CA1266936A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- CA1266936A CA1266936A CA000524831A CA524831A CA1266936A CA 1266936 A CA1266936 A CA 1266936A CA 000524831 A CA000524831 A CA 000524831A CA 524831 A CA524831 A CA 524831A CA 1266936 A CA1266936 A CA 1266936A
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- CA
- Canada
- Prior art keywords
- resin
- weight
- polyphenylene oxide
- resin composition
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- 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
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
Abstract
ABSTRACT
THERMOPLASTIC RESIN COMPOSITION
A thermoplastic resin composition containing polyphenylene oxide resin is provided, which is superior in processability and impact resistance as well as heat resistance, chemical resistance and hardness, said thermoplastic resin composition comprising (A) polyphenylene oxide resin or a resin composition containing the same, and (B) ethylene copolymer comprising 50 - 90 % by weight of ethylene, 5 - 49 % by weight of alkyl ester of .alpha.,.beta.-unsaturated carboxylic acid and 0.5 - 10 % by weight of maleic anhydride.
THERMOPLASTIC RESIN COMPOSITION
A thermoplastic resin composition containing polyphenylene oxide resin is provided, which is superior in processability and impact resistance as well as heat resistance, chemical resistance and hardness, said thermoplastic resin composition comprising (A) polyphenylene oxide resin or a resin composition containing the same, and (B) ethylene copolymer comprising 50 - 90 % by weight of ethylene, 5 - 49 % by weight of alkyl ester of .alpha.,.beta.-unsaturated carboxylic acid and 0.5 - 10 % by weight of maleic anhydride.
Description
3~
THERMOPI.ASTIC RESIN COMPOSI1'ION
.. . ..
The present invention rel~te.s to a novel thermo-plastic resin composition usable as shaped articles by irljection molding, e~trusion molding and the like.
More particularly, the present invention relates to a novel thermoplastic resin composition which is excellent in balance among physical properties and in appearance, wher~in a copolymer of ethylene, a~ alkyl ester of a,~-unsaturated carboxylic acid and maleic anhydride is incorporat2d in a polyphenyle~e oxide resin or a resin composition containing the same.
Polyphenylene oxide resin is, generally speaking,a thermoplastic resin excellent in various properties such as mechanical properties, electrical properties, chemic~l resistance, heat resistance, water resistance, flame resist-ance and dimentional stability. However, ~he resin has difficu~ties, i.e.O the melt vi6c08i~y is so high that process-ability is not good, and furthermore, the impact ~tren~th is relatively small.
One of approaches known to reduce melt viscosity in order to improve processability, without giving any unfavor-able influence to excellent properties of polyphenylen~
oxide resin, is blending polyphenylene oxide resin wi~h polystyrene resin, but this approach tends to lose heat resistance, f~ame resistance, chemical resistance and other favorable properties of polypherlylene o~ide resin, although there is ~ome improvement in practical processabillty. An improvement in impact strength is not enough even after polyphenyle~e oxide resin i5 blended with polystyrene resin.
Another approach is to use polystyrene rPsin which is modified with butadiene rubber or EPDM rubber or to use styrenic thermoplastic elastomer in order to improve impact strength. However, this approach is not satisfactory yet from a view point of shaping, sinc~ although chemical resistance is improved, too, increase in melt viscosity is ~' 3~
so large that shaping processability and appearaince of shaped articles are greatly damaged.
Further approach to reduce melt vi~cosity of a polyphenylene oxide composi~ion and to improve melt Elowability as well as processability is blending the composition with foreign high molecular resin. However, this approach is not satisfactory, either, since compatibility of the foreign high molecular resin ii6 usually so small that ~nfavorable difficulties are encountered, i.eO ~ easy peeling off of resin when molded~ impairment in appeairance of molded articles and great reduction in mechanical properties.
Under the situation above, it is important to select high molecular resin which does not give any of such unEavor-able influences as above to a polyphenylene o~ide resin composition when blended therein. Development in such resin has long been desire.d.
The present invention intends to improve process-abili~y and impact resistance which are difficulties encoun~
tered in polyphenylene oxide resin by adding thereto ethylene copolymer having specific structure, thereby to solvio the problem without impairing any of inherent favorable propertieis such as heat resiistance, hardness, etc. It is an object oE
the present invention to provide a thermoplastic resin composition containing polyphenylene oxide resin, which is superior in processability and impact resistance as well as heat resistance, che~nical xesistance and hardnesis.
AEter having wide~y and elaborately in~estigated high molecular rssin which facilitates modification of polyphenylene oxide from a viewpoint above, the present inventors have succeeded in finding ethylene copolymer which has specific structure and is able to give a good balance among impact resistance, heat resistance and hardness, and superiorities in processability and in appearance oE molded articles. The present invention is based on this inding.
~hat is, the present invention relates to a thermo-plast:ic resin composition which comprises c ., -3- ~.2 ~6~33~j (.A) polyphenylene oxide resin or a resin composition containing 1 - 99 parts polyphenylene o~ide per 100 parts thereof; and (B) an ethylene copolymer comprising 50-90% by weight of ethyléne, 5-49% by weight of an alkyl e~ter of an a,B-unsaturated carboxyli.c acid, and 0.5-10% by weight of maleic anhydride.
Polyphenylene oxide resin (A) in the present invention is u polymer obt~ined by oxidatio~ polymerizing one or two or more of phenol compounds of the formula:
OH
R5 ¦ R1 E~4 ~ 1R2 wherein R, R, R, R and R5 are respectively selec~ed Erom a hydrogen atom, a halogen atom, a hydrocarbon group and a substituted hydrocarbon group and at least one of the ~ymbols is a hydrogen atom, ~ith molecular-oxygen or a gas containing the ~ame in the presence of an oxidation polycondensation catalyst.
1 f ~1 R2 R3 R4 and R5 in the formula above are a hydro~en atom, a chlorine atom, a bromine atom, a fluorine atom, an ioAine atom, a methyl group, an ethyl group, an n- or iso-propyl group, a prim-, sec- or t-butyl group, a chloroethyl group, a hydroxyethyl group, a phenylethyl group, a benzyl group, a hydroxymethyl group, a carboxyethyl group, a methoxycarbonylethyl group, a cyanoethyl group, a phenyl group, a chlorophenyl group, a methylpheny]. group, a dimethyl-phenyl group, an ethylphenyl group and an allyl group.
E~ample~ of the compound of the formula above.are phenol, o-, m or p-cre~ol, 2,6-, 2,5-, 2,4- or 3,5-dimethyl-phenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol~ 2,3,5-, 2,3,6-- or
THERMOPI.ASTIC RESIN COMPOSI1'ION
.. . ..
The present invention rel~te.s to a novel thermo-plastic resin composition usable as shaped articles by irljection molding, e~trusion molding and the like.
More particularly, the present invention relates to a novel thermoplastic resin composition which is excellent in balance among physical properties and in appearance, wher~in a copolymer of ethylene, a~ alkyl ester of a,~-unsaturated carboxylic acid and maleic anhydride is incorporat2d in a polyphenyle~e oxide resin or a resin composition containing the same.
Polyphenylene oxide resin is, generally speaking,a thermoplastic resin excellent in various properties such as mechanical properties, electrical properties, chemic~l resistance, heat resistance, water resistance, flame resist-ance and dimentional stability. However, ~he resin has difficu~ties, i.e.O the melt vi6c08i~y is so high that process-ability is not good, and furthermore, the impact ~tren~th is relatively small.
One of approaches known to reduce melt viscosity in order to improve processability, without giving any unfavor-able influence to excellent properties of polyphenylen~
oxide resin, is blending polyphenylene oxide resin wi~h polystyrene resin, but this approach tends to lose heat resistance, f~ame resistance, chemical resistance and other favorable properties of polypherlylene o~ide resin, although there is ~ome improvement in practical processabillty. An improvement in impact strength is not enough even after polyphenyle~e oxide resin i5 blended with polystyrene resin.
Another approach is to use polystyrene rPsin which is modified with butadiene rubber or EPDM rubber or to use styrenic thermoplastic elastomer in order to improve impact strength. However, this approach is not satisfactory yet from a view point of shaping, sinc~ although chemical resistance is improved, too, increase in melt viscosity is ~' 3~
so large that shaping processability and appearaince of shaped articles are greatly damaged.
Further approach to reduce melt vi~cosity of a polyphenylene oxide composi~ion and to improve melt Elowability as well as processability is blending the composition with foreign high molecular resin. However, this approach is not satisfactory, either, since compatibility of the foreign high molecular resin ii6 usually so small that ~nfavorable difficulties are encountered, i.eO ~ easy peeling off of resin when molded~ impairment in appeairance of molded articles and great reduction in mechanical properties.
Under the situation above, it is important to select high molecular resin which does not give any of such unEavor-able influences as above to a polyphenylene o~ide resin composition when blended therein. Development in such resin has long been desire.d.
