CA2060907A1 - Polyphenylene sulfide resin composition - Google Patents
Polyphenylene sulfide resin compositionInfo
- Publication number
- CA2060907A1 CA2060907A1 CA002060907A CA2060907A CA2060907A1 CA 2060907 A1 CA2060907 A1 CA 2060907A1 CA 002060907 A CA002060907 A CA 002060907A CA 2060907 A CA2060907 A CA 2060907A CA 2060907 A1 CA2060907 A1 CA 2060907A1
- Authority
- CA
- Canada
- Prior art keywords
- resin composition
- composition according
- polyphenylene sulfide
- amino
- weight
- 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.)
- Abandoned
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 75
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 74
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- -1 polyethylene Polymers 0.000 claims abstract description 56
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000004698 Polyethylene Substances 0.000 claims abstract description 38
- 229920000573 polyethylene Polymers 0.000 claims abstract description 38
- 239000000155 melt Substances 0.000 claims abstract description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 125000003277 amino group Chemical group 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- ODPYDILFQYARBK-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2SC2=C1 ODPYDILFQYARBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 35
- 238000001723 curing Methods 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003857 carboxamides Chemical class 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000001451 organic peroxides Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000001029 thermal curing Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical class OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- SOHCOYTZIXDCCO-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene Chemical compound C=1C2=CC=CC=1S2 SOHCOYTZIXDCCO-UHFFFAOYSA-N 0.000 claims 1
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 claims 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical group C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 32
- 238000000034 method Methods 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 18
- VZNUCJOYPXKLTA-UHFFFAOYSA-N 5-chlorobenzene-1,3-diamine Chemical compound NC1=CC(N)=CC(Cl)=C1 VZNUCJOYPXKLTA-UHFFFAOYSA-N 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZUVPLKVDZNDZCM-UHFFFAOYSA-N 3-chloro-2-methylaniline Chemical compound CC1=C(N)C=CC=C1Cl ZUVPLKVDZNDZCM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229920005570 flexible polymer Polymers 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- BEWIWYDBTBVVIA-PLNGDYQASA-N (z)-4-(butylamino)-4-oxobut-2-enoic acid Chemical compound CCCCNC(=O)\C=C/C(O)=O BEWIWYDBTBVVIA-PLNGDYQASA-N 0.000 description 1
- OZMRKDKXIMXNRP-FPLPWBNLSA-N (z)-4-(dibutylamino)-4-oxobut-2-enoic acid Chemical compound CCCCN(CCCC)C(=O)\C=C/C(O)=O OZMRKDKXIMXNRP-FPLPWBNLSA-N 0.000 description 1
- BZVFXWPGZHIDSJ-WAYWQWQTSA-N (z)-4-(diethylamino)-4-oxobut-2-enoic acid Chemical compound CCN(CC)C(=O)\C=C/C(O)=O BZVFXWPGZHIDSJ-WAYWQWQTSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- SFPQFQUXAJOWNF-UHFFFAOYSA-N 1,3-diiodobenzene Chemical compound IC1=CC=CC(I)=C1 SFPQFQUXAJOWNF-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- ZVUWTCKDIHCWAI-UHFFFAOYSA-N 1-chlorocyclohexa-3,5-diene-1,3-diamine Chemical compound NC1=CC=CC(N)(Cl)C1 ZVUWTCKDIHCWAI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- FUJSJWRORKKPAI-UHFFFAOYSA-N 2-(2,4-dichlorophenoxy)acetyl chloride Chemical compound ClC(=O)COC1=CC=C(Cl)C=C1Cl FUJSJWRORKKPAI-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- RVNUUWJGSOHMRR-UHFFFAOYSA-N 3,5-dibromoaniline Chemical compound NC1=CC(Br)=CC(Br)=C1 RVNUUWJGSOHMRR-UHFFFAOYSA-N 0.000 description 1
- DHYHYLGCQVVLOQ-UHFFFAOYSA-N 3-bromoaniline Chemical compound NC1=CC=CC(Br)=C1 DHYHYLGCQVVLOQ-UHFFFAOYSA-N 0.000 description 1
- RQKFYFNZSHWXAW-UHFFFAOYSA-N 3-chloro-p-toluidine Chemical compound CC1=CC=C(N)C=C1Cl RQKFYFNZSHWXAW-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- QZVQQUVWFIZUBQ-UHFFFAOYSA-N 3-fluoroaniline Chemical compound NC1=CC=CC(F)=C1 QZVQQUVWFIZUBQ-UHFFFAOYSA-N 0.000 description 1
- FFCSRWGYGMRBGD-UHFFFAOYSA-N 3-iodoaniline Chemical compound NC1=CC=CC(I)=C1 FFCSRWGYGMRBGD-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical class C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- WRZOMWDJOLIVQP-UHFFFAOYSA-N 5-Chloro-ortho-toluidine Chemical compound CC1=CC=C(Cl)C=C1N WRZOMWDJOLIVQP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000531908 Aramides Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical class CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08L81/04—Polysulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
A polyphenylene sulfide resin composition improved in the impact strength, toughness, high temperature resistance and solvent resistance properties is disclosed. The composition comprises (A) 60 - 99.5% by weight of a thermally cured polyphenylene sulfide material having a melt viscosity of 500 - 30,000 poises and which has been derived, by thermally curing, from a polyphenylene sulfide having a melt viscosity of 400 poises of higher and containing 0.05 - 5 mol% of amino groups on the basis of the phenylene sulfide repeating units, and (B) 40 - 0.5% by weight of a modified polyethylene material comprising at least one polyethylene onto which at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymerized in a proportion of 0.1 - 10%
by weight of the total weight of said modified polyethylene material.
