CA1242041A - Polyphenylene ether resin composition - Google Patents
Polyphenylene ether resin compositionInfo
- Publication number
- CA1242041A CA1242041A CA000472625A CA472625A CA1242041A CA 1242041 A CA1242041 A CA 1242041A CA 000472625 A CA000472625 A CA 000472625A CA 472625 A CA472625 A CA 472625A CA 1242041 A CA1242041 A CA 1242041A
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/902—Core-shell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/905—Polyphenylene oxide
Abstract
ABSTRACT OF THE DISCLOSURE
A novel polyphenylene ether resin composition which possesses outstanding impact resistance and weatherability and retains the advantageous properties inherent in poly-phenylene ether is disclosed, which comprises:
(A) 10 to 90 parts by weight of a polyphenylene ether resin, (B) 0 to 88 parts by weight of a polystyrene-type resin, and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising (1) 50 to 80% by weight of a cross-linked elastic copolymer formed by copolymerizing an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and a conjugate diene as main comonomers and (2) 50 to 20% by weight of a shell of hard resin formed by graft polymerizing an aromatic monovinyl compound and methyl methacrylate as main comonomers in a plurality of steps on the aforementioned elastic core.
A novel polyphenylene ether resin composition which possesses outstanding impact resistance and weatherability and retains the advantageous properties inherent in poly-phenylene ether is disclosed, which comprises:
(A) 10 to 90 parts by weight of a polyphenylene ether resin, (B) 0 to 88 parts by weight of a polystyrene-type resin, and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising (1) 50 to 80% by weight of a cross-linked elastic copolymer formed by copolymerizing an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and a conjugate diene as main comonomers and (2) 50 to 20% by weight of a shell of hard resin formed by graft polymerizing an aromatic monovinyl compound and methyl methacrylate as main comonomers in a plurality of steps on the aforementioned elastic core.
Description
lZ42041 POLYPHENYLENE ETHER RESIN COMPOSITION
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
This invention relates to a polyphenylene ether type resin composition which excels in various mechanical properties, particularly impact resistance, and exhibits heat resistance and good moldability, and more particularly to a polyphenylene ether resin composition which comprises (A) polyphenylene ether resin, (B) a polystyrene-type resin, and (C) a specified acrylate type core-shell graft copolymer.
DESCRIPTION OF PRIOR ART
Polyphenylene ether resin, as widely known, excels in heat resistance, mechanical properties, electrical properties, and so on and, therefore, is finding extensive utility as useful engineering plastics. Thus, the high heat resistance constitutes itself one of the salient features of the polyphenylene ether resin. This resin nevertheless suffers from poor moldability because of high melt viscosity and, further, tends to succumb to deterioration at elevated temperatures possibly to the extent of even impairing its inherently possessed properties. The adverse effects of such undesirable properties are conspicuous particularly on the impact resistance.
To improve the impact resistance and the moldability of polyphenylene ether resin, U.S.P. 3,383,435, for examp]e, proposes incorporation of polystyrene in the polyphenylene ether resin and demonstrates that the impact resistance as well I., ~42V41 `
as the moldability is improved by the use of a rubber-modified polystyrene.
In this resin composition, although the moldability is indeed improved, the impact resistance is not fully satisfactory from the practical point of view andthe mold release property is not necessarily desirable. Por improvement of the impact resistance, there have been proposed several methods resorting to incorporation of a varying rubbery elastomer in the aforementioned composition (as in U.S.P. 3,660,581, U.S.P. 3,994,856, Japanese Patent Publication SHO
47(1972)-32781, Japanese Patent Publication SIiO 57 (1982)-56941, and Japanese Patent Application Laid-open SIIO 53(1978)-72248). When the rubbery elastomer is added in a smal] amount, the effect of the addition is meager. When it is added in a large amount, the added elastomer impairs the melt flowing property of the composition and causes the molded product of the composition to be degraded in appearance and mold release property.
SUMMARY OF TIIE INVENTION
It has been desired therefore to provide a polyphenylene ether resin composition which possesses improved impact resistance, weatherability, and moldability without sacrifice in heat resistance, particularly heat distorsion temperature (HDT).
According to this invention, there is provided (A) 10 to 90 parts by weight of a polyphenylene ether resin, (B) 0 to 88 parts by weight of a polystyrene-type resin, and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising:
(1) 50 to 80% by weight of a core of a cross-linked elastic copolymer formed by copolymerizing an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and a conjugated diene as main comonomers in the presence of a cross-linking agent, and lZ42~4~
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
This invention relates to a polyphenylene ether type resin composition which excels in various mechanical properties, particularly impact resistance, and exhibits heat resistance and good moldability, and more particularly to a polyphenylene ether resin composition which comprises (A) polyphenylene ether resin, (B) a polystyrene-type resin, and (C) a specified acrylate type core-shell graft copolymer.
DESCRIPTION OF PRIOR ART
Polyphenylene ether resin, as widely known, excels in heat resistance, mechanical properties, electrical properties, and so on and, therefore, is finding extensive utility as useful engineering plastics. Thus, the high heat resistance constitutes itself one of the salient features of the polyphenylene ether resin. This resin nevertheless suffers from poor moldability because of high melt viscosity and, further, tends to succumb to deterioration at elevated temperatures possibly to the extent of even impairing its inherently possessed properties. The adverse effects of such undesirable properties are conspicuous particularly on the impact resistance.
To improve the impact resistance and the moldability of polyphenylene ether resin, U.S.P. 3,383,435, for examp]e, proposes incorporation of polystyrene in the polyphenylene ether resin and demonstrates that the impact resistance as well I., ~42V41 `
as the moldability is improved by the use of a rubber-modified polystyrene.
In this resin composition, although the moldability is indeed improved, the impact resistance is not fully satisfactory from the practical point of view andthe mold release property is not necessarily desirable. Por improvement of the impact resistance, there have been proposed several methods resorting to incorporation of a varying rubbery elastomer in the aforementioned composition (as in U.S.P. 3,660,581, U.S.P. 3,994,856, Japanese Patent Publication SHO
47(1972)-32781, Japanese Patent Publication SIiO 57 (1982)-56941, and Japanese Patent Application Laid-open SIIO 53(1978)-72248). When the rubbery elastomer is added in a smal] amount, the effect of the addition is meager. When it is added in a large amount, the added elastomer impairs the melt flowing property of the composition and causes the molded product of the composition to be degraded in appearance and mold release property.
SUMMARY OF TIIE INVENTION
It has been desired therefore to provide a polyphenylene ether resin composition which possesses improved impact resistance, weatherability, and moldability without sacrifice in heat resistance, particularly heat distorsion temperature (HDT).
According to this invention, there is provided (A) 10 to 90 parts by weight of a polyphenylene ether resin, (B) 0 to 88 parts by weight of a polystyrene-type resin, and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising:
(1) 50 to 80% by weight of a core of a cross-linked elastic copolymer formed by copolymerizing an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and a conjugated diene as main comonomers in the presence of a cross-linking agent, and lZ42~4~
(2) 50 to 20% by weight of a shell of a hard resin formed by graft polymerizing an aromatic monovinyl compound and methyl methacrylate as main comonomers in the presence of a cross-linking agent onto the elastic core, wherein the sum of components (A), (B) and (C) is 100 parts by weight.
According to the present invention, there is also provided a process for producing polyphenylene ether resin, the process comprising (I) mixing the components with a suitable mixing device and (II)subsequently kneading the resultant mixture in an extruder or a roll.
According to the present invention, there is further provided a molded article produced by molding the polyphenylene ether resin composition.
DETAILED DESCRIPTION OF TIIE INVENTION
The polyphenylene ether resin (A) consti.tuting one of the components of the resin composition of this invention is a polyphenylene ether obtained by oxidatively polycondensing a monocyclic phenol represented by the following formula (I) or ~42()41 a modified polyphenylene ether obtained by grafting an aromatic vinyl compound to the aforementioned polyphenylene.
- OH
R3~
wherein Rl represents a lower alkyl group of 1 to 3 carbon atoms and R2 and R3, which may be the same or different, each represent a hydrogen atom or a straight or branched chain alkyl group of 1 to 3 carbon atoms.