The present invention intends to improve process-abili~y and impact resistance which are difficulties encoun~
tered in polyphenylene oxide resin by adding thereto ethylene copolymer having specific structure, thereby to solvio the problem without impairing any of inherent favorable propertieis such as heat resiistance, hardness, etc. It is an object oE
the present invention to provide a thermoplastic resin composition containing polyphenylene oxide resin, which is superior in processability and impact resistance as well as heat resistance, che~nical xesistance and hardnesis.
AEter having wide~y and elaborately in~estigated high molecular rssin which facilitates modification of polyphenylene oxide from a viewpoint above, the present inventors have succeeded in finding ethylene copolymer which has specific structure and is able to give a good balance among impact resistance, heat resistance and hardness, and superiorities in processability and in appearance oE molded articles. The present invention is based on this inding.
~hat is, the present invention relates to a thermo-plast:ic resin composition which comprises c ., -3- ~.2 ~6~33~j (.A) polyphenylene oxide resin or a resin composition containing 1 - 99 parts polyphenylene o~ide per 100 parts thereof; and (B) an ethylene copolymer comprising 50-90% by weight of ethyléne, 5-49% by weight of an alkyl e~ter of an a,B-unsaturated carboxyli.c acid, and 0.5-10% by weight of maleic anhydride.
Polyphenylene oxide resin (A) in the present invention is u polymer obt~ined by oxidatio~ polymerizing one or two or more of phenol compounds of the formula:
OH
R5 ¦ R1 E~4 ~ 1R2 wherein R, R, R, R and R5 are respectively selec~ed Erom a hydrogen atom, a halogen atom, a hydrocarbon group and a substituted hydrocarbon group and at least one of the ~ymbols is a hydrogen atom, ~ith molecular-oxygen or a gas containing the ~ame in the presence of an oxidation polycondensation catalyst.
1 f ~1 R2 R3 R4 and R5 in the formula above are a hydro~en atom, a chlorine atom, a bromine atom, a fluorine atom, an ioAine atom, a methyl group, an ethyl group, an n- or iso-propyl group, a prim-, sec- or t-butyl group, a chloroethyl group, a hydroxyethyl group, a phenylethyl group, a benzyl group, a hydroxymethyl group, a carboxyethyl group, a methoxycarbonylethyl group, a cyanoethyl group, a phenyl group, a chlorophenyl group, a methylpheny]. group, a dimethyl-phenyl group, an ethylphenyl group and an allyl group.
E~ample~ of the compound of the formula above.are phenol, o-, m or p-cre~ol, 2,6-, 2,5-, 2,4- or 3,5-dimethyl-phenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol~ 2,3,5-, 2,3,6-- or
2,4,6-trimethylphenol, 3-methyl-6 t-butylphenol, thimol and 2-methyl-6~allyphenol, Furth~rmore, the compound of the ,~."~
. , .~ .
6~3~
formula above ~ay be copolymerized with the other phenols than that of the above formula, e.g., polyv~lent hydroxy ~romatic compound, as of bis-phenol A, te~rabromobisphenol A, resorci~ hydroguinone and novolalc resin.
PreEerable polymers are homopolymer o~ 2~6-dimethyl-phenol or of 2,6-diphenylphenol and copolymer of a large amount of 2,6-xylenol and a small amount of 3-methyl~6--t-butylphenol or 2~3,6-trimethylphenol.
Any oxidation polycondensation catalyst for oxidation polymerization of phenol compound may be employed as long as it has polymerization ability. For instance, mention may be made of a catalyst of cuprous salts and tertiary amines such as cuprous chloride-triethylamine and cuprous chlorid2-pyridine;
a catalyst of cupric salts-amino-alkali metal hydroxides such as cupric chloride-pyridine-potassium hydroxid2; a catalyst of manganese salts and primary amines such as manganese chlorid~-ethanolamine and manganese acetate-ethylenediamine; a c~talyst of manganese salts and alcoholates or phenolates such as manganese chloride-sodium methylate and manganese chloride-sodium phenolate, a combination catalyst of cobalt salts and tertiary amines.
Furthermore, polyphenylene oxide resin in the present invention includes polyphenylene oxide ~bove grafted with styrene polymer or other polymers. The resin is prepared by organic pero~ide graft polymerization of styrene monomer and/or other polymerizable monomer in the presence of poly-phenylene oxide (Japanes0 published examined patent application Nos. 47862/1972, 12197/1973, 5623/1974, 38596/1977, 30991/1977 etc.) or melt kneading the polyphenylene oxide, polystyrene and a radical initiator (Japanese published unexamined patent application No~ 142799/1977 ~ .
The resin compo~itio~ (A) containing polyphenylene oxide in the present inventi.on is th~t consisting of the polyphenylene oxide and one or more other high molecular weight compounds. The high molscular weight compound includes polyol~fin~ cuch a~ polyethylene, polypropylene, ethylene-pxopylene ~' 33~
block copolyn~er, pol~methylpentene, ethylene-a-olefin copolymer; homopolymers or copolymers such as polyvi~yl ~hloride, polymethylmethacrylate, polyvinyl acetate, polyvinyl pyricline, polyvinyl carbazole, polyacrylamide, polyacrylonitrile, ethylene-vinyl acetate copolymer and alkenyl aromatic resin polycarbonate; polysulfone; polyethylene terephthalate;
polybutylene terephthalate; polyallylene ester (for e~ample, "U-polymer" manufactured by Yunichika K.K.); polyphenylene sulfide;polyamides ~uch as 6-nylon, 6,6~nylon and 12-nylon;
condensed high molecular compounds such as polyacetal; and rubbery pol~mer. Furthermo~e, mention may be made of various thermosetting resins ~uch a~ silicone resin, fluorine resin, polyimido, polyamidoimido, phenol resin, alkyd resin, unsaturated polyester re~in, epoxy resin and "Dapon"~ esin~
Ihe mixing ra~o of polyphenylene oxide and other high ~Dlecular compounds may widely be ~elected within the range of, for ~xample, 1 - 99 % by weight of polyphenylene oxide and 99 - 1 ~ by weight of the other h.igh molecular compounds. Optimum ratio depends on object and use of the mixture within the range.
It is easy for the skilled in ~he art to decide th~
optimum rat.io.
Preferable other high molecular compound is poly-olefln, polyamide, alkenyl aromatic resin, rubber modified alkenyl aromatic resin and r~bbery po].ymer.
The most preferable high molecular compound is alkenyl aromatic resin, rubber modified alkenyl aromatic resin and rubbery polymer.
Alkenyl aromatic resin in the present invention is selected from that having a~ least 25 ~ by weight of polymer unit derived from monomer of the formula~
F~ - C = CH2 0~
~ (Z)p '~:
~i6~3~
wherein R is a hydrogen atom, a lower alkyl gr~up such as C1 4 alkyl group, or a halogen atom; Z is a hydrogen atom, a vinyl group, a halogen atom, a hydroxyl group or a lower alkyl group; and p is zero or an integer of 1 - 5.
Exa~ples of the alkenyl aromatic resin are homo-polymer such as polystyrene, polychlorostyrene and poly~ -methylstyrene, copolymer of such polymer and styrene--conta.in-ing copolymer such as ~yrene-acrylonitrile copolymer, styrene-divinylbenzene copol~ner and styrene-acrylonitrile-~-methyl-styrene copolymer. Preferable ones are homopolystyrene, styrene-a-methylstyrene copolymer, styrene-acrylonitrile copolymer, styrene-a-chlorostyrene copolymer and styrene-methylmethacrylate copolymer. The most preferable one is homopolystyrene.
Rubber modified alkenyl aromatic resin in the presen invention is two phase one in which rubbe:r particles are dispersed i.n an alkenyl aromatic resin matrix. Method preparing thereof is mechanical mixing of rubber and alkenyl aromatic resin disclosed hereinafter~ or one in which .rubber is dissolved in alkenyl. aromatic monomer and then the alkenyl aromatic resin is polymerized. The latter method is commercially carried out for pr2paring high impact poly-styrene.
The rubber modified alkenyl resin in the present invention further includes a mixture oE polystyrene obtained by the latter method above and rubber and/or alkenyl aromatic resin.
~ ubber and rubbery polymer in the present invention means natural or artl*icial pol~ner w~ich is elastic at room temperature, for e~ample, 20 - 25 C. Examples are natural rubber; diene ~u~er, for instance, polybutadiene, pol.yisoprene and polychloroprene; copolymer of diene and vinyl monomer, for instance, styrene-butadiene randor.l copoly-mer, styrene--butadiene block copolymer, styrene-butadiene-styrene block copol~mer, styren~ grafted polybutadiene,butadiene-acrylonitxile copolymer; polyisobutylene, isobutylene-b~tadiene or -isoprene copolymex, ethylene-propylene copolymer, ethylene--propylen~-diene copolymer, "Thiokol" rubber, polysulfide rubbex, acrylic rubber, polyurethane rubber, polyether rubber, and epichlorohydrin rubber. Furthermore, it includes various rnodified ones of the rubber mentioned above, for example, hydroxy or carboxy ~erminal terminated polybutadiene, partially hydrogenated styrene-butadiene-styrene block copolymer. Diene rubber and diene-vinyl compound copolymer in which micro-structure in double bond is varied, i.e., vinyl group, cis-1,4-bondin~ and trans 1,4-bonding,are also employed as rubber or rubbery polymer in the present invention.
