JPS63277271A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent solvent cracking resistance, impact resistance, etc., by compounding a polyphenylene ether and a polyester with a specific block copolymer or graft copolymer having excellent compatibility with both polymers. CONSTITUTION:(A) 100pts.wt. of a polyphenylene ether is compounded with (B) 0-400pts.wt., preferably 0-350pts.wt. of an aromatic vinyl polymer, (C) 1-500pts.wt., preferably 10-350pts.wt. of a polyester, preferably PETF, PBTF, etc., (D) 1-400pts.wt., preferably 5-380pts.wt. of a block copolymer and/or graft copolymer containing at least two components selected from polyphenylene ether, olefin polymer and polyester, (E) 0-400pts.wt., preferably 5-380pts.wt. of a polyolefin and, if necessary, (F) 1-1,000pts.wt., preferably 5-800pts.wt. of an inorganic or organic filler.

Description

[Detailed description of the invention] The present invention relates to a polyphenylene ether resin composition, and more specifically, it has excellent solvent crack resistance, impact resistance, heat resistance, water resistance, moldability, etc. The present invention relates to a polyphenylene ether resin composition containing polyester.

Polyphenylene ether has excellent heat resistance, mechanical strength, electrical properties, water resistance, flame retardance, etc., and is used in various engineering plastic materials. It is being used for various purposes.

However, polyphenylene ether has major problems such as poor moldability due to its high melt viscosity, as well as poor solvent cracking resistance and impact resistance. It was thought that it could not be used for any purpose.

By the way, in order to mainly improve the moldability of polyphenylene ether, it has been proposed in Japanese Patent Publication No. 17812-1977 to blend aromatic vinyl polymers such as polystyrene, rubber-modified polystyrene, and styrene-acrylonitrile-butadiene copolymers into polyphenylene ether. This method has been proposed in US Pat. No. 3,384,435, and the like.

However, when polyphenylene ether is blended with the above-mentioned aromatic vinyl polymer, the moldability of the resulting polyphenylene ether resin composition is improved, but heat resistance, mechanical strength, impact resistance, water resistance, etc. There was a problem in that it decreased significantly.

In particular, there was a problem in that it became impossible to coat a polyphenylene ether resin composition containing an aromatic vinyl polymer because the heat resistance was greatly reduced.

On the other hand, in order to improve the moldability or solvent crack resistance of polyphenylene ether, an attempt to blend polyolefin into polyphenylene ether has also been disclosed, for example, in Japanese Patent Publication No. 7069/1983. However, when attempting to blend polyolefins such as polystyrene or polypropylene with polyphenylene ether, the two are extremely poor in compatibility and cannot be blended uniformly.As a result, the resulting polyphenylene ether resin composition has poor impact resistance and There was a problem in that the molded product obtained from this resin composition peeled off into layers.

For this reason, for example, JP-A-58-], JP-A-03557, JP-A-59-1001.59, and JP-A-59-140257 disclose block copolymers of alkenyl aromatic compounds and conjugated dienes. Alternatively, the hydride is blended into a polyphenylene ether resin composition consisting of polyphenylene ether and polyolefin to improve the compatibility between polyphenylene ether and polyolefin.

However, even if a block copolymer of an alkenyl aromatic compound and a conjugated diene or its hydride is blended into a polyphenylene ether resin composition consisting of polyphenylene ether and polyolefin, especially when a large amount of polyolefin is present, , polyphenylene ether and polyolefin are not sufficiently compatible with each other, and the solvent crack resistance and impact resistance of the resulting polyphenylene ether resin composition are not sufficiently improved, and the molded products obtained from this resin composition are also poor. There still remained the problem that layers could peel off.

On the other hand, the present inventors have also attempted to improve the heat resistance or moldability of polyphenylene ether resin compositions by blending polyesters such as polyethylene terephthalate into the polyphenylene ether resin compositions. The inventors have discovered that this polyester also has a problem of poor compatibility with polyphenylene ether.

DISCLOSURE OF THE INVENTION The present invention aims to solve the problems associated with the prior art as described above, and provides a polyphenylene ether resin composition comprising polyphenylene ether and polyester. By increasing the compatibility with polyester, the solvent crack resistance and mechanical strength of polyphenylene needle resin compositions are improved, and they also have excellent impact resistance, heat resistance, water resistance, and moldability, and are also economical. The purpose of the present invention is to provide a polyphenylene ether resin composition.