The polyphenylene ether may be a homopolymer or a copolymer involving two-or more monocyclic phenols.
The homopolymer is obtained from units of a monocyclic phenol and the copolymer from units of a monocyclic phenol and at least one comonomer.
The alkyl group of 1 to 3 carbon atoms denoted by Rl in the general formula embraces methyl, ethyl, n-propyl, and isopropyl groups.
Particular examples of the monocyclic phenol represented by the general formula (1) which are effectively usable herein include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, o-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylPhenOl, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimetnyl-phenol, 2,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol.
Particular exar~ples of polyphenylene ethers obtained by polycondensing the monocyclic phenols enumerated above include homopolymers such as 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-ethyl-1,4-phenylene)ether, poly(2-methyl-6-propyl-1,4-phenylene)ether, and poly(2-ethyl-6-propyl-1,4-phenylene)ether, and copolymers such as 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer, 2,6-dimethyl-phenol-2,3,6-triethylphenol copolymer, 2,6-diethylphenol-2,3,6-trimethylphenol copolymer and 2,6-dipropylphenol-2,3,6-trimethylphenol copolymer.
Among the polyphenylene ethers cited above, poly(2,6-dimethyl-1,4-phenylene)ether and 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer are particularly preferred.
The homopolymers and copolymers mentioned above can be produced by methods well known in the art such as, for example, disclosed in U.S.P. 3,306,875, 4,011,200, and 4,067,851.
The aforementioned modified polyphenylene ether to be used as the polyphenylene ether resin (A), i.e. one of the components of the resin composition of this invention, is a graft polymer obtained by grafting an aromatic vinyl compound represented by the following formula (2) to the polyphenylene ether in the form of a homopolymer or a copolymer.
C--CH
(Z)p (2) wherein R4 represents a hydrogen atom or a methyl group, Z
represents a chlorine atom or a methyl group, and p is 0 or an integer of 1 to 3.
This graft polymer can be produced, for example, by the method disclosed in Japanese Patent Application Laid-open SH0 50(1975)-126800. Examples of the aromatic vinyl compound which is effectively used herein include styrene, alpha-methylstyrene, vinyl toluene, vinyl xylene, ethylstyrene, n-propylstyrene, isopropylstyrene, chlorostyrene, and bromostyrene.
Among the possible graft polymers represented by the general formula (2), a graft polymer of poly(2,6-dimethyl-1,4-phenylene)ether with styrene and a graft polymer of 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer with styrene are particularly preferred.
The polystyrene-type resin (B), one of the components of the resin composition of the present invention, is a resin containing at least about 25% by weight of repeating units of the following general formula (3).
lZ42041 C CH--I, )p
According to the present invention, there is also provided a process for producing polyphenylene ether resin, the process comprising (I) mixing the components with a suitable mixing device and (II)subsequently kneading the resultant mixture in an extruder or a roll.
According to the present invention, there is further provided a molded article produced by molding the polyphenylene ether resin composition.
DETAILED DESCRIPTION OF TIIE INVENTION
The polyphenylene ether resin (A) consti.tuting one of the components of the resin composition of this invention is a polyphenylene ether obtained by oxidatively polycondensing a monocyclic phenol represented by the following formula (I) or ~42()41 a modified polyphenylene ether obtained by grafting an aromatic vinyl compound to the aforementioned polyphenylene.
- OH
R3~
wherein Rl represents a lower alkyl group of 1 to 3 carbon atoms and R2 and R3, which may be the same or different, each represent a hydrogen atom or a straight or branched chain alkyl group of 1 to 3 carbon atoms.
The polyphenylene ether may be a homopolymer or a copolymer involving two-or more monocyclic phenols.
The homopolymer is obtained from units of a monocyclic phenol and the copolymer from units of a monocyclic phenol and at least one comonomer.
The alkyl group of 1 to 3 carbon atoms denoted by Rl in the general formula embraces methyl, ethyl, n-propyl, and isopropyl groups.
Particular examples of the monocyclic phenol represented by the general formula (1) which are effectively usable herein include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, o-cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylPhenOl, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimetnyl-phenol, 2,6-dimethyl-3-ethylphenol, and 2,6-dimethyl-3-propylphenol.
Particular exar~ples of polyphenylene ethers obtained by polycondensing the monocyclic phenols enumerated above include homopolymers such as 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-ethyl-1,4-phenylene)ether, poly(2-methyl-6-propyl-1,4-phenylene)ether, and poly(2-ethyl-6-propyl-1,4-phenylene)ether, and copolymers such as 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer, 2,6-dimethyl-phenol-2,3,6-triethylphenol copolymer, 2,6-diethylphenol-2,3,6-trimethylphenol copolymer and 2,6-dipropylphenol-2,3,6-trimethylphenol copolymer.
Among the polyphenylene ethers cited above, poly(2,6-dimethyl-1,4-phenylene)ether and 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer are particularly preferred.
The homopolymers and copolymers mentioned above can be produced by methods well known in the art such as, for example, disclosed in U.S.P. 3,306,875, 4,011,200, and 4,067,851.
The aforementioned modified polyphenylene ether to be used as the polyphenylene ether resin (A), i.e. one of the components of the resin composition of this invention, is a graft polymer obtained by grafting an aromatic vinyl compound represented by the following formula (2) to the polyphenylene ether in the form of a homopolymer or a copolymer.
C--CH
(Z)p (2) wherein R4 represents a hydrogen atom or a methyl group, Z
represents a chlorine atom or a methyl group, and p is 0 or an integer of 1 to 3.
This graft polymer can be produced, for example, by the method disclosed in Japanese Patent Application Laid-open SH0 50(1975)-126800. Examples of the aromatic vinyl compound which is effectively used herein include styrene, alpha-methylstyrene, vinyl toluene, vinyl xylene, ethylstyrene, n-propylstyrene, isopropylstyrene, chlorostyrene, and bromostyrene.
Among the possible graft polymers represented by the general formula (2), a graft polymer of poly(2,6-dimethyl-1,4-phenylene)ether with styrene and a graft polymer of 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer with styrene are particularly preferred.
The polystyrene-type resin (B), one of the components of the resin composition of the present invention, is a resin containing at least about 25% by weight of repeating units of the following general formula (3).
lZ42041 C CH--I, )p
(3) wherein R4, Z and p have the same meanings as defined in the general formula (2).
The repeating unit of the general formula (3) is derived from a styrene monomer of the aforementioned general formula (2).
Examples of the polystyrene-type resin which is used effectively herein include polystyrene, high-impact polystyrene (rubber-modified polystyrene), styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-alpha-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-methylstyrene copolymer, poly-p-methylstyrene, high impact poly-p-methylstyrene and p-methylstyrene-maleic anhydride copolymer.
In these polystyrene-type resins, high impact polystyrene proves particularly advantageous. Polystyrene type resins modified with various rubber components such as polybutadiene, rubbery butadiene-styrene copolymer, and EPDM are also usable.
The acrylate type core-shell graft copolymer (C), one of the components of the resin composition of this invention, is a core-shell graft copolymer which comprises a core of a ~242~41 cross-linked copolymer which can be obtained by copolymerizing an alkyl acrylate having 2 to i2 carbon atoms in the alkyl group thereof and a polyfunctional polymerizable monomer possessing a conjugated diene type double bond represented by butadiene as essential components in the presence of a small amount of a cross-linking agent added thereto and a shell of a hard resin layer obtained by graft polymerizing onto the core one or more vinyl compounds and methyl methacrylate as essential components in the presence of a small amount of a cross-linking agent added thereto. In the core-shell graft copolymer, the core of cross-linked copolymer and the shell of hard resin are formed in relative amounts such that the core accounts for 50 to 80% by weight and the shell for 50 to 20% by weight, respectively, based on the core-shell graft copolymer.
Among the possible alkyl acrylates having 2 to 12 carbon atoms in the alkyl group thereof used for the formation of the core of cross-linked elastic copolymer, n-butyl acrylate and 2-ethylhexyl acrylate are particularly advantageous.