Preferable rubber and rubbery polymer is copolymer of butadiene (40 - 100 parts by weight) and styrene (60 - 0 par~ by weight), copolymer of butadiene (65 - 82 parts by weight) and acrylonitrile (35 - 18 parts by weight), styrene-butadiene or styrene-butadiene-styrene block copolymer including linear block copolymer, radial block copol~ner and other similar block copolymer~ styrene-grafted polybutadiene prepared by adding styrene to polybutadiene latex or butadiene-styrene copolymer latex and emulsion polymerizirlg in the presence of a radical initiator, ethylene-propylene copolymer and ethylene-propyléne-diene copolymer.
Polyphenylene oxide and alkenyl aromatic resin and/cx rubber modified alkenyl aromatic resin may be mixed with any ratios. Polyphenylene oxide is preferably 5 % by weight or more, mor~- prc~erably 20 ~ by weight or more.
Polyphenylene oxide and rub~ery polymer may be mixed with any ratios, ~oo, but polyphenylene oxide is about 50 % by w~ight or more, preEerably 70 % by weight or more, when it i8 used as plastics.
(B~ The ethylene copolymer moiety in the present invention .is one i~ which monomers are ethylene, alkyl est~x of u,~ unsaturated carboxylic acid and maleic anhydride and ethylene is 50 - 90 % by weight, preferably 60 - 85 ~ by weight, alkyl es~er of ~ unsaturated carbo~ylic acid is 33&~
5 - 49 % by weight, preferably 7 - 45 % by weight and maleic anhydride is 0.5 - 10 % by weigh-t, preferably 1 - 8 -~ by weight.
Alkyl ester of a, ~unsatorated carboxylic acid is 5 alkyl ester of C3 ~ unsaturatad carboxylic aicd, such as acrylic acid and methacrylic acid~ ExamplPs are methyl acrylat~, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n butyl acrylate,t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl meth-acrylate and isobutyl methacrylate, preferably ethyl acrylate, n-butyl acrylate and methyl methacrylate.
Thexe is no limitation on mi~ing ratio oE ~A) and (B) components in the present invention and the ratio is decided depending on obj~cts thereforO (B) component, for example, i~ changeable within the range of 0.5 - 99.S ~ by weight.
Preferable mixing ratio depending on objects Of the composition is that, for example, a composition compri.sing (A) polyphenylene oxide resin or polyphenyl~ne oxide/alkenyl aromatic ~esin and (B) ethylene/alkyl ester of a,~-unsaturated carboxylic acid/maleic anhydride copolymer, should contain preferably 3 - 30 % by weight, more preferably 5 - 20 ~ by weight of (B) cornponent, when the composition is employed as ~5 high impact en'gineering plastic.
The comp~sition above has unexpectedly high impact resi~tance an~ there is no decrease in the impact resistance even when it is molded at high temperature.
A compo6i.t.ion comprising (A) polyphenylen~ cxide resin, allcenyl aromatic resin and rubbery polymer and (B~
ethylene/alkyl ester of ~ unsaturated carboxylic acid/maleic anhydride ~hould contain 0.5 - 20 % by weight, preferably 1 10 ~ by weight of (B) component, although the amount is variable depending on an amount of rubbery polymer in (A) component, when the compo~ition is employed as high impact engineering plastic. There is a remarkable improvement in l.~
~6~
.impact resistaxlce even iE an amount of (B) component in the above composition is small.
A composition cornprising (A) polyphenylene oxlde resin, or polypheylane oxide/alkenyl aromatic resin or polyphenylene oxide/alkenyl aromatic xesin/rubbery polymer and (B) 2thylene copolymer of ethylerle/alkyl ester of ~
unsaturated carboxylic acid/maleic anhydride and lnorganic fillers such as glass fib~r, calcium carbonate, silica, zinc oxide and TiO2, should contain 1 - 40 ~ by weight, preferably 5 - 30 % by weight of (B) component on the basis of the total of (A) and (B) components. Mechanical properties such as impact resistance are lowered when no ~B) component is contained in the composition, but the presence of (B) component dissolves this problemO
The examples ment.ioned above are only a few examples of desirable embodiment of the present invention and are able to change widely depending on objscts and uses of the compositions.
Furthermore, the (B) cornponent copolyme~ in the 2~ present invention may include other vinyl comonomer. Examples of such vinyl comonomer are styrene, vinyl acetate, vinyl chloride, a-methylstyrene, divinylbenzene, tetrafluoro-ethylene, difluoroethylene, vinylidene chloride, acrylonitrile and acrylic amide.
Any process is employed to prepare the present compositon. A usual process known is adopted. A proc~ss preferably f.rom an economical point of view is dry blending the components in a mixer such as a Hensch~l mixer and ~hen melt-kneading and extruding the mixture.
There are no critical limitations to temperature and period of time when melt-kneading is carried out.
Tempexature is usually wi~hin the range of 150 ~ 350 C, which varies depending on composition ratio. Any process for melt-kneading is eff2cted as long as it is able to tre.at viscous melt, no matter whether it is batchwise or continuous.
Apparatuses therefox are a Ba~ury mix~r, a roll, an extrud~r
. , .~ .
6~3~
formula above ~ay be copolymerized with the other phenols than that of the above formula, e.g., polyv~lent hydroxy ~romatic compound, as of bis-phenol A, te~rabromobisphenol A, resorci~ hydroguinone and novolalc resin.
PreEerable polymers are homopolymer o~ 2~6-dimethyl-phenol or of 2,6-diphenylphenol and copolymer of a large amount of 2,6-xylenol and a small amount of 3-methyl~6--t-butylphenol or 2~3,6-trimethylphenol.
Any oxidation polycondensation catalyst for oxidation polymerization of phenol compound may be employed as long as it has polymerization ability. For instance, mention may be made of a catalyst of cuprous salts and tertiary amines such as cuprous chloride-triethylamine and cuprous chlorid2-pyridine;
a catalyst of cupric salts-amino-alkali metal hydroxides such as cupric chloride-pyridine-potassium hydroxid2; a catalyst of manganese salts and primary amines such as manganese chlorid~-ethanolamine and manganese acetate-ethylenediamine; a c~talyst of manganese salts and alcoholates or phenolates such as manganese chloride-sodium methylate and manganese chloride-sodium phenolate, a combination catalyst of cobalt salts and tertiary amines.
Furthermore, polyphenylene oxide resin in the present invention includes polyphenylene oxide ~bove grafted with styrene polymer or other polymers. The resin is prepared by organic pero~ide graft polymerization of styrene monomer and/or other polymerizable monomer in the presence of poly-phenylene oxide (Japanes0 published examined patent application Nos. 47862/1972, 12197/1973, 5623/1974, 38596/1977, 30991/1977 etc.) or melt kneading the polyphenylene oxide, polystyrene and a radical initiator (Japanese published unexamined patent application No~ 142799/1977 ~ .
The resin compo~itio~ (A) containing polyphenylene oxide in the present inventi.on is th~t consisting of the polyphenylene oxide and one or more other high molecular weight compounds. The high molscular weight compound includes polyol~fin~ cuch a~ polyethylene, polypropylene, ethylene-pxopylene ~' 33~
block copolyn~er, pol~methylpentene, ethylene-a-olefin copolymer; homopolymers or copolymers such as polyvi~yl ~hloride, polymethylmethacrylate, polyvinyl acetate, polyvinyl pyricline, polyvinyl carbazole, polyacrylamide, polyacrylonitrile, ethylene-vinyl acetate copolymer and alkenyl aromatic resin polycarbonate; polysulfone; polyethylene terephthalate;
polybutylene terephthalate; polyallylene ester (for e~ample, "U-polymer" manufactured by Yunichika K.K.); polyphenylene sulfide;polyamides ~uch as 6-nylon, 6,6~nylon and 12-nylon;
condensed high molecular compounds such as polyacetal; and rubbery pol~mer. Furthermo~e, mention may be made of various thermosetting resins ~uch a~ silicone resin, fluorine resin, polyimido, polyamidoimido, phenol resin, alkyd resin, unsaturated polyester re~in, epoxy resin and "Dapon"~ esin~
Ihe mixing ra~o of polyphenylene oxide and other high ~Dlecular compounds may widely be ~elected within the range of, for ~xample, 1 - 99 % by weight of polyphenylene oxide and 99 - 1 ~ by weight of the other h.igh molecular compounds. Optimum ratio depends on object and use of the mixture within the range.
It is easy for the skilled in ~he art to decide th~
optimum rat.io.
Preferable other high molecular compound is poly-olefln, polyamide, alkenyl aromatic resin, rubber modified alkenyl aromatic resin and r~bbery po].ymer.
