JPH075829B2 - Polyphenylene ether resin composition - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyphenylene ether-based resin composition, and more specifically, polyphenylene ether excellent in solvent crack resistance, impact resistance, heat resistance, water resistance, moldability, and the like. A resin composition.

Technical background of the invention and its problems Polyphenylene ether has excellent heat resistance and mechanical strength, electrical characteristics, water resistance, flame retardancy, etc., and is used in various applications as an engineering plastic material. It is being used.

However, polyphenylene ether has a large problem that it is inferior in moldability due to its high melt viscosity, and is inferior in solvent crack resistance and impact resistance. Therefore, polyphenylene ether is required to have the above-mentioned physical properties such as an automobile outer panel. It was thought that it could not be used for purposes.

By the way, in order to mainly improve the moldability of polyphenylene ether, it is possible to blend polyphenylene ether with an aromatic vinyl polymer such as polystyrene, rubber-modified polystyrene, and styrene-acrylonitrile-butadiene copolymer. Publication, US Patent No. 3
It is proposed in the specification of 384435. However, when polyphenylene ether is blended with the aromatic vinyl polymer as described above, the moldability of the obtained polyphenylene ether resin composition is improved, but heat resistance, mechanical strength,
There is a problem that impact resistance and water resistance are greatly reduced. In particular, there is a problem that the polyphenylene ether-based resin composition containing the aromatic vinyl polymer cannot be coated because the heat resistance is significantly reduced.

On the other hand, an attempt to blend a polyolefin with the polyphenylene ether in order to improve the solvent crack resistance, moldability or impact resistance of the polyphenylene ether is disclosed in, for example, Japanese Patent Publication No. 42-7069. However, when trying to blend a polyolefin such as polyethylene or polypropylene into polyphenylene ether, the two are remarkably poor in compatibility and are not blended uniformly, so that the resulting polyphenylene ether-based resin composition has solvent crack resistance and impact resistance. There is a problem that the molded product obtained from this resin composition is inferior in property and peels off in layers.

Therefore, for example, JP-A-58-103557 and JP-A-59
-100159 or JP-A-59-140257,
A block copolymer of an alkenyl aromatic compound and a conjugated diene or a hydrogenated product thereof is blended with a polyphenylene ether-based resin composition composed of polyphenylene ether and a polyolefin to enhance the compatibility between the polyphenylene ether and the polyolefin.

However, even if a block copolymer of an alkenyl aromatic compound and a conjugated diene or a hydrogenated product thereof is added to a polyphenylene ether resin composition composed of a polyphenylene ether and a polyolefin, especially when a large amount of the polyolefin is present. The polyphenylene ether and the polyolefin are not sufficiently compatible with each other, the solvent crack resistance and impact resistance of the resulting polyphenylene ether resin composition are not sufficiently improved, and a molded product obtained from this resin composition is also available. The problem still remains that it may peel off in layers.

OBJECT OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and a polyphenylene ether is blended with a polymer having a good compatibility with the polyphenylene ether. An object of the present invention is to provide a polyphenylene ether resin composition having improved impact resistance, heat resistance, water resistance, moldability, and economic efficiency, while improving the solvent crack resistance of the ether resin composition. .

SUMMARY OF THE INVENTION The first polyphenylene ether resin composition according to the present invention comprises (i) 100 parts by weight of polyphenylene ether, (ii) 0 to 400 parts by weight of an aromatic vinyl polymer, and (iii) a cyclic olefin. 1 to 400 parts by weight of a copolymer and (iv) 0 to 400 parts by weight of a polyolefin are blended.

The second polyphenylene ether-based resin composition according to the present invention, in addition to the above-mentioned components (i) to (iv),
(V) An inorganic filler or an organic filler is blended.