The first polyphenylene ether resin composition according to the present invention comprises <i) 100 parts by weight of polyphenylene ether, (i) 0 to 400 parts by weight of aromatic vinyl polymer, (ii)
i) 1 to 400 parts by weight of polyester, <iv) block copolymer or graft copolymer containing at least two components of polyphenylene ether, olefin polymer, and polynisdel]--400 parts by weight, and (v) 0 parts by weight of polyolefin It is characterized by containing ~400 parts by weight.

Further, the second polyphenylene ether resin composition according to the present invention contains, in addition to the above-mentioned components (i) to (v>), (
vi) It is characterized by containing an inorganic filler or an organic filler.

The polyphenylene ether resin composition according to the present invention is
In addition to polyphenylene ether and polyester, it contains a block copolymer or a graft copolymer, or both, which is highly compatible with polyphenylene ether and polyester and contains at least two components of polyphenylene ether, olefinic polymer, and polyester. As a result, the solvent crack resistance of the polyphenyleph-thyl resin composition is improved, and it also has excellent impact resistance, heat resistance, water resistance, moldability, and electrical properties. Furthermore, when a polyolefin is included in addition to the above components, a polyphenylene ether resin composition with improved compatibility or uniform dispersibility between polyphenylene ether and polyester and polyolefin can be obtained.
A polyphenylene ether resin composition which has further improved physical properties and is economically superior can be obtained.

Highlights and Description F Regarding the polyphenylene ether resin composition according to the present invention, each component thereof will be specifically explained.

i Boi phenylephyl polyphenylene ether has the formula [I] (wherein R1, R2, R3, and R4 may be the same or different from each other, hydrogen atom, halogen atom, alkyl group, alkoxy group, cyano group, nitro group, amino group, phenoxy group, or sulfo group, where n is an integer indicating the degree of polymerization, and is from 20 to 1000.

Specifically, the following polymers are used as the polyphenylene needle expressed in maximum [IU]. Poly-2,6-dimethyl-1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene ether, poly-2,6-diprobyl-1,4-phenylene ether, poly-2-methyl- 6-Ituburobiru 1
．． 4-phenylene ether, poly-2,6-simethoxy 1,4-fenlef ether, poly-2,6-cyclomethyl-1,4-phenylene ether, poly-2,6
-diphenyl-1,4-phenylene ether, poly-2
, 6-cynitrile-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,5-dimethyl-1,4-phenylene ether, and the like.

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 d1/g.

i 1 Vinyl The aromatic vinyl polymer has the following formula: [■] A halogen atom, R6 is a hydrogen atom, a lower alkyl group, or a vinyl group, and m is an integer of 1 to 5. ) is a polymer or copolymer containing at least 25 mol% or more of polymerized units derived from an aromatic vinyl compound represented by the following formula.

As such an aromatic vinyl polymer, specifically, the following polymers are used. Polystyrene, poly-α-methylstyrene, polychlorostyrene, rubber-modified polystyrene, styrene/acrylonitrile copolymer, styrene/butadiene/acrylonitrile copolymer, styrene/maleic anhydride copolymer, styrene/maleic anhydride/butadiene copolymer polymers 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. ]. ~5 dl/g.

The polyester used in the present invention is obtained by an esterification polycondensation reaction between an aromatic dicarboxylic acid component and a diol component. Examples of aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, etc. In particular, terephthalic acid or tylphthalic acid as the main component It is preferable that it is an aromatic dicarboxylic acid containing as follows. Examples of diol components include alkylene glycols such as ethylene glycol and 1,4-butylene glycol, diethylene glycol, and polyethylene glycol, but in particular alkylene glycols or diols containing alkylene glycol as a main component are exemplified. Especially desirable.

As such a polyester, terephthalic acid or an aromatic dicarboxylic acid mainly composed of terephthalic acid as an aromatic dicarboxylic acid component, and an alkylene glycol or a diol mainly composed of alkylene glycol,
Polyalkylene terephthalates formed by esterification polycondensation are preferred. Specific examples of such polyalkylene prephthalates include polyethylene terephthalate and polybutylene terephthalate.

The intrinsic viscosity [η] of such polyester measured in 0-chlorophenol at 30'C is 0.05 to 5 dl/
g, preferably 0.1 dl/, to 3 dl/g.

By including such a polyester in a polyphenylene ether resin composition, the moldability and heat resistance of this resin composition are improved.

The block copolymer or graft copolymer used in the present invention contains at least two of the three structural units derived from polyphenylene ether, olefin polymer, and polyester. Contains one.