The most preferable high molecular compound is alkenyl aromatic resin, rubber modified alkenyl aromatic resin and rubbery polymer.
Alkenyl aromatic resin in the present invention is selected from that having a~ least 25 ~ by weight of polymer unit derived from monomer of the formula~
F~ - C = CH2 0~
~ (Z)p '~:
~i6~3~
wherein R is a hydrogen atom, a lower alkyl gr~up such as C1 4 alkyl group, or a halogen atom; Z is a hydrogen atom, a vinyl group, a halogen atom, a hydroxyl group or a lower alkyl group; and p is zero or an integer of 1 - 5.
Exa~ples of the alkenyl aromatic resin are homo-polymer such as polystyrene, polychlorostyrene and poly~ -methylstyrene, copolymer of such polymer and styrene--conta.in-ing copolymer such as ~yrene-acrylonitrile copolymer, styrene-divinylbenzene copol~ner and styrene-acrylonitrile-~-methyl-styrene copolymer. Preferable ones are homopolystyrene, styrene-a-methylstyrene copolymer, styrene-acrylonitrile copolymer, styrene-a-chlorostyrene copolymer and styrene-methylmethacrylate copolymer. The most preferable one is homopolystyrene.
Rubber modified alkenyl aromatic resin in the presen invention is two phase one in which rubbe:r particles are dispersed i.n an alkenyl aromatic resin matrix. Method preparing thereof is mechanical mixing of rubber and alkenyl aromatic resin disclosed hereinafter~ or one in which .rubber is dissolved in alkenyl. aromatic monomer and then the alkenyl aromatic resin is polymerized. The latter method is commercially carried out for pr2paring high impact poly-styrene.
The rubber modified alkenyl resin in the present invention further includes a mixture oE polystyrene obtained by the latter method above and rubber and/or alkenyl aromatic resin.
~ ubber and rubbery polymer in the present invention means natural or artl*icial pol~ner w~ich is elastic at room temperature, for e~ample, 20 - 25 C. Examples are natural rubber; diene ~u~er, for instance, polybutadiene, pol.yisoprene and polychloroprene; copolymer of diene and vinyl monomer, for instance, styrene-butadiene randor.l copoly-mer, styrene--butadiene block copolymer, styrene-butadiene-styrene block copol~mer, styren~ grafted polybutadiene,butadiene-acrylonitxile copolymer; polyisobutylene, isobutylene-b~tadiene or -isoprene copolymex, ethylene-propylene copolymer, ethylene--propylen~-diene copolymer, "Thiokol" rubber, polysulfide rubbex, acrylic rubber, polyurethane rubber, polyether rubber, and epichlorohydrin rubber. Furthermore, it includes various rnodified ones of the rubber mentioned above, for example, hydroxy or carboxy ~erminal terminated polybutadiene, partially hydrogenated styrene-butadiene-styrene block copolymer. Diene rubber and diene-vinyl compound copolymer in which micro-structure in double bond is varied, i.e., vinyl group, cis-1,4-bondin~ and trans 1,4-bonding,are also employed as rubber or rubbery polymer in the present invention.
Preferable rubber and rubbery polymer is copolymer of butadiene (40 - 100 parts by weight) and styrene (60 - 0 par~ by weight), copolymer of butadiene (65 - 82 parts by weight) and acrylonitrile (35 - 18 parts by weight), styrene-butadiene or styrene-butadiene-styrene block copolymer including linear block copolymer, radial block copol~ner and other similar block copolymer~ styrene-grafted polybutadiene prepared by adding styrene to polybutadiene latex or butadiene-styrene copolymer latex and emulsion polymerizirlg in the presence of a radical initiator, ethylene-propylene copolymer and ethylene-propyléne-diene copolymer.
Polyphenylene oxide and alkenyl aromatic resin and/cx rubber modified alkenyl aromatic resin may be mixed with any ratios. Polyphenylene oxide is preferably 5 % by weight or more, mor~- prc~erably 20 ~ by weight or more.
Polyphenylene oxide and rub~ery polymer may be mixed with any ratios, ~oo, but polyphenylene oxide is about 50 % by w~ight or more, preEerably 70 % by weight or more, when it i8 used as plastics.
(B~ The ethylene copolymer moiety in the present invention .is one i~ which monomers are ethylene, alkyl est~x of u,~ unsaturated carboxylic acid and maleic anhydride and ethylene is 50 - 90 % by weight, preferably 60 - 85 ~ by weight, alkyl es~er of ~ unsaturated carbo~ylic acid is 33&~
5 - 49 % by weight, preferably 7 - 45 % by weight and maleic anhydride is 0.5 - 10 % by weigh-t, preferably 1 - 8 -~ by weight.
Alkyl ester of a, ~unsatorated carboxylic acid is 5 alkyl ester of C3 ~ unsaturatad carboxylic aicd, such as acrylic acid and methacrylic acid~ ExamplPs are methyl acrylat~, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n butyl acrylate,t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl meth-acrylate and isobutyl methacrylate, preferably ethyl acrylate, n-butyl acrylate and methyl methacrylate.
Thexe is no limitation on mi~ing ratio oE ~A) and (B) components in the present invention and the ratio is decided depending on obj~cts thereforO (B) component, for example, i~ changeable within the range of 0.5 - 99.S ~ by weight.
Preferable mixing ratio depending on objects Of the composition is that, for example, a composition compri.sing (A) polyphenylene oxide resin or polyphenyl~ne oxide/alkenyl aromatic ~esin and (B) ethylene/alkyl ester of a,~-unsaturated carboxylic acid/maleic anhydride copolymer, should contain preferably 3 - 30 % by weight, more preferably 5 - 20 ~ by weight of (B) cornponent, when the composition is employed as ~5 high impact en'gineering plastic.
The comp~sition above has unexpectedly high impact resi~tance an~ there is no decrease in the impact resistance even when it is molded at high temperature.
A compo6i.t.ion comprising (A) polyphenylen~ cxide resin, allcenyl aromatic resin and rubbery polymer and (B~
ethylene/alkyl ester of ~ unsaturated carboxylic acid/maleic anhydride ~hould contain 0.5 - 20 % by weight, preferably 1 10 ~ by weight of (B) component, although the amount is variable depending on an amount of rubbery polymer in (A) component, when the compo~ition is employed as high impact engineering plastic. There is a remarkable improvement in l.~
~6~
.impact resistaxlce even iE an amount of (B) component in the above composition is small.
A composition cornprising (A) polyphenylene oxlde resin, or polypheylane oxide/alkenyl aromatic resin or polyphenylene oxide/alkenyl aromatic xesin/rubbery polymer and (B) 2thylene copolymer of ethylerle/alkyl ester of ~
unsaturated carboxylic acid/maleic anhydride and lnorganic fillers such as glass fib~r, calcium carbonate, silica, zinc oxide and TiO2, should contain 1 - 40 ~ by weight, preferably 5 - 30 % by weight of (B) component on the basis of the total of (A) and (B) components. Mechanical properties such as impact resistance are lowered when no ~B) component is contained in the composition, but the presence of (B) component dissolves this problemO
The examples ment.ioned above are only a few examples of desirable embodiment of the present invention and are able to change widely depending on objscts and uses of the compositions.
Furthermore, the (B) cornponent copolyme~ in the 2~ present invention may include other vinyl comonomer. Examples of such vinyl comonomer are styrene, vinyl acetate, vinyl chloride, a-methylstyrene, divinylbenzene, tetrafluoro-ethylene, difluoroethylene, vinylidene chloride, acrylonitrile and acrylic amide.
Any process is employed to prepare the present compositon. A usual process known is adopted. A proc~ss preferably f.rom an economical point of view is dry blending the components in a mixer such as a Hensch~l mixer and ~hen melt-kneading and extruding the mixture.
There are no critical limitations to temperature and period of time when melt-kneading is carried out.
Tempexature is usually wi~hin the range of 150 ~ 350 C, which varies depending on composition ratio. Any process for melt-kneading is eff2cted as long as it is able to tre.at viscous melt, no matter whether it is batchwise or continuous.
Apparatuses therefox are a Ba~ury mix~r, a roll, an extrud~r
3~
and a kneader.
It is possible to add reinEorcing rnaterials such as glass fibers, carbon Eibers, an inorganic and organic fillers such as carbon black, silica and TiO2, plasticizers, stabi-lizers, fire retardants, dyes and pigments, when the presentinvention is practiced. Detail is given in reinforcing materials. They facilitate flexural strength, bending elasticity, tensile strength, tension elasticity and heat deformation temperature, and include alumina fibers, carbon fibers, glass fibers, high elastic polyamide fibers, high elastic polyester fibers, silicon carbide fibers and whisker titanata.
The amount of reinforcing material is, at least, that which i5 sufficient to facilitate reinforcement, but usually is within the range of abou~ 5-100 parts by wel~ht each 100 parts by weight of the present composition.