A polyphenylene sulfide resin composition improved in the impact strength, toughness, high temperature resistance and solvent resistance properties is disclosed. The composition comprises (A) 60 - 99.5% by weight of a thermally cured polyphenylene sulfide material having a melt viscosity of 500 - 30,000 poises and which has been derived, by thermally curing, from a polyphenylene sulfide having a melt viscosity of 400 poises of higher and containing 0.05 - 5 mol% of amino groups on the basis of the phenylene sulfide repeating units, and (B) 40 - 0.5% by weight of a modified polyethylene material comprising at least one polyethylene onto which at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymerized in a proportion of 0.1 - 10%
by weight of the total weight of said modified polyethylene material.
Description
2~09~
POLYPHENYLENE SULFIDE RESIN CO~lPOSITION
BAC~GROU~D OF THE INVENTION:
1. Field of the Invention This invention relates to a resin composition comprising a specified class of polYphenYlene sulfides containing amino groups and a modified polyethylene on to which at least one unsaturated carboxylic acid and/or derivative thereof is graft-polYmerized and, more particularly, to such a composition exhibiting excellent impact, toughness, high-temperature resistance and solvent resistance properties.
2. Prior Art PolyphenYlene sulfide resins are known as a class of highly functional resins exhibiting excellent high-temperature resistance, fire retardance, chemical resistance, moldability, shapabilitY and electrical characteristics and the like, and recently are used widely in applications including the production of electrical and electronic parts, automotive parts, etc.
Polyphenylene sulfide resins maY be substantially improved in their properties such as strength, rigidity, high-temperature resistance, toughness, dimensional stability, etc., by incorporating them with fibrous reinforcements, such as glass fibers or carbon fibers, or inorganic fillers, such as talc, clay or mica. Generally, polyphenylene sulfide resins, however, suffer from a serious drawback that they exhibit poor ductility properties and are brittle as compared with other known engineering plastics such as nylons, polycarbonates, polybu~ylene terephthalate, polyacetals and the like. Therefore, polyphenylene sulfide resins have been excluded from usin~ in a certain, relatively wi.de range of applications.
Upto the date, it has been establis}led to im~rove the toughness or impact strengtll properties of polyphellylene sulfide by blending Witll a flexible pol~mer. ~or example, Japanese Patent Public Disclosure (I~OI~Al) No. a9-207921 discloses a method in ~YhiCh a polyphenylelle sulfide ma~erial i.s blended with an epoxy resin and a modified ~-olefin 2~0~0~
copolymeric elastomer having an unsaturated carboxylic acid or anhydride or a derivative thereof graft-copolymerized thereon. Further, methods comprising blending a polyphenYlene sulfide material with an ethylene-glycidyl methacrylate copolymer are known, for example, in Japanese Patent Public Disclosures Nos. 58-1547 and 59-152953.
However, the backbones of the ordinary polYphenylene sulfide molecules lack any effectively reactive site. Therefore.
even if a significantly reactive olefin copolymer is added to such an ordinary polyphenylene sulfide material, the added copolymer may exhibit only a poor adhesion or bonding at the interface between the additive and the polyphenylene sulfide material, resulting an unacceptable improvement in the impact resistance. Furthermore, there may be serious difficulties that the resulting blend shows deteriorated high-temperature resistance and solvent resistance properties.
On the other hand, various polyphenylene sulfide compositions have been proposed, which comprise poly-phenylene sulfide materials that have been treated withtechniques to improve the adhesion or bonding at the interface between the polyphenylene sulfide and a flexible polymer additive. Examples of the compositions of this type which may be mentioned include a composition comprising a polyphenylene sulfide that has been treated with an acid and washed, in combination with a modified olefin copolymer having an unsaturated carboxylic acid or anhydride graft-copolymerized thereon, see Japanese Patent Public Disclosure No. 62-169854; and a composition comprising a polyphenylene sulfide in combination with an olefin copolymer formed of an ~-olefin and a glycidyl ester of ~,~-unsaturated carboxylic acid, see Japanese Patent Public Disclosure No. 62-153343.
However, the impact resistance properties of polyphenylene sulfide cannot be acceptably improved even Wit}l these compositions.
Further, various polyphenylene sulfide compositions has been proposed, which comprise polyphenylene sulfide materials that have been modified ~vith techni4ues to 20~9~7 improve the adhesion or bonding at the interface between the polyphenylene sulfide and a flexible polymer additive.