The polyphenylene ether resin composition according to the present invention,
In addition to polyphenylene ether, since it contains a cyclic olefin-based copolymer having excellent compatibility with the polyphenylene ether as described above, the solvent crack resistance of the polyphenylene ether-based resin composition is improved and the impact resistance is improved. , Heat resistance, water resistance, is excellent in moldability, since the compatibility or even dispersibility of the polyphenylene ether and the polyolefin is improved in the case of containing a polyolefin, a polyphenylene ether resin composition can be obtained, Is further improved, and a polyphenylene ether resin composition having excellent economy is obtained.

Detailed Description of the Invention Each component of the polyphenylene ether resin composition according to the present invention will be specifically described below.

(I) Polyphenylene ether Polyphenylene ether has the general formula [I] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group,
It is an alkoxy group, a cyano group, a nitro group, an amino group, a phenoxy group or a sulfo group, and n is an integer showing the degree of polymerization and is 20 to 1000. ) Has a structure represented by.

As the polyphenylene ether represented by the above general formula [I], specifically, the following polymers are used. Poly-2,6-dimethyl-1,4-phenylene ether,
Poly-2,6-diethyl-1,4-phenylene ether, poly-2,6-dipropyl-1,4-phenylene ether, poly-
2-methyl-6-isopropyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2, 6-diphenyl-1,4-phenylene ether, poly-2,6-dinitrile-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether,
Poly-2,5-dimethyl-1,4-phenylene ether etc.

The intrinsic viscosity [η] of these polyphenylene ethers measured in chloroform at 30 ° C. is 0.01 to 5 dl / g, preferably 0.1 to 3 dl / g.

(Ii) Aromatic Vinyl Polymer The aromatic vinyl polymer has the general formula [II] (In the formula, R ₅ is a hydrogen atom, a lower alkyl group or a halogen atom, R ₆ is a hydrogen atom, a lower alkyl group or a vinyl group, and m is an integer of 1 to 5.) It is a polymer or copolymer containing at least 25 mol% of polymerized units derived from a vinyl compound.

As such an aromatic vinyl polymer, specifically, the following polymers are used. polystyrene,
Poly-α-methylstyrene, poly-chlorostyrene, rubber modified polystyrene, styrene / acrylonitrile copolymer, styrene / butadiene / acrylonitrile copolymer, styrene / maleic anhydride copolymer, styrene / maleic anhydride / butadiene copolymer Coalescence etc.

The intrinsic viscosity [η] of these aromatic vinyl polymers measured in toluene at 30 ° C. is 0.01 to 10 dl / g, preferably 0.1.
~ 5dl / g.

(Iii) Cyclic Olefin Copolymer The cyclic olefin copolymer used in the present invention is (1) a cyclic olefin composed of an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II]. (I) the repeating unit (a) derived from ethylene is 40 to 97.
Mol% and the repeating unit (b) derived from the cyclic olefin are in the range of 3 to 60 mol%, and (ii) the repeating unit (b) derived from the cyclic olefin.
Has a structure represented by the following general formula [III] or general formula [IV], and (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
0.01 to 20 dl / g, preferably 0.05 to 10 dl / g, (iv) the molecular weight distribution (w / n) measured by gel permeation chromatography is 10 or less, preferably 8 or less, particularly preferably 4 or less. (V) glass transition temperature (Tg) is 10 to 240 ° C, preferably 20
In the range of up to 200 ° C, and (vi) the crystallinity measured by the X-ray diffraction method is 0 to 10%.
It is preferably in the range of 0 to 7%.

General formula [Wherein n and m are both positive integers and l is 3
More integers, each R ¹ to R ¹⁰ represents a hydrogen atom, a halogen atom or a hydrocarbon radical formula [In the formula, n, m, 1 and R ^{1 to} R ¹⁰ are the same as defined above. The molecular weight distribution (w / n) of the cyclic olefin random copolymer measured by gel permeation chromatography (GPC) is 10 or less, preferably 8 or less, particularly preferably 4 or less.