By blending these block copolymers, graft copolymers, or both into a polyphenylene ether resin composition, the compatibility between polyphenylene ether and polyester increases, and the solvent resistance of the resulting polyphenylene ether resin composition increases. Along with the significant improvement in crack resistance, heat resistance, water resistance, and mechanical strength are also improved. Furthermore, when polyolefin is blended, it works to improve the compatibility or uniform dispersibility of polyphenylene ether, polyester, and polyolefin, and the resulting composition also has excellent compatibility or uniform dispersibility. It has excellent solvent crack resistance, as well as excellent impact resistance, heat resistance, water resistance, and moldability, and is highly economical. The block or graft copolymer is a block or graft copolymer having at least two components selected from polyphenylene ether, polyester, or polyolefin polymer, and is, for example, an AB type 5. A-B-A type, (-A-B+. Type A-B
-C type, -(-A-B-C-)-, type, etc. block copolymers can be exemplified, and specifically A-
B type or +A-B+. Examples of the types include polyphenylene ether-polyester block copolymers, polyphenylene ether-olefin polymer block copolymers, and polynisder-olefin polymer block copolymers.

Also A-B-C type or +, '1-B-C+.

As the type of block copolymer, a block copolymer containing the three components mentioned above can be exemplified.

Examples of graft copolymers include polyphenylene ether polymers, copolymers obtained by graft copolymerizing other components onto the side chains of polyesters, and polyolefin polymers. Examples include copolymers in which polyester is grafted to the side chains of polyphenylene ether, polymers in which polyphenylene ether is grafted to the side chains of olefin polymers, and graft copolymers in which polyphenylene ether and olefin polymers are bonded to both ends of polyester. Examples include polymers.

Among these, the block copolymer can be manufactured as follows. For example, by reacting the polyphenylene ether or olefin polymer having at one or both ends an epoxy group, incyanato group, etc. that can react with a carboxyl group or a hydroxyl group, with a carboxyl group or a hydroxyl group that is the terminal functional group of the polyester, A
-B type, A-B-A type, %A-B→-. Block copolymers such as A type, A-r3-C type, etc. can be produced.

Moreover, the graft copolymer can be manufactured as follows. For example, a polyphenylene ether, polyester, or olefin polymer having a reactive functional group such as an acid anhydride group, hydroxyl group, carboxyl group, or epoxy group in its side chain, and a hydroxyl group or epoxy group that reacts with the functional group to form a bond; A graft copolymer can be produced by reacting with another of the above polymers having an isocyanate group or the like at the end.

As the polyphenylene ether constituting the block copolymer or graft copolymer, those exemplified above as (i) polyphenylene ether can be similarly exemplified, and as the aromatic vinyl polymer, the above (i)
) Those exemplified as aromatic vinyl polymers can be similarly exemplified.

Here block copolymers or graft copolymers (iv
The olefin polymers comprising > are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
It is a non-quality, low-crystalline or crystalline olefin polymer mainly composed of α-olefin components such as 1-octadecene and 1-eicosene, and in addition to these α-olefin components, a small amount of butadiene, Isoprene, 1,4
-hexadiene, 5-ethylidene-2-norbornene,
Diene components such as 5-vinyl-2-norbornene, vinyl acetate, acrylic acid salts), methacrylic acid salts), acrylic esters, methacrylic esters, maleic acid, maleic anhydride, maleic esters, 2- norbornene-5,6-dicarboxylic acid, 2-norbornene-5
, 6-dicarboxylic acid anhydride, or its derivative components may be randomly copolymerized or graft copolymerized.

Among these olefin polymers, ethylene,
Propylene copolymer, ethylene/1-butene copolymer,
Ethylene/1-hexene copolymer, propylene/1-butene copolymer, propylene/1-butene/4-methyl-
1-pentene copolymer, 1-hexene/4-methyl-1
-Pentene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, ethylene/propylene/5-vinyl-2-norbornene copolymer, ethylene/propylene/5-vinyl-2-norbornene copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, Propylene 1,4-hexadiene copolymer, ethylene/1-butene/dicyclopentadiene copolymer, ethylene/1-butene/5-ethylidene-2-norbornene copolymer, ethylene/1-butene/1. Examples include 4-hexadiene copolymer. In addition, specific examples of crystalline olefin polymers include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene・4-methyl-1
-Pentene copolymer, ethylene/1-hexene copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylic acid salt) copolymer, ethylene/methacrylic acid salt> copolymer, ethylene/methacrylic acid ester Examples include copolymers, ethylene/maleic acid copolymers, and ethylene anhydride/maleic acid copolymers.