Preferably the reinforcing material is glass~ more ; preferably glas~ fiber filaments made from borosilicate glass of lime containing relatively small amount of sodiurn content/
aluminium. This is Xnown as "E" glass~ However, other gla6æes, for example one having low sodium content, which is known as "C" glass, may be used, when electrical properties are not so important. Filam2nts are pr~pared in a usual manner such as steam or air-blowing, fire-blow:ing or mechanical stretching. Preferable filament for reinforcing plastics is prepared by mechanical stretching. Filament is within about 2 - 20~lmin diameter, but thickness is not critical in the present invention. Length of filament is not critical, either.
3~ Furthermore, it i5 not critical whether glass filaments are bundled into an assembly and then the assemble is further bundled to the form of thread, a rope or lobing or they are woven to a mat. Howeve.r~ the gla~ fila~ent is preferably in the shape of a strand cut shortly to about 0.3 - 3 cm long, rnore prPferably not longer than abou~ 0.6 om lon~, when the present composition is prepared using the same.
., ~6~3~3~
Some discussion is made to a fire retardan~. A
material useful of the present invention includes a group of compounds familiar to the ~rtisans.
Generally speaking, prefe.rabl~ compounds are thosa containing such elements as bromine, chlorine, antirnony~
phosphorus and nitrogen which give flame resistance. For instance, mention may be made of halogenated organic compounds, antimony oxide, antimony oxide/halogenated organic compounds, antimony oxide/phosphorus compourlds, phosphorus alone or phosphorus compounds, phosphorus compounds or compounds having phosphorus-nitrogen bonding/halogen-containing compounds or a mixture of the above.
Theamount o:E a fire retard~nt is not critical but that which is able to give flame resistance is ~nough. An excessiv~
amount is not desirabla because physical properties are degraded, such as lowering in softening point. It is easy for the artisan to decide the proper amount thereof. Flame ratar~ant is usually added in such an amount of 0~5 - 50 parts by weight, preferably 1 - 25 parts by weight, more preferably 3 - 15 parts by wei~At each 100 parts by weight of a mixture of polyphenylene oxide resin and rubber modified alkenyl aromatic resin.
One of useful halogen-containing compounds is ~ (,Y) ~ (~)e~ ~ (Y)d~ 1 l Ar ~ R ~ ~r~ J
wherein n is 1 - 10; R is selected from a group of an alkylene group, an alkyliderle group or an alicyclic bond group such as methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene~ cyclohe~ylene or cyclo-pentyridene, an ether yroup, a carbonyl group, an amine yroup, a sulfur-containing bond group such as sulEide, sulfo~ide or su1fone, ~ carbonate group or a phosphorus-containing groupO
R may be a group having two or more alkylene or alkylidene honds bound by such groups as aromatic, amino, ether, estert carbonyl, sulfide, sulfoxid~, sulfone or ~ phosphorus-'~
~2~6~ 3~
con-taining groupO
Ar and Ar' are monocyclic or polycyclic carbon cyclic aromatic group, such as phenylene, biphenylene, ter phenylene, naph~hylene, etc.
Ar and Ar' may be same or different.
Y is a substituent ~elected from organic, inorganic or organometallic group. Substituent represented by Y is Il) a halogen, such as chlorine, bromine, iodine or fluorine;
(2) an ether group of the formula OE wherein E is the similar monovalent hydrocarbon group to X defined below; (3) an -OH
group; (4) a monovalent hydrocarbon gro~p represented by R or (5) other substituent, such as a nitro group or a cyano group. Y may be same or different when d is 2 or more.
X is a mono~alent hydrocarbon group including an 15 alkyl group such as methyl, ethyl, propyl, isopropyl~ butyl or decyl; an aryl group such as phenyl, naphthyl, biphenyl, xylyl or tolyl; an aralkyl group such as benzyl or ethylphenyl, a cyclo aliphatic group such as cyclopentyl or cyclohexyl;
or a monovalent hydrocarbon group containing unfunctional substituents. X may be same or different when 2 or more Xs are used~
d i~ an integer from one to the ma~imum which is equal to the maximum numb~r of substituable hydrogen atoms on 2romatic ring of Ar or Ar'. e is from zero to an integer up to the maximum'which depends on number of substituable hydrogen atoms on Ro a, b and c are integers including zero. Neither a nor c is zero when b is not zero. Unless otherwise, either a or c may be zero. Aromatic groups bond each other directly by C-C ~ when b is ~,ero. ~xyl group or substit1lent y may p~sition at any of o-, m- or p on the aromatic rings ~r ~ Prl.
Examples of the compounds ha~ing the formula above are 2, 2-bis ~ 3 ~ 5 dichlorophenyl ) ~propane, bis(2-chlorophenyl)-methane, 1,2-bis(2,6-dichlorophenyl)-e~hanP, 1,1-bis(4-iodo-phenyl)-ethane, l,l-bis(2-chloro--4-iodophenyl)-ethane, 1,1-~, bis(2-chloro-4--methylphenyl)-ethane, 1,1-bis(3,5-dichloro-phenyl~-ethane, 2,2-bis(3 phenyl-4-bromophenyl)-~thane, 2 ~6~3~D
2,3-bis(4,6-dichlorollaphthyl)-propane, 2,2-bis(2,6-dichloro-phenyl)-pentane, 2,2-bis(3,5-dichlorophenyl)-hexane, bis(4-Chlor~phenyl)phenylmethane bis(3~5-dichlorophenyl)-cyclo-hexylmethane, bis(3-nitro-4-bromophenvl)-methane, bis(4-o~y-5 2,6-dichloro-3-metho~yphenyl)-methane, 2,2-bis(3,5-dibromo-4~
oxyphenyl)-propane, 2,2-bis~3,5-dichloro-4-oxyphenyl)-prop~ne, 2,2-bis(3-bromo-4-oxyphenyl)-propane; such bisaroma~ic compounds as those wherein sulfide o.r sulfoxy group is used in place of the two aliphatic groups in the compounds listed above; tetrabromobenzene, hexachlorobenzene, hexabromobenzene, 2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, 2,4'-dichloro-biphenyl, hexabromobiphenyl, octabromobiphenyl, decabromo-biphenyl, halogPnated diphenylether having 2 - 10 halogen atoms and oligomer having 1-20 of polymerization degree of 15 polycondensate between 2,2-bis(3,5-dibromo-4-oxyphenyl)-propane and phosgen.
Prefer~ble halogen compounds in the present invention are aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated ter-phenyl, brominated biphenyl and brominated terphenyl;compound containing two phenyl groups apart by a bival~nt alkylene group and having at least two chlori.ne or bromine atoms per phenyl group or a mixutre of at least two of the compounds a~ove. More preferable are hexabromobenzene;
2S and chlorinat~d-biphenyl or -terphenyl with or without antimony oxide~
A preferred phosphoru~ compound u~able in the present invention has the following ~ormula O
Q -- O -- P -- o -- Q
o I
; 35 ~, ' ,~
3~j and analogous ni-trogen compound. In -the formula above, Q is same or different and is selected from a hydrocarbon group of alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-sub-stituted alkyl; a halogen atom, a hydrogen atom and a combi-nation thereof. PreEerable ester oE phosphoric acid is phenyl-bisdodecyl phosphate, phenyl-bis-neopentyl phosphate, phenylethylene hydrogenphosphate, phenyl-bis(3,5,5'--trimethyl-hexyl)phsophate, ethyldiphenyl phosphate, 2-ethylhexyl-di--(p-tolyl)phosphate, diphenyl hydrogenphospha-te, bis(2-e-thyl-hexyl)-p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl)phosphate, phenylmethyl hydrogenphosphate, di(dodecyl)-p-tolyl phosphate, triphenyl phosphate, halogenated triphenyl phosphate, dibutylphenyl phosphate, 2-choroethyldiphenyl phospha-te, p-tolylbis(2,5,5'--trimethylhexyl)phosphate, 2-ethylhexyldiphenyl phosphate and di~henyl hydrogenphosphate. More preferable phosphate is triphenyl phosphate. Triphenyl phosphate may preferably be used with hexabromobenzeneO Triphenyl phosphate may also be used with antimony oxide.
Othex flame retardant is a compound having phosphorus-nitrogen bond such as phosphorus nitride chloride, phosphoxus ester amide, phosphoric acid amide, phosphinic acid amide, tris(aziridinyl)phosphine oxide, or tetrakis(oxymethyl) phosphonium chloride.
The present invention is explained referring to examples but these are only examples and do not restrict the prese.nt invention thereto.
~ rison examples 1 - 3 Polyphenylene oxide ([n] = 0.55, in CHC13, 25 C) obtained by oxidation polycondensation of 2,6-xylenol and ethylene/ethyl acrylate/maleic anhydxide copolymer (65/30/5 by weight, MI = 20 g/10 min.) were melt kneaded in a laboplas-t mill (manufactured by Toyo Seiki) with the ratios mentioned in Table 1. Compositions (kneadi.ng temperature was about 270 C) were compression molded to pr~pare test pieces for Izod i.mpac~ strength and tho~e for load deformation temperature.
