and 5 parts by weight of rubber latex (D) (including unreacted monomer) in a reactor,
After charging 95 parts by weight of a monomer mixture consisting of 70% by weight of α-methylstyrene and 30% by weight of acrylonitrile, 0.8 parts by weight of t-dodecyl mercaptan, and substituting with nitrogen, 1 part by weight of sodium dodecylbenzenesulfonate and potassium persulfate were charged.
0.15 parts by weight was charged and the polymerization was carried out at 60 ° C for 3 hours and 90 ° C for 2 hours. After completion of the polymerization, the polymerization rate was 98% as determined by gas chromatography. The Mw of the acetone-soluble matter in this polymer was 98,000.

Production Example 10 (Synthesis of Graft Copolymer (B-2)) 70% by Weight of α-Methylstyrene and Acrylonitrile 30
According to the same manner as in Production Example 9, except that the weight% was changed to 60% by weight of α-methylstyrene, 20% by weight of acrylonitrile and 20% by weight of methylmethacrylate, the graft copolymer (B-
2) was obtained. The polymerization rate was 98%.

[Production of Graft Copolymer (C)] Production Example 11 (Synthesis of Graft Copolymer (C-1)) 240 parts by weight of deionized water, 1.0 part by weight of potassium oleate, and 0.14 parts of sodium formaldehyde sulfoxylate in a reaction vessel. Parts by weight, rubber latex (D) 60 parts by weight (including solid content and unreacted monomer), styrene 28 parts by weight, acrylonitrile 12 parts by weight, kyumen hydroperoxide 0.14 parts by weight and t-dodecyl mercaptan
Add 0.16 parts by weight, replace with nitrogen, and raise the temperature to 65 ° C for 6 hours, 90
Polymerization was carried out at 0 ° C for 2 hours. The polymerization rate calculated from the solid content of the latex after polymerization was 95%. This latex is referred to as a graft copolymer (C-1). The Mw of the acetone-soluble component was 140,000.

Production Example 12 (Synthesis of Graft Copolymer (C-2)) Instead of the rubber latex (D), the reaction was conducted up to a polymerization rate of 90% in Production Example 8, and the temperature was raised to 90 ° C. at this time,
The procedure was the same as in Production Example 11 except that the rubber latex obtained by polymerizing for 2 hours and reacting until the polymerization rate reached 98% was used. The obtained latex is used as a graft copolymer (C-2). The polymerization rate was 96% and the Mw of the acetone-soluble matter in the graft copolymer (C-2) was 140,000.

Production Example 13 (Synthesis of Graft Copolymer (C-3)) The procedure of Production Example 11 was repeated except that the rubber latex (D) was changed to butadiene rubber (Sumitomo Nogataku, trade name SN-800, Latex). . The obtained latex was used as a graft copolymer (C-3). The polymerization rate is 96%,
The Mw of the acetone-soluble matter of the graft copolymer (C-3) was 13
Thank you.

Production Example 14 (Synthesis of Graft Copolymer (C-4)) According to Production Example 11 except that the rubber latex obtained without using butadiene rubber in Production Example 8 was used in place of the rubber latex (D). I went. The obtained latex was used as a graft copolymer (C-4). The polymerization rate was 97%.

In the above, in order to obtain the polymerization rate by gas chromatography, a part of latex was sampled, dissolved in dimethylformamide, dissolved, subjected to gas chromatography analysis, and determined from the amount checked against the calibration curve.

The polymerization rate from the solid content of the latex was obtained by taking a part of the latex and heating it to volatilize the residual monomer and water to obtain the solid content (% by weight). From this value (a), it was calculated by the following formula. .

However, the non-volatile components are those that do not volatilize during the preparation and during the preparation, and include resins, emulsifiers, polymerization initiators and the like.

Examples 1 to 10 and Comparative Examples 1 to 3 The respective latexes of the obtained copolymer (A), graft copolymer (B) and graft copolymer (C) were mixed in the composition shown in Table 1. Next, after coagulating with Kali-Myoban, it was dehydrated and dried.

The obtained resin powder was pelletized by an extruder and then molded by an injection molding machine. The results of measuring the physical properties of the molded products are shown in Table 1.

As can be seen from Table 1, Comparative Example 1 using the copolymer (A-5) as the copolymer (A) has low heat resistance and impact resistance and cannot be put to practical use. Comparative Example 2, which uses the copolymer (A-6) as the copolymer (A), has extremely low impact resistance and fluidity, and cannot be put to practical use. Further, Comparative Example 3 using the copolymer (A-7) as the copolymer (A) has a remarkably low heat resistance and cannot be put to practical use.

In addition, Example 8 using the graft copolymer (C-2) as the graft copolymer (C) is excellent in heat resistance and fluidity, but tends to be slightly inferior in impact resistance.

(Effect of the Invention) The N-arylmaleimide copolymer according to the present invention has good compatibility with a graft copolymer obtained by graft-polymerizing an aromatic vinyl compound and a vinyl cyanide compound on a rubber-like polymer. The composition with this graft copolymer is excellent in heat resistance, impact resistance and fluidity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isamu Hattori 14 Goi Minamikaigan, Ichihara City, Chiba Prefecture Goi Plant, Hitachi Chemical Co., Ltd. (72) Inventor Hisashi Takagame 14 Goi Minamikaigan, Ichihara City, Chiba Hitachi Kasei Kogyo Co., Ltd.Goi factory (72) Inventor Kiyotaka Mashita 14 Goi south coast, Ichihara city, Chiba Hitachi Chemical Co., Ltd. Goi factory

Claims (1)

(57) [Claims] 1. An aqueous solution preliminarily emulsified by adding a serial transfer agent and an emulsifier, to an aqueous solution of 10 to 60% by weight of N-arylmaleimide, 16 to 65% by weight of an aromatic vinyl compound, a vinyl cyanide compound, an acrylic acid ester and methacrylic acid. A method for producing an N-arylmaleimide-based copolymer, which comprises adding a monomer containing 60 to 15% by weight of at least one compound selected from the group consisting of an ester and a polymerization initiator to carry out a copolymerization reaction. .