An example which may be mentioned is a composition compris-ing an amino and/or amide-containing polyphenylene sulfide and a thermoplastic elastomer, see Japanese Patent Public Disclosure No. 61-207462. ~y this approach, the adhesion or bonding at the interface between the polyphenylene sulfide and the thermoplastic elastomer may be improved only to an extent that is unsatisfactorY in practice.
10 SUMMARY OF THE INVENTION:
An object of primary importance of the invention is to provide a polyphenylene sulfide resin composition that is significantly improved in the impact resistance and toughness properties and is substantially freed from the problems and difficulties experienced with the above-discussed prior art.
Accordingly, the present invention relates to a resin composition comprising a thermally cured, specific polyphenylene sulfide material modified by inclusion of amino groups in the molecule and which has a viscosity in a specified range before curing and another specified viscosity after curing, in conjunction with a modified polyethylene material on to which 0.5 - 10% by weight of at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymeri~ed. In the composition, the modified polyethylene material exhibits an enhanced adhesion or bonding at the interface between the polyphenylene sulfide and polyethylene materials and permits formation of a homogeneous dlspersion.
Accordingly, the invention provides a polyphenylene sulfide resin composition which comprises (A) 60 - 99.5% by weight of a thermally cured polyphenylene sulfide material having a melt viscosity of 500 - 30,000 poises and which has been derived, by thermally curing, from a polyphenylene sulfide having a melt viscosity of 400 poises or higher and containing 0.05 - S mol% of amino groups on the basis of the phenylene sulfide repeating units, and 3f~
~4-(B) 40 - 0.5% by weight of a modified polyethylene material comprising at least one polyethylene onto which at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymerized in a proportion of 0.1 - 10%
by weight of the total weight of said modified polyethylene material.
DETAILED DESCRIPTION OF THE INVENTION:
The invention will be described in more detail.
Preferably, the amino-containing polYphenylene sulfide material which is used in the present invention has an amino-group content of 0.05 - 5 mol% and, particularly, o-f 0.1 - 3 mol%. If the amino-group content is-less than 0.05 mol%, there is little advantage achieved by the inclusion of amino groups. If the amino-group content is greater than 5 mol%, then the advantageous effect by the inclusion of amino groups is undesirably offset by deterioration of the mechanical strength properties.
The amino-containing polyphenylene sulfide material which is used in the inventi.on should have a melt viscosity of not less than 400 poises, preferably not less than 500 poises before curing, as measured in a KOHKA type flow tester at 300C using an orifice of a 0.5 mm diameter and a 2 mm length under a load of 10 kg, and should have a melt viscosity in the range of from 500 to 30,000 poises, 25 preferably from 1,000 to 20,000 poi.ses after curing as measured simi.larly. If the polyphenylene sulride material has a melt viscosity of less than 400 poises before curing or a melt viscosity less than 500 poises af-ter curing, the intended improvement in the toughness properties of the composition is achieved only to an unsa-tisfactory extent. If the cured polyphenylene sulfide material has a melt viscosity of greater than 30,000 poises, then the moldability of the composition becomes unacceptably deteriorated.
The method for preparing the amino-containing polyphenylene sulfide materials to be used in the present invention is not limited to any specific one. Ilowever, a preferred example of the methods for this purpose comprises 2~60~07 conducting a polymerization by reacting an alkali metal sulfide with a dihalobenzene in an organic amide solvent in the presence of an amino-containing aromatic halide compound. Especially, it is preferred that the amino groups are introduced at ends of the molecule of polyphenylene sulfide.
Examples of the alkali metal sulfides which may be used include lithium, sodium, potassium, rubidium and cesium sulfide and mixtures thereof. These may be in hydrated form. The alkali metal sulfide may be prepared by reacting an alkali metal hydrosulfide with an alkali metal base. The alkali metal sulfide may be formed in situ prior to introduction of the dihalobenzene reactant into the polymerization system, or may be prepared out the polymerization system before use.
The amino-containing polyphenylene sulfide material should preferably comprises at least 70 mol% and more preferably at least 90 mol% of structural unit represented by:
~ S -The polyphenylene sulfide material may comprise less than 30 mol%, preferably less than 10 mol%, of one or more comonomer.
-6- 2~0907 ~- S -m-phenylene sulfide, S
o-phenylene sulfide, S ~ SO2 - phenylene sulfide sulfone, ~ S ~ CO - phenylene sulfide ketone, 5 ~ S ~ O - phenylene sulfide ether, 0~ S - dlphenylene sulfide.
The amino-containing aromatic halide reactants which may be used in the synthesis of the amino-containing polyphenylene sulfide material according to the invention are of the general ~ormula:
X ~ (~)n where X is a halogen, Y is hydrogen, -NH2 or a halogen, each R is a hydrocarbyl group containing 1 - 12 carbon atoms, and n is an integer of O - 4.
.
.. . .. .
~7~ 2~907 Typical examples of the halide reactants include m-fluoroaniline, m-chloroaniline, 3,5-dichloroaniline1 3,5-diaminochlorobenzene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline and m-iodoaniline and mixtures thereof. Especially preferred is 3,5-diaminochlorobenzene.
Examples of the dihalobenzene reactants include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene and the like.