As examples of the conjugated diene, l-methyl-2-vinyl-4,6-heptadien-~-4~, 7-methyl-3-methylene-1, 6-octadiene, and 1,3,7-octatriene may be cited besides the aforementioned butadiene.
The cross-linking agent used in the formation of the core and the shell mentioned above must be selected on the condition that it is satisfactorily copolymerizable with the monomers during the course of polymerization. Examples of the cross-linking agent usable advantageously herein include aromatic polyfunctional vinyl compounds represented by divinyl lZg20~
benzene dimethacrylate, diethylene glycol dimethacrylate,and triethylene dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate, ar.d diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glyco~
diacrylate, and 1,3-butane diol diacrylate.
Optionally in the copolymerization of the alkyl acrylate and the polyfunctional polymerizable monomer possessing a conjugate diene type double bond, a monofunctional polymer-izable monomer properly selected from the group consisting of aromatic vinyl cornpounds represented by styrene, methacrylates represented by methyl methacrylate, vinyl nitriles represented by acrylonitrile, vinyl ether compounds represented by methyl vinyl ether, halogenated vinyl compounds represented by vinyl chloride, and vinyl ester compounds represented by vinyl acetate, particularly from the group of methacrylates represented by methyl methacrylate, can be used as part of the alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof.
As examples of the vinyl compound to be used for the graft copolymerization on the core of cross-linked elastic copolymer, there may be cited methacrylates represented by methyl methacrylate, aromatic vinyl compounds represented by styrene, vinyl nitriles represented by ~crylollitrile, and halogenated vinyl compounds represented by vinyl chloride.
these polymerizable monomers may be used eit.ler alorle or in the form of a mixture of two or more members. During the _ g _ course of the graft polymerization, this vinyl compound may be used in combination with the aforementioned cross-]inking agent.
In a preferred embodiment of this invention, the core of the core-shell graft copolymer (C) is a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 40 to 95%
by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of o.Ol to 3~ weight of a cross-linking agent and the shell of the core-shell graft copolymer comprises an inner shell layer and an outer shell layer formed by polymerization in two steps on said core of the cross-linked elastic copolymer, the inner shell layer being formed of a cross-linked polymer obtained by a graft polymerization either of (A) a monomer mixture containing styrene as a major component and methyl methacrylate or of (B) a monomer mixture containing (i) styrene or both methyl methacrylate and styrene and (ii) acrylonitrile in the presence of 0.01 to 3% by weight of a cross-linking agent and the outer shell layer being formed of a cross-linked polymer obtained by a graft polymerization of a monomer preponderantly of methyl methacrylate in the presence of 0.01 to 2% by weight of a cross-linking agent.
Typical methods available for the production of the acrylate type core-shell graft copolymer are described below.
A method comprises:
preparing coagulated particles having an average particle diameter of 0.12 to 0.3 em, preferably 0.05 to 0.1 em, by adding a coagulating agent such as, for example, a mineral acid like hydrochloric acid or sulfuric acid to a latex which has an average particle diameter, preferably, 0.05 to 0.1 em and contains 50 to 75 parts by weight of a cross-linked elastic copolymer obtained by ~Z42041 an emulsion polymerization of a monomer mixture consisting of 70 to 95 parts by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 30 to 5 parts by weight of butadiene, and 0.01 to 3 parts by weight, preferably 0.05 to 1.5 parts by weight, of a cross-linking agent, dividing 50 to 25 parts by weight of a monomer mixture which consists of 10 to 90% by weight of styrene and 9o to 10% by weight of methyl methacrylate and contains 0.01 to 2.0 parts by weight of a cross-linking agent,into (a) a mixture portion consisting of styrene as a major component and methyl methacrylate and containing said cross-linking agent and (b) a methyl methacrylate portion containing said cross-linking agent, subjecting the former divided portion (a) to an addition polymerization with the coagulated elastic latex and, subsequently subjecting the latter divided portion (B) to the addition polymerization with the resultant addition polymer.
Another typical method comprises:
preparing coagulated particles having an average particle diameter of 0.12 to 0.5 em by adding a coagulating agent to a latex containing 50 to 80 parts by weight of a cross-linked elastic copolymer obtained by the emulsion polymerization of a monomer mixture consisting of 40 to 95% by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of 0.01 to 3% by weight, preferably 0.05 to 1.5% by weight, of a cross-linking agent added thereto, subjecting 45 to 10 parts by weight of a monomer mixture consisting of 10 to 50% by weight of acrylonitrile, 50 to 90% by weight of styrene or both methyl methacrylate and styrene, and 0.01 to 3% by weight of a cross-lZ420~
linking agent copolyMerizable therewith to an addition polymerization with said coagulated particles and subsequently subjecting 5 to 25 parts by weight of an alkyl methacrylate monomer having l to 4 carbon atoms in the alkyl group thereof and containing 0.01 to 3% by weight of a cross-linking agent to the addition polymerization with the resultant addition polymer.
The graft polymerization may be carried out in one step or it may be performed in a plurality of steps by dividing the component monomers for the graft copolymerization into as many portions of varying compositions as required. The preferred methods for the production of the core-shell graft copolymer have been demonstrated as being performed in the form of emulsion polymerization. This does not mean that the emulsion polymerization is the only manner of polymerization available. Of course, the acrylate type graft copolymer contemplated by this invention can be produced by any of the methods of polymerization known in the art. As commercially available examples of the acrylate type core-shell graft copolymer, the resins marketed under the trade marks "IIIA-15","HIA-28", and "~lIA-30" by Kureha Kagaku Kogyo K.K. can be advantageously utilized.
In the polyphenylene ether type resin composition of the present invention, the polyphenylene ether resin (A) accounts for 10 to 90% preferably 25 to 70% by weight, the styrene-type resin (B) for 0 to 88%, preferably 30 to 75% by weight, and the acrylate type core-shell graft copolymer for 1 to 25% by weight, preferably 5 to 25% by weight.
If the proportion of the polyphenylene ether resin is less than 10% by weight, the properties inherent in the polyphenylene ether resin are not fully manifested. If it exceeds 90% by weight, the improvement of ~Z42041 moldability is not sufficient. If the proportion of the styrene-type resin exceeds 88% by weight, the properties due to the use of the polyphenylene ether are not fully manifested. If the proportion of the acrylate type core-shell graft copolymer is less than 1% by weight, the improvement with respect to the jetting at the gate portion is obtained with difficulty and the improvement in impact resistance is not sufficient. The term jetting is understood to mean turbulent flow of resin from an undersized gate or thin section into a thicker mold section, as opposed to laminar flow of material progressing radially from a gate to the extremities of the cavity.
The preparation of the polyphenylene ether type resin composition of the present invention can be effected by adopting any of the methods known to the art. For example, it may be - 12a -~2~2(~4~
r accomplished by mixing the components with a suitable mixing device such as a V blender or a Henshell mixer and subsequently kneading the resultant mixture in an extruder, a Banbury mixer, or a roll.
Optionally, the polyphenylene ether type resin composition of this invention may contain therein any of various additives known to the art. Examples of the additives advantageously usable for the purpose include flame retardants represented by organic phosphates and halogenated organic compounds, flame-retarding aids represented by antimony oxide and other antimony compounds, stabilizers, ultraviolet ray absorbents, pigments, dyes, lubricants, and fillers and reinforcing agents such as inorganic and organic powders and fibers. The polyphenylene ether type resin composition may further contain, when necessary, other elastomer or other resin components within the range not harmful to the properties of the product of this invention. Examples of the elastomer which is advantageously used for this purpose include A-B-A' type elastomeric block copolymers (wherein A and A' each represent a block resulting from polymerization of an aromatic vinyl compound and B
represents a block resulting from polymerization of a conjugated diene), A-B'-A' type elastomeric block copolymers (wherein A
and A' are the same as above and B' represents a block resulting from hydrogenation of the aforementioned block B), polybutadiene, polyisoprene, an elastomeric copolymer of a diene compound and an aromatic vinyl compound, a nitrile rubber, an elastomeric 12~%~41 ethylene-propylene copolymer, an ethylene-propylene-diene copolymer (EPDM), thiokol rubbers, polysulfide rubbers, acrylic rubbers, a grafted product of butyl rubber and polyethylene, polyurethane rubbers, and polyester elastomers. For example, the polycarbonate oligomer from bisphenol A or tetrabromo-bisphenol A may be incorporated for the improvement of moldability, flame retardancy, and surface properties, thermo-plastic aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate and polyolefins such as polyethylene and ethylene-propylene copolymer for the improvement of chemical resistance, and heat-resistant polyesters such as polyester carbonate and polyallylate (such as are marketed by Unitika under trademark deisgnation of U polymers) for the improvement of heat resistance.