The cyclic olefin random copolymer can be produced by the following method. That is, in the presence of a catalyst formed of a soluble vanadium compound and an organoaluminum compound, ethylene and an unsaturated monomer represented by the above general formula [I] and general formula [II] in a liquid phase composed of a hydrocarbon medium. In the method for copolymerizing at least one cyclic olefin selected from the group consisting of, the concentration of the soluble vanadium compound supplied in the polymerization reaction system is maintained at 10 times or less the concentration of the soluble vanadium compound in the polymerization reaction system. While continuously supplying the ratio of aluminum atom to vanadium atom in the liquid phase of the polymerization reaction system (Al
/ V) of 2 or more, the repeating unit (a) derived from the ethylene component in the copolymer is 40 to 97 mol% and the repeating unit (b) derived from the cyclic olefin component is 3 to 60 mol%. It can be produced by continuously supplying ethylene and the cyclic olefin so as to be in the range and continuously copolymerizing.

The cyclic olefin used as the polymerization raw material is at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the above general formulas [I] and [II]. The cyclic olefin represented by the general formula [I] can be easily produced by condensing cyclopentadiene and the corresponding olefin by the Diels-Alder reaction, and the cyclic olefin represented by the general formula [II] can also be produced. Similarly, it can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the general formula [I] include 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,
In addition to 8a-octahydronaphthalene, 2-methyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4, Four
a, 5,8,8a-octahydronaphthalene, 2-propyl-1,
4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2, 3-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-chloro-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-Promo-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-fluoro-1,4,5,
8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n- Butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-
Isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene such as octahydronaphthalene, and compounds such as the following can be exemplified: 5,10-dimethyltetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] -3
-Dodecene, 2,10-dimethyltetracyclo [4,4,0,
1 ^2.5 , 1 ^7.10 ] -3-dodecene, 11,12-dimethyltetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] -3-dodecene, 2,7,9-
Trimethyltetracyclo [4,4,0,1 ^2.5 , 1 ^7.30 ] -3-dodecene, 9-ethyl-2,7-dimethyltetracyclo [4,
4,0,1 ^2.5 , 1 ^7.10 ] -3-dodecene, 9-isobutyl-2,
7-dimethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3
Dodecene, 9,11,12-trimethyltetracyclo [4,4,0,1
^2.5, 1 ^7.10] -3-dodecene, 9-ethyl-11,12-dimethyl-tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene, 9-isobutyl-11,12-dimethyl-3 -Tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] -3-dodecene, 5,8,9,10-
Tetramethyltetracyclo [4,4,0,12.5,17.10] -3-
Dodecene, hexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0 ^2.7 , 0
^0.14] -4-heptadecene, 12-methyl hexa cyclo [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^0.14] -4-heptadecene, 12-ethylhexanoate cyclo [6,6,1,1 ^3.6 , 1 ^10.13 ,
0 ^2.7 , 0 ^0.14 ] -4-heptadecene, 12-isobutylhexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0 ^2.7 , 0 ^9.14 ] -4-heptadecene, 1,6,10-trimethyl-12- Isobutylhexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0 ^2.7 , 0 ^9.14 ] -4-heptadecene, octacyclo [8,8,1 ^2.0 , 1 ^4.7 , 1 ^11.10 , 1 ^13.16 ,
0,0 ^3.8 , 0 ^12.17 ] -5-dococene, 15-methyloctacyclo [8,8,1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 1 ^13.16 , 0,0 ^3.8 , 0 ^12.17 ]
-5-dococene, 15-ethyloctacyclo [8,8,1 ^2.8 , 1
^4.7 , 1 ^11.18 , 1 ^13.16 , 0,0 ^3.8 , 0 ^12.17 ] -5-dococene Further, specific examples of the cyclic olefin represented by the general formula [II] include the following compounds and the like. be able to.