The molar ratio of the alkali metal sulfide reactant to the total of the dihalobenzene and amino-containing aromatic halide reactants is preferably in the range of from 1.00:0.90 to 1.00:1.10.
As the polymerization medium, a polar solvent, in particular an organic amide solvent that is aprotic and is stable agains~ alkali at raised temperatures is preferred.
Typical examples of suitable organic amide solvents include N,N-dimethyl acetamide, N,N-dimethyl formamide, hexamethyl phosphoramide, N-methyl-E-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethyl-sulfoxide, sulfolane, tetramethylurea and the like and mixtures thereof.
The organic amide solvent may be used in an amount of 150 - 3500%, preferably 250 - 1500%, by weight of the welght of polymer to be produced by the polymerization.
The polymerization is effected with stirring at a temperature of 200 - 300C, preferablY 220 - 280C, for a period of 0.5 - 30 hours, preferablY l - 15 hours.
The polymerization degree of the product polymer produced by the above method may be enhance by heating the product polymer in an oxygen-containing atmosphere, e.g. air or by adding, for example, a peroxide to the polymer and then heating the mixture so as to cure the polymer. Such a thermal curing treatment may be effected, for example, at temperatures in the range of 200 - 280C for 1 - 12 hours.
-8- 2~6~07 Especially, in order to obtain a composition of excellent impact resistance and toughness properties, preferably, the amino-containing polyphenylene sulfide is cured by heating it in a nonoxidizing, inert gas at a temperature in the range of about 200 - about 280C for a period of 1 - 24 hours. Examples of the nonoxidizing, inert gases which may be used include helium, argon, nitrogen, carbon dioxide, steam and the like and mixtures thereof. For an economical operation, nitrogen is preferablY used.
The modified polyethylene material used in the invention is a polyethylene on to which 0.1 - 10% by weight of an unsaturated carboxylic acid and/or derivative is graft-copolymerized.
The term "polYethylene" as used herein is intended to refer at lease one, such as high density polyethylene, low density polyethylene, linear low density polyethylene and the like, with high density polyethylene most pre*erred.
The modified polyethylene material used in the invention has a content of unsaturated carboxylic acid and/or derivative ranging from 0.1 to 10%, preferablY from 1 to 5%, by weight. If the content is less than 0.1 wt.%, the advantageous effect achieved by modification with the acid component is not significant. On the other hand, if the content is greater than 10 wt.%, then the mechanical strength properties become seriously deteriorated.
Examples of the unsaturated carboxylic acids and/or derivatives thereof which may be used include acrylic, methacrylic, maleic, fumaric, itaconic and citraconic acids and derivatives thereof. Such an acid or derivative will be referred to as "monomer" hereinafter.
Examples of acid derivatives include anhydrides, esters, amides, imides and metal salts. Particular examples include maleic, citraconic and itaconic anhydrides; methyl-, ethyl- and butyl-acrylates and methacrylates; glycidyl acrylate; mono- and di-ethyl malates; mono- and di-me~hyl fumarates; mono- and di-ethyl itaconates; acryl and _9_ methacryl amides; maleic m.ono- and di-amides; maleic-N-rnonoethyl amide, maleic-N,N-diethyl amide, maleic-N-monobutyl amide, maleic-N,N-dibutyl amide, fumaric mono-and di-amides, fumaric-~-monoethyl amide, fumaric-N,N-S diethyl amide, fumaric-N-monobutyl amide, fumaric-~,N-dibutyl amide, maleimide, N-butyl maleimide, N--phenyl maleimide, sodium acrylate and methacrylate, potassium acrylate and methacrylate, and the like. Tllese monorners may be used singly or in combination. Maleic anhydride is most preferred.
An example of the techniques for graft-copolymerizing the monomer acid on to a polyethylene substrate is a process comprising mixing the polyethylene substrate with the monomer and a radical generator, for example, a peroxide and subjecting the mixture to melt-extrusion operation under copolymeri%ation conditions. An alternative process is to suspend or dissolve a polYethylene substrate in an appropriate solvent and add a monomer and a radical generator to the suspension or solution, which is then heated so as to cause the graft-polymerization to proceed.
The peroxides used for modification in the melt-extrusion process are preferably organic peroxides. Any known organic peroxide may be used. Exampl.es of the peroxides include:
2,5-dimethy]-2,5-di(tert.-bIl~y:I. pcroxy)hexyrIe-3;
2,5-dimethyl-2,5-di(tert.-buI;y:l peroxy)hexaIle;
2,2-bis(tert.-butyl peroxy)-p-diiso-propyl ben%ene dicumyl peroxide;
di(tert.-butyl peroxide;
tert.-butyl peroxy benzoate;
1,1-bis(tart.-butyl peroxy)-3,3,5--trimethyl cyclohexane;
2,4-dich]orobenzoyl peroxi.de;
benzoyl peroxide;
p-chlorobenzoyl peroxide;
a%obisisobutyroni.trile; and the li.ke.
Preferably, 2,5-dime~hyl-2,5-di(~ert.-butyl peroxy)hexane or 2,5-di.mei;hyl-2,5-di.(tert~-butyl peroxy)hexyne-3 i.s used.