Now, the present invention will be described more specifi-cally below with reference to working examples and comparative experiments. Wherever "percent" and "molecular weight" are mentioned, they are based on respective amounts by weight unless otherwise specified.
Examples 1-8 and Comparative Experiments 1-4:
Compositions using polyphenylene ether resin which is a copolymer of 2,6-dimethyl phenol and 2,3,6-trimethyl phenol, polystyrene-type resin (HI-polystyrene produced by Asahi-Dow and marketed under the trade mark "Styron 492"), and acrylate type graft copolymers (produced by Kureha Kagaku Kogyo K.K. and marketed under the trade marks "HIA-15 lZ4;;~
and HIA-28", simply indicated as "HIA-15" and "HIA-28" in the following table examples 1-4) and compositions using the components just mentioned plus various polyolefins, i.e. ethylene-propylene copolymer (produced by Japan Synthetic Rubber Co.,Ltd. and marketed under the trade mark "JSR EP 07C", simply indicated as (a) in the following table), an olefinic elastomer (produced by Mitsui Petrochemical Co.,Ltd. and marketed under the trade mark "Milastomer 9590B," simply indicated as (b) in the following table), or ethyleneethyl acrylate copolymer (produced by Japan Unicar Co.,Ltd. and marketed under the trade mark "~UC Copolymer DPDJ-6169," simply indicated as (c) in the following table) (Examples 5-8) were kneaded in proportions indicated in Table 1 in a blender.
The resultant mixtures were each supplied to a biaxial extruder, melted and kneaded at a cylinder temperature of 280C, and convcrted into pellets. The pellets were dried at 100C for at least two hours in a hot-air drier and injection molded to produce test pieces for determination of physical properties. The results are shown in Table 1.
Ion comparison, the procedure of the foregoing working examples was followed by using a composition of polyphenylene ether resin and polystyrene-type resin (Comparative Experiment 1), a composition equalling the composition of Example 1 minus the acrylate type graft copolymer (Comparative Experiment 2), a composition equalling the composition of Example 2 minus the lZ42041 acrylate type graft copolymer (Comparative Experiment 3), and a composition equalling the composition of Example 3 minus the acrylate type graft copolymer (Comparative Experiment 4). The results are shown in Table 1.
In Table 1, the data given under the heading "HDT (*l)"
and the heading " jetting" (*2) were determined as follows:
*1: The procedure defined by ASTM D1238 under the con-ditions of 3.8 kg of load and 250C of temperature.
*2: A given sample of predried pellets was treated with a Sumitomo-Nestar injection molder (Neomat N350/120) ; to produce a test piece measuring 89.5 mm x 49.5 mm x 3.2 mm and having a gate cross section of 3 mm in thickness and 7 mm in width under the conditions of 280C of cylinder temperature, 80C of mold temper-ature, 1100 kg/cm of injection pressure, FCV 7/12, 14 seconds of injection time, and 25 seconds of cooling time. The test piece was visually inspected with respect to the condition of jetting in the gate portion.
12420~
_ O O O I r-J O a a O o o f r O In CO l or o I) r o or ED
CO O G O ED f D o U ) ,_i~1 0 O ~0 æ
,' l ~0 do ~0 ED ox ED O O f ED O r- ED a - I` 'i'I æ
us O o ox I O n co n a a) f or I, n O
l 1 LD~ o on O l 1 - tip Lo n f a~I~ a i Ln Ln O
o Ln Ln ED n Ln o o Ln Ln I_ Ln I
9c) O î o O ~j z o on L .~
6 o x O I 3 l X . _ t . A
f _ g 13 o I; Ln o c (I .~ ~3 _ .
1242~41 Examples 9 and Comparative Experiments 5 and 6:
The test pieces obtained under the conditions of Examples 1-4 were tested for Izod impact strength at low temperatures.
The results are shown in Table 2.
For comparison, a composition equalling the composition of Examples 1-4 except that MBS resin (produced by Japan Synthetic Rubber Co., Ltd.and marketed under trademark design-ation of JSR MBS 67) was used instead of HIA-15 (Comparative Experiment 5) and a composition equalling the composition of Examples 1-4 except that MAS resin (produced by Mitsubishi Rayon Co., Ltd. and marketed under trademark designation Metablen W529) was used instead of HIA-15 (Comparative Experi-ment 6) were treated and tested under the conditions of Examples 1-4. The results are also shown in Table 2.
Table 2 Example Comparative Comparative i 9 Experiment 5 Exaperiment 6 Polyphenylene 40 40 40 ether resin compo- Polystyrene-type 45 45 45 sition HIA-15 15 (%) MBS resin 15 MAS resin 15 23C 21.6 21.2 20.9 trength (notch), 1/8" 0 20.5 18.6 13.7 kg.cm/cm l 8.5 10.2 Example lO and Comparative Experiment 7:
The test pieces obtained under the same conditions as those of Examples 1-4 were treated for prescribed lengths of time with a sunshing weather meter, and then tested for tensile strength and retention of tensile elongation. The results A are shown in Table 3.
For comparison, a composition equalling the composition of Examples 1-4 except that MBS resin (produced by Japan Synthetic Rubber Co., Ltd. and marketed under trademark designation of "JSR MBS 67") was used instead of HIA-15 (Comparative Experiment
The repeating unit of the general formula (3) is derived from a styrene monomer of the aforementioned general formula (2).
Examples of the polystyrene-type resin which is used effectively herein include polystyrene, high-impact polystyrene (rubber-modified polystyrene), styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-alpha-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-methylstyrene copolymer, poly-p-methylstyrene, high impact poly-p-methylstyrene and p-methylstyrene-maleic anhydride copolymer.
In these polystyrene-type resins, high impact polystyrene proves particularly advantageous. Polystyrene type resins modified with various rubber components such as polybutadiene, rubbery butadiene-styrene copolymer, and EPDM are also usable.
The acrylate type core-shell graft copolymer (C), one of the components of the resin composition of this invention, is a core-shell graft copolymer which comprises a core of a ~242~41 cross-linked copolymer which can be obtained by copolymerizing an alkyl acrylate having 2 to i2 carbon atoms in the alkyl group thereof and a polyfunctional polymerizable monomer possessing a conjugated diene type double bond represented by butadiene as essential components in the presence of a small amount of a cross-linking agent added thereto and a shell of a hard resin layer obtained by graft polymerizing onto the core one or more vinyl compounds and methyl methacrylate as essential components in the presence of a small amount of a cross-linking agent added thereto. In the core-shell graft copolymer, the core of cross-linked copolymer and the shell of hard resin are formed in relative amounts such that the core accounts for 50 to 80% by weight and the shell for 50 to 20% by weight, respectively, based on the core-shell graft copolymer.
Among the possible alkyl acrylates having 2 to 12 carbon atoms in the alkyl group thereof used for the formation of the core of cross-linked elastic copolymer, n-butyl acrylate and 2-ethylhexyl acrylate are particularly advantageous.
As examples of the conjugated diene, l-methyl-2-vinyl-4,6-heptadien-~-4~, 7-methyl-3-methylene-1, 6-octadiene, and 1,3,7-octatriene may be cited besides the aforementioned butadiene.