1,3-Dimethylpentacyclo [6,6,1,1 ^3.6 , 0 ^2.7 , 00.14]
-4-hexadecene, 1,6-dimethylpentacyclo [6,
6,1,1 ^3.6, 0 ^2.7, 0 ^9.14] -4-hexadecene, 15,16-dimethyl-penta cyclo [6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14] -4-
Hexadecene, pentacyclo [6,5,1,1 ^3.6, 0 ^2.7,
0 ^9.13 ] -4-Pentadecene, 1,3-dimethylpentacyclo [6,5,1,1 ^3.6 , 0 ^2.7 , 0 ^9.13 ] -4-Pentadecene, 1,6
-Dimethylpentacyclo [6,5,1,1 ^3.6 , 0 ^2.7 , 0 ^9.13 ]-
4-pentadecene, 14,15-dimethylpentacyclo [6,
5,1,1 ^3.6 , 0 ^2.7 , 0 ^0.13 ] -4-pentadecene, pentacyclo [6,6,1,1 ^3.6 , 0 ^2.7 , 0 ^9.13 ] -4-hexadecene,
Heptacyclo [8,7,1 ^2.0 , 1 ^4.7 , 1 ^11.17 , 0,0 ^3.3 , 0 ^12.16 ]
5-icosene, pentacyclo [8,8,1 ^2.0, 1 ^4.7,
1 ^11.17 , 0,0 ^3.3 , 0 ^12.17 ] -5-Henikosen etc.

(Iv) Polyolefin The polyolefin used in the present invention means ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1.
-Pentene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene or the like consisting of a homopolymer or copolymer containing an α-olefin component as a main component It is a low crystalline or crystalline polymer and has a crystallinity of 0.5 to 95%, preferably 1 to 90% as measured by an X-ray diffraction method. Specific examples of the polyolefin include polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 1-hexene, poly 1-octene, ethylene.
Propylene copolymer, ethylene / 1-butene copolymer,
Examples of ethylene 4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, propylene / 1-butene copolymer, 4-methyl-1-pentene / 1-octene copolymer, and the like. You can

The intrinsic viscosity [η] of these polyolefins measured in decalin at 135 ° C is 0.01 to 30 dl / g, preferably 0.1 to 25 d.
l / g.

(V) Inorganic Filler or Organic Filler In the present invention, in addition to the above components, an inorganic filler or an organic filler, or both of them can be included.

Specific examples of the inorganic filler include silica, silica-alumina, alumina, glass powder, glass beads, glass fiber, glass fiber cloth, glass fiber mat, asbestos, graphite, carbon fiber, carbon fiber cloth, carbon fiber mat. , Titanium oxide, molybdenum disulfide, magnesium hydroxide, talc, celite, metal powder, metal fiber and the like are used.

Specific examples of the organic filler include polyterephthaloyl-p-phenylenediamine, polyterephthaloylisophthaloyl-p-phenylenediamine, polyisophthaloyl-p-phenylenediamine, polyisophthaloyl-m.
-Fibrous materials of wholly aromatic polyamines such as phenylenediamine, or nylon 66, nylon 6, nylon 10
A fibrous material such as polyamide is used.

These fibrous materials can be in the form of single fiber, strand, cloth, mat, or the like.

Mixing ratio of each component In the polyphenylene ether resin composition according to the present invention, each of the above components is contained in the following ratio with respect to 100 parts by weight of (i) polyphenylene ether.

(Ii) Aromatic vinyl-based polymer 0-400 parts by weight, preferably 0-350 parts by weight The aromatic vinyl-based polymer does not necessarily have to be contained in the polyphenylene ether-based resin composition. By blending the resin-based polymer into the polyphenylene ether-based resin composition, the moldability of the resin composition can be improved.

If the amount of the aromatic vinyl polymer exceeds 400 parts by weight with respect to 100 parts by weight of the polyphenylene ether, the heat resistance and mechanical strength of the obtained polyphenylene ether resin composition will be deteriorated, which is not preferable.