Further, as the olefin polymer, acrylic acid, methacrylic acid, methacrylic ester, maleic acid, maleic anhydride, 2
-Olefin polymers obtained by graft copolymerization of unsaturated carboxylic acids such as -norbornene-5,6-dicarboxylic acid and 2-norbornene-5,6-dicarboxylic anhydride or derivative components thereof can be similarly exemplified.

The intrinsic viscosity [η] of these olefin polymers measured in decalin at 135° C. is 0.01 to 30 dl/g, preferably 0.05 to 25 dl/g.

) Polyolefin The polyolefin used in the present invention includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1
- From homopolymers or copolymers whose main component is an α-olefin component such as pentene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. It is a low-crystalline to crystalline polymer, and the degree of crystallinity measured by X-ray diffraction is 0.5 to 95%, preferably 1 to 90%. Specifically, polyolefins 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 include ethylene/4-methyl-1-pentene copolymer, ethylene/1-octene copolymer, propylene/1-butene copolymer, 4-methyl-1-pentene/1-octene copolymer, etc. Can be done.

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

In the present invention, at least two of the above three components of polyphenylene ether, aromatic vinyl polymer, polyphenylene ether/polyolefin polymer, and polyester are used. In addition to the polyolefin, block copolymers or graft copolymers containing inorganic fillers or organic fillers or both can be included.

Specifically, inorganic fillers include silica, silica-alumina, alumina, glass powder, glass beads, glass fiber, glass fiber cloth, glass fiber mat, asbestos, graphite, carbon fiber, carbon fiber cloth, and carbon fiber mat. , titanium oxide, molybdenum disulfide, magnesium hydroxide, talc, celite, metal powder,
Metal fiber etc. are used.

Specific examples of the organic filler include polyterephthaloyl-phenylenediamine, polyterephthaloyl isophthaloyl-p-phenylenediamine, polyisophthaloyl-phenylenediamine, and polyisophthaloyl-m-phenylene. Fibers of fully aromatic boria mint such as diamine, or nylon 66, nylon 6, nylon]-
A fibrous material such as polyalkylene terephthalate is used.

These fibrous materials can take the form of a monofilament, a strip/land, a cross, a mat, or the like.

In the polyphenylene ether resin composition according to the present invention, each of the above-mentioned components is <i) contained in the following proportions per 100 parts by weight of polyphenylene ether. .

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

If the amount of the aromatic vinyl polymer exceeds 400 parts by weight based on 100 parts by weight of polyphenylene ether, it is not preferable because the heat resistance, mechanical strength, etc. of the resulting polyphenylene ether resin composition will decrease. .

<iii> By blending 1 to 500 parts by weight of polyester, preferably 10 to 350 parts by weight, polyester into a polyphenylene ether resin composition in an amount of 1 part by weight or more per 100 parts by weight of polyphenylene ether, this composition , heat resistance and moldability are improved, but if it is added in an amount exceeding 500 parts by weight, the water resistance of the composition in particular decreases, which is undesirable. (iv) 1 to 400 parts by weight of block copolymer or graft copolymer, preferably 5 to 3 parts by weight
By blending 80 parts by weight of the above-described block copolymer or graft copolymer into the polyphenylene ether-based resin composition, the compatibility between polyphenylene ether, polyolefin, and polyester is improved, as described above.
A polyphenylene ether resin composition in which polyphenylene ether, polyolefin, and polyester are uniformly mixed is obtained.

If the amount of the block copolymer or graft copolymer as described above is less than 1 part by weight based on 100 parts by weight of polyphenylene ether, the compatibility between polyphenylene ether and polyolefin will hardly be improved, which is undesirable. If it exceeds 400 parts by weight, it is not preferable because good heat resistance cannot be obtained.

(v) By blending 1 to 400 parts by weight of polyolefin, preferably 5 to 380 parts by weight of polyolefin, in the polyphenylene ether resin composition, the solvent crack resistance of this resin composition is improved, and the moldability is also improved. It is possible to obtain a polyphenylene ether-based resin composition which has a low cost and is inexpensive.

The amount of this polyolefin is polyphenylene ether 10
If it is less than 1 part by weight based on 0 parts by weight, the solvent crack resistance of the resulting polyphenylene ether resin composition will not be improved much, so it is not preferable. On the other hand, if it exceeds 400 parts by weight, good heat resistance cannot be obtained, so it is not preferable. do not have.