2~09~
The amount of organic peroxide added ranges from O.G05% to 2%, preferably from 0.1% to 1%, by weight of the weight of polyethylene substrate.
The present resin composition comprises 60 - 99.5%, preferably 80 - 97% by weight of the cured, amino-containing polyphenylene sulfide material; and 40 - 0.5%, preferablY
20 - 3%, by weight of the modified polyethylene material having 0.5 - 10 wt.% of an unsaturated carboxylic acid and/or derivative thereof graft-copolymerized thereonto.
If the modified polyethylene material is used in a proportion of less than 0.5% by weight, the intended improvement cannot be achieved satisfactorily. If the modified polyethylene material in a proportion exceeding 40%
by weight, then the desirable high-temperature resistance, chemical resistance and rigidity properties possessed by the polyphenylene sulfide are seriouslY damaged and the moldability of the composition tends to largely decline.
The composition according to the invention may be prepared by various known methods. The starting material amino-containing polyphen~lene sulfide is thermally cured before use. The cured polyphenylene sulfide may be mixed -with the modified polYethylene material having the acid . and/or derivative graft-polymerized thereonto, in a mixer, such as tumbler mixer, Henschel mixer, ball mill, ribbon blender and the like. The mixture in powder or pelletized form may be fed into a melt-mixing or blending machine to give a resin composition according to the invention.
Alternatively, the cured polyphenylene sulfide and modified polyethylene materials may be fed to a melt-mixing or blending machine and combined into a composition according to the invention. Melt-blending may be effected at a temperature of 250 - 350C in a suitable machine, such as kneader, Banbury mixer, extruder or the like. ~or ease of operation, an extruder may be desirably employed for 3s this purpose.
Provided that the object of the invention is not significantly spoiled, any conventional fibrous or powdery filler may be incorporated in the present resin composition;
~06~3~
for example, fibers of glass, carbon, silica, alumina, silicon carbide, zirconia, calcium titanate, and calcium sulfate; fibers of aramide and wholly aromatic polyester, powders or particulates of wollastonite, calcium carbonate, magnesium carbonate, talc, mica, clay, silica, alumina, kaolin, zeolites, gypsum, calcium silicate, magnesium silicate, calcium sulfate, titanium oxide, magnesium oxide.
carbon black, graphite, iron oxides, zinc oxide, copper oxide, glass, quartz and quartz glass; glass beads; and glass balloons. These fillers may be used a mixture thereof. If desired, the fillers may be treated with, for example, a silane or titanate coupling agent before use.
Glass fibers, for example, chopped strands of a fiber length 1.5 - 12 mm and a fiber diameter 3 - 24 ~m, milled fibers of a fiber diameter 3 - 8 ~m, glass flakes and powder of less than 325 mesh size may be mentioned as suitable examples.
In addition, provided that the ob;ect of the invention is not significantly spoiled, the present composition may include additives, such as releasing agent, lubricant, heat stabilizer, antioxidant, UV absorber, nucleating agent, blowing agent, rust-proofing agent, ion-trapping agent, flame-retardant, flame-proofing aid, colorant (e.g. dye or pigment), antistatic agent or the like; wax; and a minor proportion of other polymer. These may be present singly or in combination.
Examples of the other polymers which may be optionally incorporated includes various thermoplastic elastomer, such as olefin-, styrene-, urethane-, ester-, fluoride-, amide- and acrylate-based elastomers;
rubbery polymers, such as polybutadlene, polyisoprene, polychloroprene, polybutene, styrene-butadiene rubber and hydrogenates thereof, acrylonitrile-butadiene rubber, ethylene-propylene copolymer and ethylene-propylene-ethylidene-norbornene copolymer; polyamides, such as nylon-6, -6/6, -4/6, -6/10, -ll and -12; polyesters, such as polyethylene terephthalate, polybutylene terephthalate and polyarylates; polYstyrene, poly ~-methylstyrene.
; . . ................... .. . . .
. ,: .
~o~oi~
polyvinyl acetate, polyvinyl chloride, polyacrylates, polymethacrylates, polyacrylonitrile, polyurethanes, polyacetals, polyphenylene oxides, polycarbonates, polysulfones, polyether sulfones, polyaryl sulfones, polyphenylene sulfide sulfones, polyphenYlene sulfide ketones, polyether ketones, polyether ether ketones, polyamide imides, polyimides, silicone resins, phenoxy resins, fluorine resins and the like. Also may be mentioned as example, a class of resins which, when molten, form an anisotropic melt phase and may be melt-processed. The above-listed optional additive polymers may be used in a variety of forms, for example, as a homopolymer or as a random or block graft copolymer. TheY may be used singly or in any suitable combination and may be modified before use, if desired.
Incorporation of the additives into the present composition Inay be effected in any suitable manner.
For example, the additives may be added to component (A) and/or (B) before or during the composition is prepared.
Alternatively, the additive may be incorporated into the composition after the composition is formulated from components (A) and (B), in particular when the composition is molten before use.