(Iii) Cyclic olefin-based copolymer 1 to 400 parts by weight, preferably 5 to 380 parts by weight By incorporating the cyclic olefin-based copolymer into the polyphenylene ether-based resin composition, as described above,
The polyphenylene ether-based resin composition in which the compatibility between the polyphenylene ether and the polyolefin is improved and the polyphenylene ether and the polyolefin are uniformly mixed can be obtained.

When the amount of the cyclic olefin-based copolymer is less than 1 part by weight based on 100 parts by weight of the polyphenylene ether, the compatibility between the polyphenylene ether and the polyolefin is hardly improved, which is not preferable, while when it exceeds 400 parts by weight, it is good. It is not preferable because excellent heat resistance cannot be obtained.

(Iv) 1 to 400 parts by weight of polyolefin, preferably 5 to 380 parts by weight By compounding the polyolefin into the polyphenylene ether resin composition, the solvent crack resistance of this resin composition is improved and the moldability is also improved. In addition, an inexpensive polyphenylene ether resin composition can be obtained.

The amount of this polyolefin is polyphenylene ether 100
If it is less than 1 part by weight, the solvent crack resistance of the obtained polyphenylene ether resin composition is not improved so much, and if it exceeds 400 parts by weight, good heat resistance cannot be obtained, which is not preferable. .

(V) Inorganic filler or organic filler 1-1000 parts by weight, preferably 5-800 parts by weight The inorganic filler or organic filler is compounded in the polyphenylene ether resin composition for various purposes, for example, the composition It is used in an amount suitable for the purpose in order to improve the heat resistance or flame retardancy of the product or to color the composition.

Polyphenylene ether-based composition containing each component as described above, each component is melt-mixed by various kneaders such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Brabender blastgram, and the like. It can be prepared by cooling. In some cases, it can also be prepared by mixing each component in the form of a solution or emulsion, then mixing, and then removing the solvent.

Effects of the Invention The polyphenylene ether resin composition according to the present invention,
In addition to polyphenylene ether, since it contains a cyclic olefin polymer excellent in compatibility with this polyphenylene ether, the polyphenylene ether resin composition of the present invention has good compatibility or uniform dispersibility, solvent crack resistance, It has excellent impact resistance, heat resistance, and moldability,
Furthermore, the polyphenylene ether resin composition containing a polyolefin in addition to the above components is also excellent in compatibility or uniform dispersibility, solvent crack resistance, heat resistance, water resistance, excellent moldability, and a polyphenylene ether resin excellent in economic efficiency. A resin composition is obtained.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

EXAMPLES The following abbreviations used in the methods for evaluating the composition of the present invention, Examples, and Comparative Examples represent the following compounds, respectively.

PPO: poly 2,6-dimethyl-1,4-phenylene ether (test
Work, chloroform, intrinsic viscosity at 30 ℃ 0.47dl /
g) PP: Polypropylene (Mitsui Petrochemical Co., Ltd., Hypo
Le , J 300, limiting viscosity in decalin at 135 ℃ 2.
8dl / g) PSt: Polystyrene (manufactured by Mitsui Toatsu Chemicals, Inc.
Cous 500-51) GF: Glass fiber (Nittobo Co., Ltd., CS3PA, 3 mm) [I] Method for producing composition PPO, PSt, cyclic olefin-based copolymer shown in Reference Example,
Dry blend by mixing PP and filler at the ratio shown in Table 1.
The thing was prepared. Set this dry blend to 270 ° C
, Twin screw extruder, (L / D = 42, 30mmφ)
A blend was obtained. After that, injection molding is performed under the following conditions.
I made a physical property measurement specimen.

Cylinder temperature: 290 ℃ Injection pressure: 1000kg / cm ² / 800kg / cm ² = Primary / secondary mold temperature: 80 ℃ [II] Evaluation method of composition ・ Bending test: 1/8 ″ thick test piece Used, ASTM D-790
Bending elastic modulus FM (kg / cm ² ) was measured by -80.