(vi) Inorganic filler or organic filler 1 to 1000 parts by weight, preferably 5 to 800 parts by weight The inorganic filler or organic filler is blended into the polyphenylene ether resin composition for various purposes, for example, the composition It is used in an amount depending on the purpose to improve the heat resistance or flame retardance of a product or to color the composition.

A polyphenylene ether composition containing each component as described above is obtained by melt-mixing each component using various kneading machines such as a single-screw extruder, twin-screw extruder, Banbury mixer, roll, Brabender blastogram, etc. 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, and then removing the solvent.

The polyphenylene ether resin composition according to the present invention is
In addition to polyphenylene ether and polyester,
Contains a block copolymer or a graft copolymer, or a mixture of both, which contains at least two components of polyphenylene ether, olefin polymer, and aromatic vinyl polymer that are highly compatible with the polyphenylene ether and polyester. Therefore, the polyphenylene ether resin composition of the present invention has good compatibility or uniform dispersibility, and has excellent solvent crack resistance, impact resistance, heat resistance,
Excellent moldability. Furthermore, a polyphenylene ether resin composition containing a polyolefin in addition to the above components also has excellent compatibility or uniform dispersibility, excellent solvent crack resistance, heat resistance, water resistance, and moldability, and is also economically superior.

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

[Example] The following abbreviations used in the evaluation method of the composition of the present invention, Examples, and Comparative Examples indicate the following compounds, respectively.

ppo+Poly 2.6-dimethyl-1,4-phenylene ether (prototype, in chloroform, intrinsic viscosity 0.47 dJJ/g at 30°C) PP: Polypropylene (manufactured by Mitsui Petrochemical Co., Ltd., Highball 1, J 300 Intrinsic viscosity in decalin at 135°C: 2.8 d!J/g) pst: Polystyrene (manufactured by Mitsui Toatsu Chemical Co., Ltd., TOBOLEX ■500-51> GF Niglass fiber (manufactured by Nittobo Co., Ltd., CS 3PA, 3)
[I] Production method of composition PPO, pst, polyester, the block copolymer or graft copolymer shown in the reference example, PP, and filler were mixed in the proportions shown in Table 1 to prepare a triblend. . This triblend product was supplied to a twin screw extruder (L/D=42.30+rwnφ) set at 270°C to obtain a melt blend product.

Thereafter, injection molding was performed under the following conditions to create specimen for measuring physical properties.

Cylinder temperature = 290℃ Injection pressure crab 1000kg/cd/800kg/cot
-Primary/secondary mold temperature = 80°C II II] Composition evaluation method MFR: Measured under the conditions of ASTM D-1238-79.0.

・Bending test: using a 1/8” thick test piece, ASTM
Flexural modulus FM (kg/C-
J) was measured.

- Izod impact strength: Measurement was performed according to ASTM D-256 using a 1/8" thick test piece.

・Heat deformation temperature: Load 18.6kg/ca! and 4.
H according to ASTM D-648 at conditions of 6 feet/d.
DT ('C) was measured.

- Heat deflection: The amount of deflection was measured after being left in an oven at 160°C for 51 hours.

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

[II] Production method of block or graft copolymer (polyalkylene terephthalate graph) PPO) Intrinsic viscosity measured at 25°C using chloroform 0.8
0 dN/g poly(2,6-dimethylphenylene-1
, 4-ether) powder, 20 g of glycidyl methacrylate, and 10 g of dicumyl peroxide were tri-blended at room temperature, and then
Using a co-rotating vented twin-screw extruder with L/D = 40, the cylinder temperature was 300°C and the screw rotation speed was 15.
The mixture was melt-kneaded under the conditions of ORPM, extruded with a residence time of 2 minutes, passed through a cooling bath, and then formed into pellets. 6g of this pellet
The sample was collected, pulverized into fine powder using a pulverizer, and heated under reflux for 48 hours using a Soxhlet extractor using 100 ml of acetone. Then, dry under reduced pressure at 110°C for 5 hours to obtain a sample.

The presence of an NZ structure derived from the reaction of glycidyl methacrylate in this sample was confirmed by ultraviolet absorption spectrum.

50 parts by weight of epoxidized PP0 produced as above and polybutylene terephthalate (intrinsic viscosity [η] measured at 30°C in orthochlorophenol is 0.5d, Q/
g, hereinafter abbreviated as PBT) was fed to a twin-screw extruder set at 270°C, extruded with a residence time of 2 minutes, and ventized.
A graft polymer of PPO and polyethylene terephthalate was produced.