The cross-linking agent used in the formation of the core and the shell mentioned above must be selected on the condition that it is satisfactorily copolymerizable with the monomers during the course of polymerization. Examples of the cross-linking agent usable advantageously herein include aromatic polyfunctional vinyl compounds represented by divinyl lZg20~
benzene dimethacrylate, diethylene glycol dimethacrylate,and triethylene dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate, ar.d diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glyco~
diacrylate, and 1,3-butane diol diacrylate.
Optionally in the copolymerization of the alkyl acrylate and the polyfunctional polymerizable monomer possessing a conjugate diene type double bond, a monofunctional polymer-izable monomer properly selected from the group consisting of aromatic vinyl cornpounds represented by styrene, methacrylates represented by methyl methacrylate, vinyl nitriles represented by acrylonitrile, vinyl ether compounds represented by methyl vinyl ether, halogenated vinyl compounds represented by vinyl chloride, and vinyl ester compounds represented by vinyl acetate, particularly from the group of methacrylates represented by methyl methacrylate, can be used as part of the alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof.
As examples of the vinyl compound to be used for the graft copolymerization on the core of cross-linked elastic copolymer, there may be cited methacrylates represented by methyl methacrylate, aromatic vinyl compounds represented by styrene, vinyl nitriles represented by ~crylollitrile, and halogenated vinyl compounds represented by vinyl chloride.
these polymerizable monomers may be used eit.ler alorle or in the form of a mixture of two or more members. During the _ g _ course of the graft polymerization, this vinyl compound may be used in combination with the aforementioned cross-]inking agent.
In a preferred embodiment of this invention, the core of the core-shell graft copolymer (C) is a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 40 to 95%
by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of o.Ol to 3~ weight of a cross-linking agent and the shell of the core-shell graft copolymer comprises an inner shell layer and an outer shell layer formed by polymerization in two steps on said core of the cross-linked elastic copolymer, the inner shell layer being formed of a cross-linked polymer obtained by a graft polymerization either of (A) a monomer mixture containing styrene as a major component and methyl methacrylate or of (B) a monomer mixture containing (i) styrene or both methyl methacrylate and styrene and (ii) acrylonitrile in the presence of 0.01 to 3% by weight of a cross-linking agent and the outer shell layer being formed of a cross-linked polymer obtained by a graft polymerization of a monomer preponderantly of methyl methacrylate in the presence of 0.01 to 2% by weight of a cross-linking agent.
Typical methods available for the production of the acrylate type core-shell graft copolymer are described below.
A method comprises:
preparing coagulated particles having an average particle diameter of 0.12 to 0.3 em, preferably 0.05 to 0.1 em, by adding a coagulating agent such as, for example, a mineral acid like hydrochloric acid or sulfuric acid to a latex which has an average particle diameter, preferably, 0.05 to 0.1 em and contains 50 to 75 parts by weight of a cross-linked elastic copolymer obtained by ~Z42041 an emulsion polymerization of a monomer mixture consisting of 70 to 95 parts by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 30 to 5 parts by weight of butadiene, and 0.01 to 3 parts by weight, preferably 0.05 to 1.5 parts by weight, of a cross-linking agent, dividing 50 to 25 parts by weight of a monomer mixture which consists of 10 to 90% by weight of styrene and 9o to 10% by weight of methyl methacrylate and contains 0.01 to 2.0 parts by weight of a cross-linking agent,into (a) a mixture portion consisting of styrene as a major component and methyl methacrylate and containing said cross-linking agent and (b) a methyl methacrylate portion containing said cross-linking agent, subjecting the former divided portion (a) to an addition polymerization with the coagulated elastic latex and, subsequently subjecting the latter divided portion (B) to the addition polymerization with the resultant addition polymer.
Another typical method comprises:
preparing coagulated particles having an average particle diameter of 0.12 to 0.5 em by adding a coagulating agent to a latex containing 50 to 80 parts by weight of a cross-linked elastic copolymer obtained by the emulsion polymerization of a monomer mixture consisting of 40 to 95% by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of 0.01 to 3% by weight, preferably 0.05 to 1.5% by weight, of a cross-linking agent added thereto, subjecting 45 to 10 parts by weight of a monomer mixture consisting of 10 to 50% by weight of acrylonitrile, 50 to 90% by weight of styrene or both methyl methacrylate and styrene, and 0.01 to 3% by weight of a cross-lZ420~
linking agent copolyMerizable therewith to an addition polymerization with said coagulated particles and subsequently subjecting 5 to 25 parts by weight of an alkyl methacrylate monomer having l to 4 carbon atoms in the alkyl group thereof and containing 0.01 to 3% by weight of a cross-linking agent to the addition polymerization with the resultant addition polymer.
The graft polymerization may be carried out in one step or it may be performed in a plurality of steps by dividing the component monomers for the graft copolymerization into as many portions of varying compositions as required. The preferred methods for the production of the core-shell graft copolymer have been demonstrated as being performed in the form of emulsion polymerization. This does not mean that the emulsion polymerization is the only manner of polymerization available. Of course, the acrylate type graft copolymer contemplated by this invention can be produced by any of the methods of polymerization known in the art. As commercially available examples of the acrylate type core-shell graft copolymer, the resins marketed under the trade marks "IIIA-15","HIA-28", and "~lIA-30" by Kureha Kagaku Kogyo K.K. can be advantageously utilized.
In the polyphenylene ether type resin composition of the present invention, the polyphenylene ether resin (A) accounts for 10 to 90% preferably 25 to 70% by weight, the styrene-type resin (B) for 0 to 88%, preferably 30 to 75% by weight, and the acrylate type core-shell graft copolymer for 1 to 25% by weight, preferably 5 to 25% by weight.
If the proportion of the polyphenylene ether resin is less than 10% by weight, the properties inherent in the polyphenylene ether resin are not fully manifested. If it exceeds 90% by weight, the improvement of ~Z42041 moldability is not sufficient. If the proportion of the styrene-type resin exceeds 88% by weight, the properties due to the use of the polyphenylene ether are not fully manifested. If the proportion of the acrylate type core-shell graft copolymer is less than 1% by weight, the improvement with respect to the jetting at the gate portion is obtained with difficulty and the improvement in impact resistance is not sufficient. The term jetting is understood to mean turbulent flow of resin from an undersized gate or thin section into a thicker mold section, as opposed to laminar flow of material progressing radially from a gate to the extremities of the cavity.
The preparation of the polyphenylene ether type resin composition of the present invention can be effected by adopting any of the methods known to the art. For example, it may be - 12a -~2~2(~4~
r accomplished by mixing the components with a suitable mixing device such as a V blender or a Henshell mixer and subsequently kneading the resultant mixture in an extruder, a Banbury mixer, or a roll.
Optionally, the polyphenylene ether type resin composition of this invention may contain therein any of various additives known to the art. Examples of the additives advantageously usable for the purpose include flame retardants represented by organic phosphates and halogenated organic compounds, flame-retarding aids represented by antimony oxide and other antimony compounds, stabilizers, ultraviolet ray absorbents, pigments, dyes, lubricants, and fillers and reinforcing agents such as inorganic and organic powders and fibers. The polyphenylene ether type resin composition may further contain, when necessary, other elastomer or other resin components within the range not harmful to the properties of the product of this invention. Examples of the elastomer which is advantageously used for this purpose include A-B-A' type elastomeric block copolymers (wherein A and A' each represent a block resulting from polymerization of an aromatic vinyl compound and B
represents a block resulting from polymerization of a conjugated diene), A-B'-A' type elastomeric block copolymers (wherein A
and A' are the same as above and B' represents a block resulting from hydrogenation of the aforementioned block B), polybutadiene, polyisoprene, an elastomeric copolymer of a diene compound and an aromatic vinyl compound, a nitrile rubber, an elastomeric 12~%~41 ethylene-propylene copolymer, an ethylene-propylene-diene copolymer (EPDM), thiokol rubbers, polysulfide rubbers, acrylic rubbers, a grafted product of butyl rubber and polyethylene, polyurethane rubbers, and polyester elastomers. For example, the polycarbonate oligomer from bisphenol A or tetrabromo-bisphenol A may be incorporated for the improvement of moldability, flame retardancy, and surface properties, thermo-plastic aromatic polyester resins such as polyethylene terephthalate and polybutylene terephthalate and polyolefins such as polyethylene and ethylene-propylene copolymer for the improvement of chemical resistance, and heat-resistant polyesters such as polyester carbonate and polyallylate (such as are marketed by Unitika under trademark deisgnation of U polymers) for the improvement of heat resistance.