ExamPle The invention will be further illustrated with re~erence to the following Examples by which the scope of the invention is not restricted.
PreParation 1 Synthesis of amlno-containin~ Polyphenylene sulfide A 15 liter-capacity autoclave was charged with 5 liters of N-methyl-2-pyrrolidone (referred to as ~MP
hereinafter) and heated to a temperature of 120C. To the heated autoclave, 1.866 g of Na2S-2.8H20 was introduced.
The mixture was heated slowly to 205C over a period of about 2 hours with stirring so as to dis~ill 407 g of water off the autoclave. After the reaction system was cooled down to 140C, 2080 g of p-dichlorobenzene was added. The autoclave was sealed and the reaction mixture was heated 2~3~0~3r7 to 225C and allowed to polymerize for 3 hours at this temperature. Then the temperature of the reaction was raised up to 250C. When 250C was attained, a solution of 3,5-diaminochlorobenzene 20.2 g (corresponding to about 1 mol% of the p-chloroben~ene used hereinabove) in 50 mQ NMP
was injected into the reaction system, which was allowed to be polymerized at 250C for a further period of 3 hours Upon completion of the polymerization, the reaction system was cooled to room temperature. A sample of the resulting slurry mixture was taken and filtered to give a filtrate. The proportion of unconverted 3,5-diaminochloro-benzene remaining in the filtrate was determined using a gas chromatograph apparatus (GC-12A manufactured by Shimadzu Seisakusho Ltd.). It was found that 38% of the 3,5-diaminochlorobenzene was converted.
The slurry from the above polymerization was poured into a mass of water so as to precipitate the product polymer, which was then filtered off, washed with pure water, and hot-vacuum dried overnight. The thus isolated PPS had a melt viscosity of 500 poises as measured in a KOHKA type flow tester at 300C using an orifice of a 0.5 mm diameter and a 2 mm length under a load of 10 kg.
The polymer was thermally cured at 235C for a further period of 2 hours in air to give a cured polymer product having an lncreased melt viscositY of 8,000 poises as measured by the above-specified method. The thus resulting cured, amino-containing polYphenylene sulfide material will be referred to as PPS-I.
Preparation 2 Curing of PPS under a non-oxidizing inert atmosphere The procedure of Preparation 1 was repeated to give an uncured PPS, which was then heated to 230C for 10 hours under a nitrogen atmosphere. The thus thermally cured amino-containing polyphenylene sulfide had a melt viscosity of 1,500 poises. This product will be referred to as PPS-II.
2~907 PreParation 3 Synthesis of amino-containing polyPhenylene sulfide The general procedure of the preceding Preparation 1 was repeated except that 2009 g p-dichlorobenzene and 19.0 g 3,5-diaminochlorobenzene (corresponding to about 1 mol% of the p-dichlorobenzene used herein) were used in Preparation 3 and that the temperature of the reaction mixture was slowly raised to 250C over a period of one hour and 20 minutes and allowed to polymerize at 250C for a further 3 hours so as to give an amino-containing polyphenylene sulfide having a melt viscosity of 110 poises. The proportion of unconverted 3,5-diaminochlorobenzene remaining in the filtrate was determined by gas chromatography technique using Shimadzu GC-12A. It was found that 36% of the supplied 3,5-diaminochlorobenzene was converted. This polymer was thermally cured in air at 235C for a further 2 hours to attain an increased melt viscosity of 8,000 poises.
The thus resulting cured, amino-containing polyphenylene sulfide material will be referred to as PPS-III.
PreParation 4 Synthesis of PolyPhenylene sulfide free of amino grouPs The general procedure of Preparation 1 was repeated except that 2080 g p-dichlorobenzene was used with omitting the amino-containing aromatic halide, i.e. 3,5-diamino-chlorobenzene.
The resulting polYmer had a melt viscosity of 550 poises. Then the polymer was thermally cured in air at 235C for 2 hours to attain an increased melt viscosity of 8000 poises. The thus resulting cured polyphenylene sulfide material will be referred to as PPS-IV.
PrePa-ration 5 Synthesis of amino-containinF PolyPhenylene sulfide An amino-containing polyphenYlene sulfide resin was prepared by repeating the general procedure of the preceding Preparation 1 except that 2080 g p-dichlorobenzene and 18.4 g 2-chloroaniline (corresponding to about 1 mol% of the p-dichlorobenzene) were employed in this Preparation 5, 2~0907 and that the temperature of the reaction mixture was slowly raised to 250C over a period of one hour and 20 minutes and then the mixture was allowed to polymerize at 250C
for a further 3 hours. The resulting amino-containing polyphenylene sulfide had a melt viscosity of 480 poises.
Analysis of the unconverted 2-chloroaniline remaining in the filtrate by gas chromatography (using Shimadzu GC-12A
gas chromatograph apparatus) revealed a 2-chloroaniline conversion of 35%.
The polymer was thermally cured in air at 235C
for a further 2 hours to give a cured amino-containing polyphenylene sulfide having a melt viscosity of 8,000 poises. This cured polymer will be referred to as PPS-V.