Roasted (ppo grafted polyolefin) polypropylene (manufactured by Mitsui Petrochemical Industries, Ltd., highball■
Add 1000 parts by weight of P-xylene to B200 > 50 parts by weight, dissolve at 125°C under a nitrogen stream, and dropwise add 5 parts by weight of glycidyl methacrylate (GMA) and 0.5 parts by weight of dicumyl peroxide to initiate a graft reaction. I went. After the reaction mixture was cooled to room temperature, a large amount of acetone was added to remove the precipitate. The precipitated polymer was washed repeatedly with acetone and then vacuum dried. The GMA content of this modified polypropylene was 3.2% by weight, [η] −1−
, so d,! l! It was 7g.

GMA modified polypropylene 50 obtained by the above method
Parts by weight and 50 parts by weight of the above PPO were triblended, and then supplied to a 30 mmφ twin-screw extruder (L/D=40) and melt-kneaded at 270°C. As a result of measuring the hydroxyl equivalent of this pellet by titration, it was found that the reaction was almost quantitative.

Hair boiled ■yu (PPO, PBT, olefin copolymer-containing graft copolymer) 100 parts by weight of the epoxidized PP0 shown in Reference Example 1,
100 parts by weight of the epoxidized polyolefin shown in Reference Example 2 and 100 parts by weight of PBT shown in Reference Example] were triblended and fed to a twin screw extruder set at 270 ° C.
Melt kneading/beltizing with a residence time of 2 minutes to achieve PP0
A graft copolymer of -PBT-PP was obtained.

Reference example 4 <PP0-olefin polymer-PET
Block copolymer) Internal volume: 30. Put 10ρ of epichlorohydrin into a Q stainless steel autoclave, and then add 300g of PP. Next, after maintaining the temperature at 100°C for about 30 minutes to completely dissolve the polymer, 50 cc of ]-0% caustic soda aqueous solution was added, and the mixture was reacted at 100°C for 3 hours under a nitrogen atmosphere. After the reaction is completed, epichlorohydrin is distilled off under reduced pressure, and the resulting polymer is dissolved in chloroform 51. After removing the solids liberated during polymer dissolution (formed NaC+ and excess Na0H), methanol/water (5
Add a mixed solvent of 0150) to reprecipitate the polymer,
Same solvent 10. After washing with Q four times, the mixture was dry-lit at -00°C for about 20 hours to obtain glycidylated polyphenylene ether (hereinafter abbreviated as GPPO).

The polymer obtained by this operation was titrated using toluene as a solvent according to the method specified in 15O-3001, and the amount of glycidyl groups contained in 100 g of the polymer was 6×10 −3 mol.

Since the number average molecular weight determined by osmotic pressure was 18,000, it was confirmed that there was one glycidyl group per molecule. From the above, it is clear that the following reaction proceeded almost quantitatively.

Terminal epoxidized PPO100 obtained as above
parts by weight, 50 parts by weight of one-end epoxidized product of hydride of 1,2-polybutadiene (prototype, Mn = 3000), and PET ([η]] = 0.4d, !2/g, ortho- Measured in chlorophenol) was fed to a twin-screw extruder set at 270° C., and melt-kneaded and pentized with a residence time of 2 minutes to obtain a block copolymer of PP0-polyolefin-PET.

The compositions shown in Table 1 were molded by the method described in [Technique] and their physical properties were evaluated. The results are shown in Table 1.

Note that Nonyl (534J) in the table is the trade name of a composition (manufactured by Engineering Plastics Co., Ltd.) consisting of PPO and polystyrene.

Claims (1)

[Scope of Claims] 1) (i) 100 parts by weight of polyphenylene ether, (ii) 0 to 400 parts by weight of aromatic vinyl polymer, (i)
ii) 1 to 500 parts by weight of polyester, (iv) 1 to 400 parts by weight of a block copolymer or graft copolymer containing at least two components among polyphenylene ether, olefin polymer, and polyester, and (v) 0 to 400 parts by weight of polyolefin. 400 parts by weight of a polyphenylene ether resin composition. 2) (i) 100 parts by weight of polyphenylene ether, (ii) 0 to 400 parts by weight of aromatic vinyl polymer, (i)
ii) 1 to 500 parts by weight of polyester, (iv) 1 to 400 parts by weight of a block copolymer or graft copolymer containing at least two components among polyphenylene ether, olefin polymer, and polyester (v) 0 to 400 parts by weight of polyolefin parts by weight, and (vi
) A polyphenylene ether resin composition containing 1 to 1000 parts by weight of an inorganic filler or an organic filler.