-Izod impact strength: 1/8 "thick test piece, ASTM
The measurement was performed according to D-256.

-Heat distortion temperature: HDT (° C) was measured according to ASTM D-648 under the conditions of a load of 18.6 kg / cm ² and 4.6 kg / cm ² .

-Heat deflection: 160 degreeC 1 hour, after leaving in an oven, the amount of deflection was measured.

Solvent cracking property: A 1/8 "-thick test piece with 1% strain added to acetone at room temperature was immersed for 48 hours, and the presence or absence of cracks was visually determined.

[III] Production Example of Cyclic Olefin Copolymer Reference Example 1 Using a 2-polymerizer equipped with a stirring blade, ethylene and 1,4,5,8-dimethano-1,2,3,4, A copolymerization reaction of 4a, 5,8,8a-octahydronaphthalene ((a) in Table 2: hereinafter abbreviated as DMON) was carried out. That is, the cyclohexane solution of DMON from the upper part of the polymerization vessel was adjusted to 0.4 per hour so that the concentration of DMON in the polymerization vessel was 60 g / hour, and the cyclohexane solution of VO (CO ₂ H ₅ ) Cl ₂ as a catalyst was vanadium in the polymerization vessel. Concentration is 0.7 mmol /
So that 0.7 hourly (the concentration of vanadium supplied at this time is 2.86 times the concentration in the polymerization vessel) and a cyclohexane solution of ethylaluminum sesquichloride (Al (C ₂ H ₅ ) ₁₅ Cl ₁₅ ) in the polymerization vessel. Aluminum concentration of 5.6 mol /
0.4 per hour and cyclohexane per hour so that
It is continuously fed into the polymerization reactor at a rate of 0.5, while the polymerization liquid in the polymerization reactor is continuously withdrawn from the lower portion of the polymerization reactor so that the polymerization liquid is always 1. Further, ethylene is fed at a rate of 80, nitrogen is fed at a rate of 80, and hydrogen is fed at a rate of 0.2 at a rate of 0.2 from the top of the polymerization vessel. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant in a jacket attached outside the polymerization vessel. When the copolymerization reaction is performed under the above conditions, ethylene / DM
A polymerization reaction mixture containing an ON random copolymer is obtained.
Cyclohexane /
The polymerization reaction was stopped by adding an isopropyl alcohol (1/1) mixed solution. Thereafter, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 part of water was brought into contact with the polymerization solution at a ratio of 1: 1 with a homomixer under strong stirring to transfer the catalyst residue to a water tank. The above-mentioned mixed solution was allowed to stand still, the water tank was removed, and further washed twice with distilled water to purify and separate the polymerization solution.

The obtained polymerization liquid was brought into contact with 3 times the amount of acetone under vigorous stirring, the solid portion was collected by filtration, and thoroughly washed with acetone. After that, the resulting solid part was poured into acetone so as to be 40 g /, Examples and Comparative Examples The compositions of Table 4 were molded by the method [I] and the physical properties were evaluated.
The results are shown in Table 4.

In the table, nonyl (534J) is a composition consisting of PPO and polystyrene (Engineering Plastics Co., Ltd.).
Product name).

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Claims (2)

[Claims] 1. (ii) 0 to 400 parts by weight of an aromatic vinyl polymer, (iii) 1 to 400 parts by weight of a cyclic olefin copolymer, and (iv) per 100 parts by weight of polyphenylene ether. ) A polyphenylene ether resin composition comprising 0 to 400 parts by weight of a polyolefin. 2. (i) 0 to 400 parts by weight of an aromatic vinyl polymer, (iii) 1 to 400 parts by weight of a cyclic olefin copolymer, (iv) a polyolefin based on 100 parts by weight of polyphenylene ether. A polyphenylene ether resin composition comprising 0 to 400 parts by weight, and (v) 1 to 1000 parts by weight of an inorganic filler or an organic filler.