~%~6~3~
I70d impact strength and load deforrnation temperature were observed according to JIS K 7110 and K 7207, respect:ively.
For comparison~ lo~ density polyethylene ("S~ka~ene"~
F 101-1, prepared by Surnitomo Chemical Company, L,imited) was used in place of the ethylene/ethyl acrylate/maleic anhydride and Izod impact strength and load deformation ternperature were similarly observed to those as in the examples.
Table 1 shows the results.
As is apparent from Table 1, impac~ strengths of compositions of polyphenylene oxide and polyethylene in comparison examples are low but those of the present compositions of polyphenylene oxide and ethylene/ethyl acrylate~maleic anhydride are very high and no lowering in load deformation temperature is seen in the latter~ This substantiates the fact that compatibility with polyphenylene oxide is good for the presPnt compositon.
Examples 3 - 5 and comparison example 4 Polyphenylene o~ide used in Example 1, high impact polystyrene~ ("Bsbrite'~ 500A, manufactured by Nippon Poly-styrene Co. Ltd.) and ethylene/ethyl acrylate/rnaleic anhydride copolymer used in Example 1 were melt kneaded in a laboplast mill as in Example 1 and Izod impact strength was cbserved.
Table 2 S2l0Ws cornposition ratio of respective resins and Iæod impact strength.
For comparison, no ethylene/ethyl acrylat~maleic anhydride copolymer was used.
Table 2 shows that increase is observed in impac-t strength by incoxporating a small amouilt of ethylene/ethyl acrylate/n~leic anhydride copolymer in a composition of polyphenylene and rubber modiied polystyrene~
Examples 6 - 7 Polyphenylene oxide (90 parts by weight) used in Example 1 and ethylene/alkyl ester of a,~-ur~aturated carboxylic acid/maleic anhydride copolymer (10 parts by weight) having composition as in Table 3 were melt ~neaded as in Exatnple 1 and I~od impact strength and load deforrnation *I~ademarks 6~3~ 3~i temperature were observed. Table 3 shows the resl~lts.
As explained above, the present thermoplastic resin composition clisplays remarkable eEfects in respect of well-balanced properties of shaped articles as well as good processability.
Novel resin composition provided by the present invention may be easily shaped into articles by ~haping processes familiar to usual polyphenylene o~ide thermoplastic resin, such as injection molding, extrusion molding, etc. to provide articles having good and uniform appearance as well as well-balanced properties in impact resistance, heat resist-ance and hardness.
3~
_ _ _ . ___ __ ~' ~ e .~
~ ~ O .,~ O .,. .,, O
h a~ ~ O~ L/l O~ co ~-1 -- ~1 ~-1 r-l r-o a) ~ ,~
~_ _ . .. __ _~___ _ a~
rl tJ~ Ll ) r-l ~ r~
o ~ Lf) ~ ~r O ~ O ~ ~Y) r~l N ~) ~
~ U~
__ __ _ _______ _ _~
a .
__ U~
Q~
I l I ~ O
3 r-l r~l ~1 ~4 ~ ._ ._ _ __ ... .___ __ r u~ ,~
E~
CLI ~ q) h ~r~ a) ~ h O O 3 -lJ ~ l ~ r-l r~
Il) ~ 1 0 S~ ~ q 0 .. _ _ _ __ .. _ V ~ O O 0 r-i ~r~ SJ~ t~ r l _~X _ __ ___ / ~
/ ~ ~ u~ m tn / a~ a~ ~
/ r-l r-l ~ r-l S-l r-l ~ r l / Ql ~ 1~
/ ~ ~ ~
/ ~ X 0~ 0~ OX
/ ~ ~ V ~ V ~
~_ ._ .. _ _ ______.___ 33~
. _ _ . _ ___ _ _ E~ ~ ~ ~ ~ o r--I
o~
r~
O ~1 0 N IJ 1: ~;
1~
- .__ ___ ,~ ~
R r r-l r ~ ~ C~ 0 0 ~
~ __ __ O _ _ ___ ~) r U S
_, ~ ~
S~ ~ ~
E-1 ~ ~r-l ~1 O O O C::l ~ L~ Ll-~ L~ ~1 .1 O .. ~____ _____ _ ~.. ___ ~ O C~l O ~
~; 11"1 Ll~ Ln Ln ~0 'X
I O
_ __7 __ __ / ~
/ ~ ~ U~ o~
~; / ~ l r-l / ~ C,~l ~
' 3~
____ ~ U~
_ ._ __ ,... .. ~ _ ,~ ~U~
~ ~ ..
_ . ~. .
,, ~; oo .q ~0,l IUJ~ _ _ _ , , , d~ ~ 0 ~' ~ ,~, ,o~ .. ..
~_ ~ ___ /. ... .
/' ~
~ .. _ ._
and a kneader.
It is possible to add reinEorcing rnaterials such as glass fibers, carbon Eibers, an inorganic and organic fillers such as carbon black, silica and TiO2, plasticizers, stabi-lizers, fire retardants, dyes and pigments, when the presentinvention is practiced. Detail is given in reinforcing materials. They facilitate flexural strength, bending elasticity, tensile strength, tension elasticity and heat deformation temperature, and include alumina fibers, carbon fibers, glass fibers, high elastic polyamide fibers, high elastic polyester fibers, silicon carbide fibers and whisker titanata.
The amount of reinforcing material is, at least, that which i5 sufficient to facilitate reinforcement, but usually is within the range of abou~ 5-100 parts by wel~ht each 100 parts by weight of the present composition.
Preferably the reinforcing material is glass~ more ; preferably glas~ fiber filaments made from borosilicate glass of lime containing relatively small amount of sodiurn content/
aluminium. This is Xnown as "E" glass~ However, other gla6æes, for example one having low sodium content, which is known as "C" glass, may be used, when electrical properties are not so important. Filam2nts are pr~pared in a usual manner such as steam or air-blowing, fire-blow:ing or mechanical stretching. Preferable filament for reinforcing plastics is prepared by mechanical stretching. Filament is within about 2 - 20~lmin diameter, but thickness is not critical in the present invention. Length of filament is not critical, either.
3~ Furthermore, it i5 not critical whether glass filaments are bundled into an assembly and then the assemble is further bundled to the form of thread, a rope or lobing or they are woven to a mat. Howeve.r~ the gla~ fila~ent is preferably in the shape of a strand cut shortly to about 0.3 - 3 cm long, rnore prPferably not longer than abou~ 0.6 om lon~, when the present composition is prepared using the same.
., ~6~3~3~
Some discussion is made to a fire retardan~. A
material useful of the present invention includes a group of compounds familiar to the ~rtisans.
Generally speaking, prefe.rabl~ compounds are thosa containing such elements as bromine, chlorine, antirnony~
phosphorus and nitrogen which give flame resistance. For instance, mention may be made of halogenated organic compounds, antimony oxide, antimony oxide/halogenated organic compounds, antimony oxide/phosphorus compourlds, phosphorus alone or phosphorus compounds, phosphorus compounds or compounds having phosphorus-nitrogen bonding/halogen-containing compounds or a mixture of the above.
Theamount o:E a fire retard~nt is not critical but that which is able to give flame resistance is ~nough. An excessiv~
amount is not desirabla because physical properties are degraded, such as lowering in softening point. It is easy for the artisan to decide the proper amount thereof. Flame ratar~ant is usually added in such an amount of 0~5 - 50 parts by weight, preferably 1 - 25 parts by weight, more preferably 3 - 15 parts by wei~At each 100 parts by weight of a mixture of polyphenylene oxide resin and rubber modified alkenyl aromatic resin.
One of useful halogen-containing compounds is ~ (,Y) ~ (~)e~ ~ (Y)d~ 1 l Ar ~ R ~ ~r~ J
wherein n is 1 - 10; R is selected from a group of an alkylene group, an alkyliderle group or an alicyclic bond group such as methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene~ cyclohe~ylene or cyclo-pentyridene, an ether yroup, a carbonyl group, an amine yroup, a sulfur-containing bond group such as sulEide, sulfo~ide or su1fone, ~ carbonate group or a phosphorus-containing groupO
R may be a group having two or more alkylene or alkylidene honds bound by such groups as aromatic, amino, ether, estert carbonyl, sulfide, sulfoxid~, sulfone or ~ phosphorus-'~
~2~6~ 3~
con-taining groupO
Ar and Ar' are monocyclic or polycyclic carbon cyclic aromatic group, such as phenylene, biphenylene, ter phenylene, naph~hylene, etc.
Ar and Ar' may be same or different.
Y is a substituent ~elected from organic, inorganic or organometallic group. Substituent represented by Y is Il) a halogen, such as chlorine, bromine, iodine or fluorine;
(2) an ether group of the formula OE wherein E is the similar monovalent hydrocarbon group to X defined below; (3) an -OH
group; (4) a monovalent hydrocarbon gro~p represented by R or (5) other substituent, such as a nitro group or a cyano group. Y may be same or different when d is 2 or more.