Now, the present invention will be described more specifi-cally below with reference to working examples and comparative experiments. Wherever "percent" and "molecular weight" are mentioned, they are based on respective amounts by weight unless otherwise specified.
Examples 1-8 and Comparative Experiments 1-4:
Compositions using polyphenylene ether resin which is a copolymer of 2,6-dimethyl phenol and 2,3,6-trimethyl phenol, polystyrene-type resin (HI-polystyrene produced by Asahi-Dow and marketed under the trade mark "Styron 492"), and acrylate type graft copolymers (produced by Kureha Kagaku Kogyo K.K. and marketed under the trade marks "HIA-15 lZ4;;~
and HIA-28", simply indicated as "HIA-15" and "HIA-28" in the following table examples 1-4) and compositions using the components just mentioned plus various polyolefins, i.e. ethylene-propylene copolymer (produced by Japan Synthetic Rubber Co.,Ltd. and marketed under the trade mark "JSR EP 07C", simply indicated as (a) in the following table), an olefinic elastomer (produced by Mitsui Petrochemical Co.,Ltd. and marketed under the trade mark "Milastomer 9590B," simply indicated as (b) in the following table), or ethyleneethyl acrylate copolymer (produced by Japan Unicar Co.,Ltd. and marketed under the trade mark "~UC Copolymer DPDJ-6169," simply indicated as (c) in the following table) (Examples 5-8) were kneaded in proportions indicated in Table 1 in a blender.
The resultant mixtures were each supplied to a biaxial extruder, melted and kneaded at a cylinder temperature of 280C, and convcrted into pellets. The pellets were dried at 100C for at least two hours in a hot-air drier and injection molded to produce test pieces for determination of physical properties. The results are shown in Table 1.
Ion comparison, the procedure of the foregoing working examples was followed by using a composition of polyphenylene ether resin and polystyrene-type resin (Comparative Experiment 1), a composition equalling the composition of Example 1 minus the acrylate type graft copolymer (Comparative Experiment 2), a composition equalling the composition of Example 2 minus the lZ42041 acrylate type graft copolymer (Comparative Experiment 3), and a composition equalling the composition of Example 3 minus the acrylate type graft copolymer (Comparative Experiment 4). The results are shown in Table 1.
In Table 1, the data given under the heading "HDT (*l)"
and the heading " jetting" (*2) were determined as follows:
*1: The procedure defined by ASTM D1238 under the con-ditions of 3.8 kg of load and 250C of temperature.
*2: A given sample of predried pellets was treated with a Sumitomo-Nestar injection molder (Neomat N350/120) ; to produce a test piece measuring 89.5 mm x 49.5 mm x 3.2 mm and having a gate cross section of 3 mm in thickness and 7 mm in width under the conditions of 280C of cylinder temperature, 80C of mold temper-ature, 1100 kg/cm of injection pressure, FCV 7/12, 14 seconds of injection time, and 25 seconds of cooling time. The test piece was visually inspected with respect to the condition of jetting in the gate portion.
12420~
_ O O O I r-J O a a O o o f r O In CO l or o I) r o or ED
CO O G O ED f D o U ) ,_i~1 0 O ~0 æ
,' l ~0 do ~0 ED ox ED O O f ED O r- ED a - I` 'i'I æ
us O o ox I O n co n a a) f or I, n O
l 1 LD~ o on O l 1 - tip Lo n f a~I~ a i Ln Ln O
o Ln Ln ED n Ln o o Ln Ln I_ Ln I
9c) O î o O ~j z o on L .~
6 o x O I 3 l X . _ t . A
f _ g 13 o I; Ln o c (I .~ ~3 _ .
1242~41 Examples 9 and Comparative Experiments 5 and 6:
The test pieces obtained under the conditions of Examples 1-4 were tested for Izod impact strength at low temperatures.
The results are shown in Table 2.
For comparison, a composition equalling the composition of Examples 1-4 except that MBS resin (produced by Japan Synthetic Rubber Co., Ltd.and marketed under trademark design-ation of JSR MBS 67) was used instead of HIA-15 (Comparative Experiment 5) and a composition equalling the composition of Examples 1-4 except that MAS resin (produced by Mitsubishi Rayon Co., Ltd. and marketed under trademark designation Metablen W529) was used instead of HIA-15 (Comparative Experi-ment 6) were treated and tested under the conditions of Examples 1-4. The results are also shown in Table 2.
Table 2 Example Comparative Comparative i 9 Experiment 5 Exaperiment 6 Polyphenylene 40 40 40 ether resin compo- Polystyrene-type 45 45 45 sition HIA-15 15 (%) MBS resin 15 MAS resin 15 23C 21.6 21.2 20.9 trength (notch), 1/8" 0 20.5 18.6 13.7 kg.cm/cm l 8.5 10.2 Example lO and Comparative Experiment 7:
The test pieces obtained under the same conditions as those of Examples 1-4 were treated for prescribed lengths of time with a sunshing weather meter, and then tested for tensile strength and retention of tensile elongation. The results A are shown in Table 3.
For comparison, a composition equalling the composition of Examples 1-4 except that MBS resin (produced by Japan Synthetic Rubber Co., Ltd. and marketed under trademark designation of "JSR MBS 67") was used instead of HIA-15 (Comparative Experiment
4) was tested under the same conditions as those of Examples 1-4. The results are shown in Table 3.
Table 3 Example Compa.ative lO Experiment 7 Polyphenylene ether resin 43 43 Resin Polystyrene-type resin 47 47 compo- HIA-15 lO
(%) MBS resin lO
Tensile500 hrs 102 98 Weather- Ratio of strength lO00 hrs 101 92 l) retention r/ (%) Elongation 250o hrrS 61 31 (Note) l) The data given in this bracket represent the results determined after the treatment for specified lengths of time with the sunshine weatehr meter.
Table 3 Example Compa.ative lO Experiment 7 Polyphenylene ether resin 43 43 Resin Polystyrene-type resin 47 47 compo- HIA-15 lO
(%) MBS resin lO
Tensile500 hrs 102 98 Weather- Ratio of strength lO00 hrs 101 92 l) retention r/ (%) Elongation 250o hrrS 61 31 (Note) l) The data given in this bracket represent the results determined after the treatment for specified lengths of time with the sunshine weatehr meter.
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polyphenylene ether resin composition comprising:
(A) 10 to 90 parts by weight of a polyphenylene ether resin, (B) 0 to 88 parts by weight of a polystyrene-type resin, and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising:
(1) 50 to 80% by weight of a core of a cross-linked elastic copolymer formed by copolymerizing an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and a conjugated diene as main comonomers in the presence of a cross-linking agent, and (2) 50 to 20% by weight of a shell of a hard resin formed by graft polymerizing an aromatic monovinyl compound and methyl methacrylate as main comonomers in the presence of a cross-linking agent onto the elastic core, wherein the sum of components (A), (B) and (C) is 100 parts by weight and the polystyrene-type resin contains at least about 35% by weight of repeating units of the general formula:
(3) wherein R4 represents a hydrogen atom or a methyl group, Z represents a chlorine atom or a methyl group and p is 0 or an integer of 1 to 3.
(A) 10 to 90 parts by weight of a polyphenylene ether resin, (B) 0 to 88 parts by weight of a polystyrene-type resin, and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising:
(1) 50 to 80% by weight of a core of a cross-linked elastic copolymer formed by copolymerizing an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and a conjugated diene as main comonomers in the presence of a cross-linking agent, and (2) 50 to 20% by weight of a shell of a hard resin formed by graft polymerizing an aromatic monovinyl compound and methyl methacrylate as main comonomers in the presence of a cross-linking agent onto the elastic core, wherein the sum of components (A), (B) and (C) is 100 parts by weight and the polystyrene-type resin contains at least about 35% by weight of repeating units of the general formula:
(3) wherein R4 represents a hydrogen atom or a methyl group, Z represents a chlorine atom or a methyl group and p is 0 or an integer of 1 to 3.