Preparation 6 Synthesis of amino-containinF Polyphenylene sulfide An amino-containing polyphenylene sulfide resin was prepared by repeating the general procedure of the preceding Preparation 1 except that 1789 g p-dichlorobenzene, and 310 g 3,5-diaminochlorobenzene (corresponding to about 15 mol% of the total amount of the p-dichlorobenzene and 3,5-diaminochlorobenzene present) were employed in this Preparation 6, and that the temperature of the reaction mixture was slowly raised to 250C over a period of one hour and 20 minutes and then the mixture was allowed to polymerize at 250C for a further 3 hours. The resulting amino-containing polYphenylene sulfide had a melt viscosity that was too low to be determined by the above-specified flow tester method. Analysis of the unconverted 3,5-diaminochlorobenzene remaining in the filtrate by gas chromatography (using Shimadzu GC-12A gas chromatograph apparatus) revéaled a 3,5-diaminochlorobenzene conversion of 38%.
The polymer was thermally cured in a.ir at 235C for a further 10 hours to give a cured amino-containing polyphenylene sulfide having an increased melt viscosity of 6,600 poises. This cured polYmer will be referred to as PPS-VI.
-16- 2~6~907 PreParation 7 Graft copolymerization of Polyethylene with acid - A high densitY polyethylene 97.5 weight % was premixed with maleic anhydride 2 weight % and 2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexane 0.5 weight %. The premix was fed to an extruder machine with a cylinder maintained at a temperature of 210C. During passage through the extruder, the premix was kneaded and allowed to react.
By this procedure, pellets of a graft copolymerized, high - 10 density polyethYlene were prepared.
PreParation 8 PreParation of carboxylic ~roup-containinF olefinic coPolymer An ethylene-butene-1 copolymer (commercially avail-able under trade mark TAFMER A4090) 100 parts by weight waspremixed with maleic anhydride 1 part by weight and 1,3-bis(tert.-butyl peroxy propyl) benzene 0.5 parts by weight.
The premix was fed to an extruder machine with a cylinder maintained at 220G. During passage through the extruder, the premix was kneaded and allowed to react. By this procedure, pellets of a carboxylic group-containing olefinic copolymer were prepared.
By IR spectrography, the quantity of maleic anhydride grafted on to the ethylene-butene-l copolymer substrate was confirmed to be 0.75 parts by weight of maleic anhydride per 100 parts by weight of ethylene-butene-1 copolymer. This graft copolymer will be referred to as "modifled P0".
ExamPle PPS-I from Preparation 1 and the graft copolymerized polyethylene from Preparation 7 were mixed in relative proportions of 90% and 10% by weight and fed to a vent-type vacuum twin-screw extruder which had a venting pressure of 30 Torrs at the vent. In the extruder, the mixture was kneaded at 300C to produce pellets thereof. A sample of the pellets was in~ection molded at a temperature of 300C
to prepare various test specimens to be sub~ected to tests of:
-17- 2~6~07 Izod Impact Strength; notched, according to ASTM D-256 Tensile Elongation; according to ASTM D638, at 5 mm/minute Heat Distortion Temperature; according to ASTM D648, with a load of 18.6 kg/cm2 In addition, a 1/8 inch thick test specimen prepared for the heat distortion temperature test was subjected to a solvent resistance test, where the specimen was immersed in a gasohol mixture comprising gasoline and methanol in a weight ratio of 80:20, at a temperature of 125C for 8 hours. The weight of the specimen was measured before and after the immersion test. The solvent resistance performance was rated by the difference of the two weights.
The results are set forth in Table 1.
Example 2 PPS-II from Preparation 2 and the graft copolymerized polyethylene from Preparation 7 were mixed in relative proportions of 90% and lO~o by weight. The mixture was processed and tested as in Example 1.
The results are set forth in Table 1.
ExamPle 3 PPS-I from Preparation 1, the grafted polyethylene from Preparation 7, and glass fibers were mixed in relative proportions of 63%, 7% and 30% by weight. The mixture was processed and tested as in Example 1. The results are set forth in Table 1.
ExamPle 4 PPS-V from Preparation 5 and the grafted polyethylene from Preparation 7 were mixed in relative proportions of 90% and 10% by weight. The mixture was processed and tested as in Example 1. The results are set forth in Table 1.
Comparative ExamPles 1 and 2 The procedure of Example 1 was repeated using either PPS-III or PPS-IV as an amino-containing polyphenylene sulfide material. The results are shown in Table 1.
ComParatiVe ExamPles 3 - 6 PPS-I from Preparation 1, the grafted polyethylene from Preparation 7 and glass fiber were mi.xed in various .
3 ~
relative proportions as given in Table 1. Each of the mixtures was processed and tested as in Example l. I`he results are al.so shown in Table l.
Comparative Example 7 PPS-I from Preparation 1 and an unmodified high density polyethylene were mixed in relative proportions of 90% and 10% by weight. The mixture was processed and tested as in Example 1. The results are sho~Yn in Table 1.
Comparative Example 8 PPS-VI from Preparation 6 and the grafted polyethylene from Preparation 7 were mixed in relative proportions of 90% and 10% by weight. The mixture was processed and tested as in Example 1. The results are shown in Table 1.