X is a mono~alent hydrocarbon group including an 15 alkyl group such as methyl, ethyl, propyl, isopropyl~ butyl or decyl; an aryl group such as phenyl, naphthyl, biphenyl, xylyl or tolyl; an aralkyl group such as benzyl or ethylphenyl, a cyclo aliphatic group such as cyclopentyl or cyclohexyl;
or a monovalent hydrocarbon group containing unfunctional substituents. X may be same or different when 2 or more Xs are used~
d i~ an integer from one to the ma~imum which is equal to the maximum numb~r of substituable hydrogen atoms on 2romatic ring of Ar or Ar'. e is from zero to an integer up to the maximum'which depends on number of substituable hydrogen atoms on Ro a, b and c are integers including zero. Neither a nor c is zero when b is not zero. Unless otherwise, either a or c may be zero. Aromatic groups bond each other directly by C-C ~ when b is ~,ero. ~xyl group or substit1lent y may p~sition at any of o-, m- or p on the aromatic rings ~r ~ Prl.
Examples of the compounds ha~ing the formula above are 2, 2-bis ~ 3 ~ 5 dichlorophenyl ) ~propane, bis(2-chlorophenyl)-methane, 1,2-bis(2,6-dichlorophenyl)-e~hanP, 1,1-bis(4-iodo-phenyl)-ethane, l,l-bis(2-chloro--4-iodophenyl)-ethane, 1,1-~, bis(2-chloro-4--methylphenyl)-ethane, 1,1-bis(3,5-dichloro-phenyl~-ethane, 2,2-bis(3 phenyl-4-bromophenyl)-~thane, 2 ~6~3~D
2,3-bis(4,6-dichlorollaphthyl)-propane, 2,2-bis(2,6-dichloro-phenyl)-pentane, 2,2-bis(3,5-dichlorophenyl)-hexane, bis(4-Chlor~phenyl)phenylmethane bis(3~5-dichlorophenyl)-cyclo-hexylmethane, bis(3-nitro-4-bromophenvl)-methane, bis(4-o~y-5 2,6-dichloro-3-metho~yphenyl)-methane, 2,2-bis(3,5-dibromo-4~
oxyphenyl)-propane, 2,2-bis~3,5-dichloro-4-oxyphenyl)-prop~ne, 2,2-bis(3-bromo-4-oxyphenyl)-propane; such bisaroma~ic compounds as those wherein sulfide o.r sulfoxy group is used in place of the two aliphatic groups in the compounds listed above; tetrabromobenzene, hexachlorobenzene, hexabromobenzene, 2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, 2,4'-dichloro-biphenyl, hexabromobiphenyl, octabromobiphenyl, decabromo-biphenyl, halogPnated diphenylether having 2 - 10 halogen atoms and oligomer having 1-20 of polymerization degree of 15 polycondensate between 2,2-bis(3,5-dibromo-4-oxyphenyl)-propane and phosgen.
Prefer~ble halogen compounds in the present invention are aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated ter-phenyl, brominated biphenyl and brominated terphenyl;compound containing two phenyl groups apart by a bival~nt alkylene group and having at least two chlori.ne or bromine atoms per phenyl group or a mixutre of at least two of the compounds a~ove. More preferable are hexabromobenzene;
2S and chlorinat~d-biphenyl or -terphenyl with or without antimony oxide~
A preferred phosphoru~ compound u~able in the present invention has the following ~ormula O
Q -- O -- P -- o -- Q
o I
; 35 ~, ' ,~
3~j and analogous ni-trogen compound. In -the formula above, Q is same or different and is selected from a hydrocarbon group of alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-sub-stituted alkyl; a halogen atom, a hydrogen atom and a combi-nation thereof. PreEerable ester oE phosphoric acid is phenyl-bisdodecyl phosphate, phenyl-bis-neopentyl phosphate, phenylethylene hydrogenphosphate, phenyl-bis(3,5,5'--trimethyl-hexyl)phsophate, ethyldiphenyl phosphate, 2-ethylhexyl-di--(p-tolyl)phosphate, diphenyl hydrogenphospha-te, bis(2-e-thyl-hexyl)-p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl)phosphate, phenylmethyl hydrogenphosphate, di(dodecyl)-p-tolyl phosphate, triphenyl phosphate, halogenated triphenyl phosphate, dibutylphenyl phosphate, 2-choroethyldiphenyl phospha-te, p-tolylbis(2,5,5'--trimethylhexyl)phosphate, 2-ethylhexyldiphenyl phosphate and di~henyl hydrogenphosphate. More preferable phosphate is triphenyl phosphate. Triphenyl phosphate may preferably be used with hexabromobenzeneO Triphenyl phosphate may also be used with antimony oxide.
Othex flame retardant is a compound having phosphorus-nitrogen bond such as phosphorus nitride chloride, phosphoxus ester amide, phosphoric acid amide, phosphinic acid amide, tris(aziridinyl)phosphine oxide, or tetrakis(oxymethyl) phosphonium chloride.
The present invention is explained referring to examples but these are only examples and do not restrict the prese.nt invention thereto.
~ rison examples 1 - 3 Polyphenylene oxide ([n] = 0.55, in CHC13, 25 C) obtained by oxidation polycondensation of 2,6-xylenol and ethylene/ethyl acrylate/maleic anhydxide copolymer (65/30/5 by weight, MI = 20 g/10 min.) were melt kneaded in a laboplas-t mill (manufactured by Toyo Seiki) with the ratios mentioned in Table 1. Compositions (kneadi.ng temperature was about 270 C) were compression molded to pr~pare test pieces for Izod i.mpac~ strength and tho~e for load deformation temperature.
~%~6~3~
I70d impact strength and load deforrnation temperature were observed according to JIS K 7110 and K 7207, respect:ively.
For comparison~ lo~ density polyethylene ("S~ka~ene"~
F 101-1, prepared by Surnitomo Chemical Company, L,imited) was used in place of the ethylene/ethyl acrylate/maleic anhydride and Izod impact strength and load deformation ternperature were similarly observed to those as in the examples.
Table 1 shows the results.
As is apparent from Table 1, impac~ strengths of compositions of polyphenylene oxide and polyethylene in comparison examples are low but those of the present compositions of polyphenylene oxide and ethylene/ethyl acrylate~maleic anhydride are very high and no lowering in load deformation temperature is seen in the latter~ This substantiates the fact that compatibility with polyphenylene oxide is good for the presPnt compositon.
Examples 3 - 5 and comparison example 4 Polyphenylene o~ide used in Example 1, high impact polystyrene~ ("Bsbrite'~ 500A, manufactured by Nippon Poly-styrene Co. Ltd.) and ethylene/ethyl acrylate/rnaleic anhydride copolymer used in Example 1 were melt kneaded in a laboplast mill as in Example 1 and Izod impact strength was cbserved.
Table 2 S2l0Ws cornposition ratio of respective resins and Iæod impact strength.
For comparison, no ethylene/ethyl acrylat~maleic anhydride copolymer was used.
Table 2 shows that increase is observed in impac-t strength by incoxporating a small amouilt of ethylene/ethyl acrylate/n~leic anhydride copolymer in a composition of polyphenylene and rubber modiied polystyrene~
Examples 6 - 7 Polyphenylene oxide (90 parts by weight) used in Example 1 and ethylene/alkyl ester of a,~-ur~aturated carboxylic acid/maleic anhydride copolymer (10 parts by weight) having composition as in Table 3 were melt ~neaded as in Exatnple 1 and I~od impact strength and load deforrnation *I~ademarks 6~3~ 3~i temperature were observed. Table 3 shows the resl~lts.
As explained above, the present thermoplastic resin composition clisplays remarkable eEfects in respect of well-balanced properties of shaped articles as well as good processability.
Novel resin composition provided by the present invention may be easily shaped into articles by ~haping processes familiar to usual polyphenylene o~ide thermoplastic resin, such as injection molding, extrusion molding, etc. to provide articles having good and uniform appearance as well as well-balanced properties in impact resistance, heat resist-ance and hardness.
3~
_ _ _ . ___ __ ~' ~ e .~
~ ~ O .,~ O .,. .,, O
h a~ ~ O~ L/l O~ co ~-1 -- ~1 ~-1 r-l r-o a) ~ ,~
~_ _ . .. __ _~___ _ a~
rl tJ~ Ll ) r-l ~ r~
o ~ Lf) ~ ~r O ~ O ~ ~Y) r~l N ~) ~
~ U~
__ __ _ _______ _ _~
a .