2. A resin composition according to claim 1, wherein the polyphenylene ether resin is one member selected from the group consisting oE phenylene ether homopolymer, phenylene ether copolymer, and grafted phenylene ether polymer.
3. A resin composition according to claim 1, wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene)-ether, 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer, or a phenylene ether polymer having styrene grafted thereto.
4. A resin composition according to Claim 1, wherein the polystyrene-type resin is one member selected from the group consisting of polystyrene, rubber-modified polystyrene, styrene/butadiene/acrylonitrile copolymer, styrene-maleic anhydride copolymer, poly-p-methylstyrene, high impact poly-p-methylstyrene, and p-methylstyrene-maleic anhydride copolymer.
5. A polyphenylene ether resin composition comprising:
(A) 10 to 90 parts by weight of a polyphenylene ether resin which is obtained by oxidatively polycondensing a monocyclic phenol represented by the formula:
(1) wherein R1 represents a lower alkyl group of 1 to 3 carbon atoms and R2 and R3, which may be the same or different, each represent a hydrogen atom or a straight or branched chain alkyl group of 1 to 3 carbon atoms, or a modified polyphenylene ether obtained by grafting to the aforementioned polyphenylene ether an aromatic vinyl compound represented by the formula:
(2) wherein R4 represents a hydrogen atom or a methyl group, Z represents a chlorine atom or a methyl group, and p is O or an integer of 1 to 3, (B) O to 88 parts by weight of a polystyrene-type resin containing at least about 25% by weight of repeating units of the formula:
(3) wherein R4, Z and p have the same meanings as defined in the general formula (2), and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising:
(1) 50 to 80% by weight of a core of a cross-linked elastic copolymer formed by the emulsion polymerization of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group and a conjugated diene as essential comonomers, in the presence of a cross-linking agent and (2) 50 to 20% by weight of a shell of a hard resin formed on the elastic core by the graft-polymerization of styrene and methyl methacrylate as essential components in the presence of a cross-linking agent.
(A) 10 to 90 parts by weight of a polyphenylene ether resin which is obtained by oxidatively polycondensing a monocyclic phenol represented by the formula:
(1) wherein R1 represents a lower alkyl group of 1 to 3 carbon atoms and R2 and R3, which may be the same or different, each represent a hydrogen atom or a straight or branched chain alkyl group of 1 to 3 carbon atoms, or a modified polyphenylene ether obtained by grafting to the aforementioned polyphenylene ether an aromatic vinyl compound represented by the formula:
(2) wherein R4 represents a hydrogen atom or a methyl group, Z represents a chlorine atom or a methyl group, and p is O or an integer of 1 to 3, (B) O to 88 parts by weight of a polystyrene-type resin containing at least about 25% by weight of repeating units of the formula:
(3) wherein R4, Z and p have the same meanings as defined in the general formula (2), and (C) 1 to 25 parts by weight of an alkyl acrylate-type core-shell graft copolymer comprising:
(1) 50 to 80% by weight of a core of a cross-linked elastic copolymer formed by the emulsion polymerization of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group and a conjugated diene as essential comonomers, in the presence of a cross-linking agent and (2) 50 to 20% by weight of a shell of a hard resin formed on the elastic core by the graft-polymerization of styrene and methyl methacrylate as essential components in the presence of a cross-linking agent.
6. A resin composition according to Claim 1, 4 or 5, wherein the core of the core-shell graft copolymer (C) is a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 40 to 95% by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of 0.01 to 3% by weight of a cross-linking agent and the shell of the core-shell graft copolymer comprises an inner shell layer and an outer shell layer formed by polymerization in two steps on said core of the cross-linked elastic copolymer, the inner shell layer being formed of a cross-linked polymer obtained by a graft polymerization either of (A) a monomer mixture containing styrene as a major component and methyl methacrylate or of (B) a monomer mixture containing (i) styrene or both methyl methacrylate and styrene and (ii) acrylonitrile in the presence of 0.01 to 3% by weight of a cross-linking agent and the outer shell layer being formed of a cross-linked polymer obtained by a graft polymerization of a monomer preponderantly of methyl methacrylate in the presence of 0.01 to 2% by weight of a cross-linking agent.
7. A resin composition according to Claim 1, or 5, wherein the core-shell graft copolymer (C) is produced by:
preparing coagulated particles having an average particle diameter of 0.12 to 0.3 µm by adding a coagulating agent to a latex which has an average particle diameter of 0.05 to 0.1 µm and contains 50 to 75 parts by weight of a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 70 to 95 parts by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 30 to 5 parts by weight of butadiene, and 0.01 to 3 parts by weight of a cross-linking agent, dividing 50 to 25 parts by weight of a monomer mixture which consists of 10 to 90% by weight of styrene and 90 to 10% by weight of methyl methacrylate and contains 0.01 to 2.0 parts by weight of a cross-linking agent into (a) a mixture portion consisting of styrene as a major component and methyl methacrylate and containing the cross-linking agent and (b) a methyl methacrylate portion containing the cross-linking agent, subjecting the former divided portion (a) to an addition polymerization with the coagulated elastic latex and, subsequently subjecting the latter divided portion (b) to an addition polymerization with the resultant addition polymer.
preparing coagulated particles having an average particle diameter of 0.12 to 0.3 µm by adding a coagulating agent to a latex which has an average particle diameter of 0.05 to 0.1 µm and contains 50 to 75 parts by weight of a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 70 to 95 parts by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 30 to 5 parts by weight of butadiene, and 0.01 to 3 parts by weight of a cross-linking agent, dividing 50 to 25 parts by weight of a monomer mixture which consists of 10 to 90% by weight of styrene and 90 to 10% by weight of methyl methacrylate and contains 0.01 to 2.0 parts by weight of a cross-linking agent into (a) a mixture portion consisting of styrene as a major component and methyl methacrylate and containing the cross-linking agent and (b) a methyl methacrylate portion containing the cross-linking agent, subjecting the former divided portion (a) to an addition polymerization with the coagulated elastic latex and, subsequently subjecting the latter divided portion (b) to an addition polymerization with the resultant addition polymer.
8. A resin composition according to Claim 1, 4 or 5 wherein the core-shell graft copolymer (C) is produced by:
preparing coagulated particles having average particle diameter of 0.12 to 0.5 µm by adding a coagulating agent to a latex containing 50 to 80 parts by weight of a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 40 to 95% by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of 0.01 to 3% by weight of a cross-linking agent subjecting 45 to 10 parts by weight of a monomer mixture consisting of 10 to 50% by weight of acrylonitrile, 50 to 90% by weight of styrene or both methyl methacrylate and styrene, and 0.01 to 3% by weight of a cross-linking agent copolymerizable therewith to an addition polymerization with the coagulated particles and, subsequently subjecting 5 to 25 parts by weight of an alkyl methacrylate monomer having 1 to 4 carbon atoms in the alkyl group thereof and containing 0.01 to 3% by weight of a cross-linking agent to an addition polymerization with the resultant addition polymer.
preparing coagulated particles having average particle diameter of 0.12 to 0.5 µm by adding a coagulating agent to a latex containing 50 to 80 parts by weight of a cross-linked elastic copolymer obtained by an emulsion polymerization of a monomer mixture consisting of 40 to 95% by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof, 5 to 40% by weight of butadiene, and 0 to 30% by weight of methyl methacrylate in the presence of 0.01 to 3% by weight of a cross-linking agent subjecting 45 to 10 parts by weight of a monomer mixture consisting of 10 to 50% by weight of acrylonitrile, 50 to 90% by weight of styrene or both methyl methacrylate and styrene, and 0.01 to 3% by weight of a cross-linking agent copolymerizable therewith to an addition polymerization with the coagulated particles and, subsequently subjecting 5 to 25 parts by weight of an alkyl methacrylate monomer having 1 to 4 carbon atoms in the alkyl group thereof and containing 0.01 to 3% by weight of a cross-linking agent to an addition polymerization with the resultant addition polymer.