__ U~
Q~
I l I ~ O
3 r-l r~l ~1 ~4 ~ ._ ._ _ __ ... .___ __ r u~ ,~
E~
CLI ~ q) h ~r~ a) ~ h O O 3 -lJ ~ l ~ r-l r~
Il) ~ 1 0 S~ ~ q 0 .. _ _ _ __ .. _ V ~ O O 0 r-i ~r~ SJ~ t~ r l _~X _ __ ___ / ~
/ ~ ~ u~ m tn / a~ a~ ~
/ r-l r-l ~ r-l S-l r-l ~ r l / Ql ~ 1~
/ ~ ~ ~
/ ~ X 0~ 0~ OX
/ ~ ~ V ~ V ~
~_ ._ .. _ _ ______.___ 33~
. _ _ . _ ___ _ _ E~ ~ ~ ~ ~ o r--I
o~
r~
O ~1 0 N IJ 1: ~;
1~
- .__ ___ ,~ ~
R r r-l r ~ ~ C~ 0 0 ~
~ __ __ O _ _ ___ ~) r U S
_, ~ ~
S~ ~ ~
E-1 ~ ~r-l ~1 O O O C::l ~ L~ Ll-~ L~ ~1 .1 O .. ~____ _____ _ ~.. ___ ~ O C~l O ~
~; 11"1 Ll~ Ln Ln ~0 'X
I O
_ __7 __ __ / ~
/ ~ ~ U~ o~
~; / ~ l r-l / ~ C,~l ~
' 3~
____ ~ U~
_ ._ __ ,... .. ~ _ ,~ ~U~
~ ~ ..
_ . ~. .
,, ~; oo .q ~0,l IUJ~ _ _ _ , , , d~ ~ 0 ~' ~ ,~, ,o~ .. ..
~_ ~ ___ /. ... .
/' ~
~ .. _ ._
Claims (3)
1. A thermoplastic resin composition comprising:
(A) polyphenylene oxide resin or a resin composition containing 1 - 99 parts polyphenylene oxide per 100 parts thereof; and (B) an ethylene copolymer comprising 50-90% by weight of ethylene, 5-49% by weight of an alkyl ester of an .alpha.,.beta.-unsaturated carboxylic acid, and 0.5-10% by weight of maleic anhydride.
(A) polyphenylene oxide resin or a resin composition containing 1 - 99 parts polyphenylene oxide per 100 parts thereof; and (B) an ethylene copolymer comprising 50-90% by weight of ethylene, 5-49% by weight of an alkyl ester of an .alpha.,.beta.-unsaturated carboxylic acid, and 0.5-10% by weight of maleic anhydride.
2. A thermoplastic resin composition according to claim 1 wherein the polyphenylene oxide resin is that obtained by oxidation polycondensation of one or two or more of phenols of the formula wherein R1, R2, R3, R4 or R5 is any of a hydrogen atom, a halogen atom, a hydrocarbon residue or a substituted hydrocarbon residue and one of them is a hydrogen atom.
3. A thermoplastic resin composition according to claim 1 wherein (A) resin composition containing polyphenylene oxide is one comprising polyphenylene oxide resin, and an alkenyl aromatic resin and/or rubbery polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60279917A JPS62138552A (en) | 1985-12-12 | 1985-12-12 | Thermoplastic resin composition |
| JP279917/85 | 1985-12-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1266936A true CA1266936A (en) | 1990-03-20 |
Family
ID=17617709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000524831A Expired - Fee Related CA1266936A (en) | 1985-12-12 | 1986-12-09 | Thermoplastic resin composition |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4740558A (en) |
| EP (1) | EP0229498B1 (en) |
| JP (1) | JPS62138552A (en) |
| BE (1) | BE1000662A5 (en) |
| CA (1) | CA1266936A (en) |
| CH (1) | CH673464A5 (en) |
| DE (1) | DE3679052D1 (en) |
| NL (1) | NL8701458A (en) |
| SE (1) | SE465827B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62199637A (en) * | 1986-02-28 | 1987-09-03 | Asahi Chem Ind Co Ltd | Hydrogenated block copolymer composition having improved oil resistance |
| DE3731457A1 (en) * | 1987-09-18 | 1989-03-30 | Basf Ag | THERMOPLASTIC MOLDING MATERIALS BASED ON STYRENE POLYMERISATS AND POLYPHENYLENE ETHERS |
| NL8801199A (en) * | 1988-05-09 | 1989-12-01 | Gen Electric | POLYMER MIXTURE CONTAINING A POLYPHENYLENE ETHER AND A POLYARYLENE SULFIDE. |
| JP2542686B2 (en) * | 1988-10-12 | 1996-10-09 | 三菱化学株式会社 | Resin composition |
| US5122578A (en) * | 1990-04-19 | 1992-06-16 | General Electric Company | Polyphenylene ether-polyarylene sulfide compositions |
| JP2856500B2 (en) * | 1990-04-21 | 1999-02-10 | 大倉工業株式会社 | Multi-layer heat-shrinkable film for packaging processed meat products and its package |
| JPH0488063A (en) * | 1990-07-30 | 1992-03-19 | Nippon Petrochem Co Ltd | Thermoplastic resin composition |
| JPH06345918A (en) * | 1993-06-10 | 1994-12-20 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL141540B (en) * | 1965-01-06 | 1974-03-15 | Gen Electric | PROCESS FOR PREPARING A POLYSTYRENE CONTAINING POLYMER MIXTURE WHICH CAN BE PROCESSED INTO PRODUCTS WITH HIGH BENDING AND TENSILE STRENGTHS, AS WELL AS SUCH PRODUCTS. |
| US3665058A (en) * | 1970-04-20 | 1972-05-23 | Uniroyal Inc | Modified polyphenylene oxide resin compositions |
| US4128602A (en) * | 1970-04-24 | 1978-12-05 | General Electric Company | Polyphenylene ether compositions containing rubber modified polystyrene |
| JPS5531442B2 (en) * | 1972-05-06 | 1980-08-18 | ||
| US4128603A (en) * | 1974-07-18 | 1978-12-05 | General Electric Company | Compositions comprising polyphenylene ether and rubber modified polystyrene |
| US4128604A (en) * | 1974-07-18 | 1978-12-05 | General Electric Company | Polyphenylene ether compositions |
| FR2314013A1 (en) * | 1975-06-11 | 1977-01-07 | Rouchaud Et Lamassiaude Ets | MACHINE FOR MILLING GEAR TEETH INPUTS |
| JPS5931534B2 (en) * | 1976-05-24 | 1984-08-02 | 旭化成株式会社 | Method for producing graft copolymer |
| JPS57108153A (en) * | 1980-12-25 | 1982-07-06 | Sumitomo Chem Co Ltd | Resin composition |
| JPS585356A (en) * | 1981-07-02 | 1983-01-12 | Eng Plast Kk | Novel resin composition |
| JPS5817142A (en) * | 1981-07-23 | 1983-02-01 | Eng Plast Kk | Novel resin composition |
| JPS58103556A (en) * | 1981-12-15 | 1983-06-20 | Mitsubishi Petrochem Co Ltd | Impact resistant polyphenylene ether composition |
| US4405753A (en) * | 1982-02-03 | 1983-09-20 | Monsanto Company | Polyblends |
| US4410651A (en) * | 1982-03-26 | 1983-10-18 | General Electric Company | Impact resistant polyphenylene ether resin compositions |
| DE3226427A1 (en) * | 1982-07-15 | 1984-01-19 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| JPS60200162A (en) * | 1984-03-23 | 1985-10-09 | Nissan Motor Co Ltd | Apparatus for measuring concentration of oxygen |
| JPS61123612A (en) * | 1984-11-20 | 1986-06-11 | Mitsubishi Petrochem Co Ltd | Ethylene copolymer |
-
1985
- 1985-12-12 JP JP60279917A patent/JPS62138552A/en active Granted
-
1986
- 1986-12-09 CA CA000524831A patent/CA1266936A/en not_active Expired - Fee Related
- 1986-12-11 DE DE8686309689T patent/DE3679052D1/en not_active Expired - Fee Related
- 1986-12-11 US US06/940,610 patent/US4740558A/en not_active Expired - Fee Related
- 1986-12-11 EP EP86309689A patent/EP0229498B1/en not_active Expired
-
1987
- 1987-06-19 CH CH2328/87A patent/CH673464A5/de not_active IP Right Cessation
- 1987-06-19 BE BE8700681A patent/BE1000662A5/en not_active IP Right Cessation
- 1987-06-22 SE SE8702583A patent/SE465827B/en not_active IP Right Cessation
- 1987-06-22 NL NL8701458A patent/NL8701458A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0229498B1 (en) | 1991-05-02 |
| BE1000662A5 (en) | 1989-03-07 |
| CH673464A5 (en) | 1990-03-15 |
| NL8701458A (en) | 1989-01-16 |
| SE8702583D0 (en) | 1987-06-22 |
| JPH0515747B2 (en) | 1993-03-02 |
| US4740558A (en) | 1988-04-26 |
| DE3679052D1 (en) | 1991-06-06 |
| EP0229498A1 (en) | 1987-07-22 |
| SE465827B (en) | 1991-11-04 |
| JPS62138552A (en) | 1987-06-22 |
| SE8702583L (en) | 1988-12-23 |
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