9. A resin composition according to Claim 5, wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene)-ether, 2,6-dimethylphenol-2,3,6-trimethylphenol copolymer, or a phenylene ether polymer having styrene grafted thereto.
10. A resin composition according to claim 9, wherein the polystyrene-type resin is one member selected from the group consisting of polystyrene, rubber-modified polystyrene, styrene/butadiene/acrylonitrile copolymer, styrene-maleic anhydride copolymer, poly-p-methylstyrene, high impact poly-p-methylstyrene, and p-methylstyrene-maleic anhydride copolymer.
11. A process for producing the polyphenylene ether resin composition as defined in claim 1 or 5, which process comprises:
(I) mixing the components with a suitable mixing device and (II) subsequently kneading the resultant mixture in an extruder or a roll.
(I) mixing the components with a suitable mixing device and (II) subsequently kneading the resultant mixture in an extruder or a roll.
12. A molded article produced by molding the polyphenylene ether resin composition as defined in claim 1 or 5.
13. A resin composition according to claim 5, wherein the polyphenylene ether resin is phenylene ether homopolymer or phenylene ether copolymer.
14. A resin composition according to claim 13, wherein the amount of the polystyrene-type resin (B) is 30 to 75 parts by weight and the polystyrene-type resin is a member selected from the group consisting of polystyrene, rubber-modified polystyrene, styrene/butadiene copolymer, styrene/butadiene/acry-lonitrile copolymer, styrene/.alpha.-methylstyrene copolymer, poly-.alpha.-methylstyrene and rubber-modified skyrene/.alpha.-methylstyrene copolymer, provided that any of the resins contain at least about 25% by weight of repeating units derived from styrene or .alpha.-methylstyrene.
15. A resin composition according to claim 14, wherein the amount of the polyphenylene ether resin (A) is 25 to 70 parts by weight and the amount of the alkyl acrylate-type core-shell graft copolymer (C) is 5 to 25% parts by weight, wherein the sum of components (A), (B) and (C) is 100 parts by weight.
16. A resin composition according to claim 13, 14 or 15, wherein the core of the core-shell graft copolymer (C) is a cross-linked elastic copolymer obtained by an emulsion poly-merization of a monomer mixture consisting of 40 to 95% by weight of an alkyl acrylate having 2 to 12 carbon atoms in the alkyl group thereof and 5 to 40% by weight of butadiene in the presence of 0.01 to 3% by weight of a cross-linking agent and the shell of the core-shell graft copolymer comprises an inner shell layer and an outer shell layer formed by polymerization in two steps on said core of the cross-linked elastic copolymer, the inner shell layer being formed of a cross-linked polymer obtained by a graft polymerization either of (A) a monomer mixture containing styrene as a major component and methyl methacrylate or of (B) a monomer mixture containing methyl methacrylate, styrene and acrylonitrile in the presence of 0.01 to 3% by weight of a cross-linking agent and the outer shell layer being formed of a cross-linked polymer obtained by a graft polymerization of methyl methacrylate in the presence of 0.01 to 2% by weight of a cross-linking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59010614A JPS60155260A (en) | 1984-01-24 | 1984-01-24 | Polyphenylene ether resin composition |
| JP10,614/84 | 1984-01-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1242041A true CA1242041A (en) | 1988-09-13 |
Family
ID=11755112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000472625A Expired CA1242041A (en) | 1984-01-24 | 1985-01-23 | Polyphenylene ether resin composition |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4617346A (en) |
| JP (1) | JPS60155260A (en) |
| CA (1) | CA1242041A (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU617339B2 (en) * | 1987-08-06 | 1991-11-28 | Ge Chemicals, Inc | High molecular weight polystyrene and method and blends with ppe and hips |
| JP2707312B2 (en) * | 1988-03-10 | 1998-01-28 | 三菱レイヨン株式会社 | Polyphenylene ether resin composition |
| US5159027A (en) * | 1989-01-27 | 1992-10-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Stabilized polyphenylene ether resin and process for the preparation of the same |
| JPH0395245A (en) * | 1989-05-25 | 1991-04-19 | Dainippon Ink & Chem Inc | Thermoplastic resin composition |
| CA2021100A1 (en) * | 1989-09-15 | 1991-03-16 | William R. Haaf | Polyphenylene ether compositions having improved flow |
| WO1991005016A1 (en) * | 1989-10-06 | 1991-04-18 | Asahi Kasei Kogyo Kabushiki Kaisha | A shaped resin article |
| US5183108A (en) * | 1991-08-19 | 1993-02-02 | The Gates Rubber Company | Inflatable packer |
| DE4127978A1 (en) * | 1991-08-23 | 1993-02-25 | Basf Ag | THERMOPLASTIC MOLDS WITH IMPROVED MULTIAXIAL TOUGHNESS |
| DE4208339A1 (en) * | 1992-03-16 | 1993-09-23 | Basf Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON POLYARYLENETHERS, POLYCARBONATES AND GRAFT RUBBER |
| JPH07268151A (en) * | 1994-03-31 | 1995-10-17 | Sumitomo Chem Co Ltd | Thermoplastic resin |
| US5767168A (en) | 1995-03-30 | 1998-06-16 | The Proctor & Gamble Company | Biodegradable and/or compostable polymers made from conjugated dienes such as isoprene and 2,3-dimethyl-1, 3-butadiene |
| US5922780A (en) * | 1995-01-10 | 1999-07-13 | The Procter & Gamble Company | Crosslinked polymers made from 1,3,7-octatriene and like conjugated polyenes |
| US20050228074A1 (en) * | 2004-04-05 | 2005-10-13 | Bridgestone Corporation | Amphiphilic polymer micelles and use thereof |
| JP5053507B2 (en) * | 2004-11-09 | 2012-10-17 | 出光興産株式会社 | Thermoplastic resin composition and molded body |
| US9061900B2 (en) | 2005-12-16 | 2015-06-23 | Bridgestone Corporation | Combined use of liquid polymer and polymeric nanoparticles for rubber applications |
| US8288473B2 (en) | 2005-12-19 | 2012-10-16 | Bridgestone Corporation | Disk-like nanoparticles |
| US8877250B2 (en) | 2005-12-20 | 2014-11-04 | Bridgestone Corporation | Hollow nano-particles and method thereof |
| US8697775B2 (en) | 2005-12-20 | 2014-04-15 | Bridgestone Corporation | Vulcanizable nanoparticles having a core with a high glass transition temperature |
| EP2046575A4 (en) * | 2006-07-28 | 2010-01-13 | Bridgestone Corp | Polymeric core-shell nanoparticles with interphase region |
| ES2527600T3 (en) | 2008-12-31 | 2015-01-27 | Bridgestone Corporation | Procedure of formation of nanoparticles first forming the nucleus, nanoparticle and composition |
| US9062144B2 (en) | 2009-04-03 | 2015-06-23 | Bridgestone Corporation | Hairy polymeric nanoparticles with first and second shell block polymer arms |
| US9115222B2 (en) | 2009-12-29 | 2015-08-25 | Bridgestone Corporation | Well defined, highly crosslinked nanoparticles and method for making same |
| US9428604B1 (en) | 2011-12-30 | 2016-08-30 | Bridgestone Corporation | Nanoparticle fillers and methods of mixing into elastomers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128602A (en) * | 1970-04-24 | 1978-12-05 | General Electric Company | Polyphenylene ether compositions containing rubber modified polystyrene |
| DE3102254A1 (en) * | 1981-01-24 | 1982-09-02 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDING |
| DE3108424A1 (en) * | 1981-03-06 | 1982-09-23 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
-
1984
- 1984-01-24 JP JP59010614A patent/JPS60155260A/en active Granted
-
1985
- 1985-01-23 CA CA000472625A patent/CA1242041A/en not_active Expired
-
1986
- 1986-01-13 US US06/818,073 patent/US4617346A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4617346A (en) | 1986-10-14 |
| JPS60155260A (en) | 1985-08-15 |
| JPH0480943B2 (en) | 1992-12-21 |
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