Comparative ExamPle 9 PPS-I from Preparation ] and the modified P0 from Preparation 8 were mixed in relative proportions of 90% and 10% by weight. The mixtllre was subjected to the process as described in Example 1. However, during the melt-kneading - 20 in the vented twin-screw extruder, part of -the melt was expelled through the vent. This made the extrusion procedure unstable. Further, it was found that the resulting pellets had bubbles caught therein. Furthermore, the moldings showed a poor appearance. The test results are shown in Table 1.
As above-illustrated, according to -I;he invel-ltion, a specially prepared polypherlylelle suJ.f:i(le ma-(;el:ial. contaiJlirlg a speci-fied amount of amino groups is formulated with a specially modified polyethylene material so as to provide a po].yphenylene su].fide resin composition which retains the desired proper-ties, SUC}l as high temperature resistance and chemical resis-tance, possessed originally by the unmodified polyphenylene sul.fide itseli` and is significantly improved in the toughness properties, such as impact strength, and in the tensile elongation properties.
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POLYPHENYLENE SULFIDE RESIN CO~lPOSITION
BAC~GROU~D OF THE INVENTION:
1. Field of the Invention This invention relates to a resin composition comprising a specified class of polYphenYlene sulfides containing amino groups and a modified polyethylene on to which at least one unsaturated carboxylic acid and/or derivative thereof is graft-polYmerized and, more particularly, to such a composition exhibiting excellent impact, toughness, high-temperature resistance and solvent resistance properties.
2. Prior Art PolyphenYlene sulfide resins are known as a class of highly functional resins exhibiting excellent high-temperature resistance, fire retardance, chemical resistance, moldability, shapabilitY and electrical characteristics and the like, and recently are used widely in applications including the production of electrical and electronic parts, automotive parts, etc.
Polyphenylene sulfide resins maY be substantially improved in their properties such as strength, rigidity, high-temperature resistance, toughness, dimensional stability, etc., by incorporating them with fibrous reinforcements, such as glass fibers or carbon fibers, or inorganic fillers, such as talc, clay or mica. Generally, polyphenylene sulfide resins, however, suffer from a serious drawback that they exhibit poor ductility properties and are brittle as compared with other known engineering plastics such as nylons, polycarbonates, polybu~ylene terephthalate, polyacetals and the like. Therefore, polyphenylene sulfide resins have been excluded from usin~ in a certain, relatively wi.de range of applications.
Upto the date, it has been establis}led to im~rove the toughness or impact strengtll properties of polyphellylene sulfide by blending Witll a flexible pol~mer. ~or example, Japanese Patent Public Disclosure (I~OI~Al) No. a9-207921 discloses a method in ~YhiCh a polyphenylelle sulfide ma~erial i.s blended with an epoxy resin and a modified ~-olefin 2~0~0~
copolymeric elastomer having an unsaturated carboxylic acid or anhydride or a derivative thereof graft-copolymerized thereon. Further, methods comprising blending a polyphenYlene sulfide material with an ethylene-glycidyl methacrylate copolymer are known, for example, in Japanese Patent Public Disclosures Nos. 58-1547 and 59-152953.
However, the backbones of the ordinary polYphenylene sulfide molecules lack any effectively reactive site. Therefore.
even if a significantly reactive olefin copolymer is added to such an ordinary polyphenylene sulfide material, the added copolymer may exhibit only a poor adhesion or bonding at the interface between the additive and the polyphenylene sulfide material, resulting an unacceptable improvement in the impact resistance. Furthermore, there may be serious difficulties that the resulting blend shows deteriorated high-temperature resistance and solvent resistance properties.
On the other hand, various polyphenylene sulfide compositions have been proposed, which comprise poly-phenylene sulfide materials that have been treated withtechniques to improve the adhesion or bonding at the interface between the polyphenylene sulfide and a flexible polymer additive. Examples of the compositions of this type which may be mentioned include a composition comprising a polyphenylene sulfide that has been treated with an acid and washed, in combination with a modified olefin copolymer having an unsaturated carboxylic acid or anhydride graft-copolymerized thereon, see Japanese Patent Public Disclosure No. 62-169854; and a composition comprising a polyphenylene sulfide in combination with an olefin copolymer formed of an ~-olefin and a glycidyl ester of ~,~-unsaturated carboxylic acid, see Japanese Patent Public Disclosure No. 62-153343.
However, the impact resistance properties of polyphenylene sulfide cannot be acceptably improved even Wit}l these compositions.
Further, various polyphenylene sulfide compositions has been proposed, which comprise polyphenylene sulfide materials that have been modified ~vith techni4ues to 20~9~7 improve the adhesion or bonding at the interface between the polyphenylene sulfide and a flexible polymer additive.
An example which may be mentioned is a composition compris-ing an amino and/or amide-containing polyphenylene sulfide and a thermoplastic elastomer, see Japanese Patent Public Disclosure No. 61-207462. ~y this approach, the adhesion or bonding at the interface between the polyphenylene sulfide and the thermoplastic elastomer may be improved only to an extent that is unsatisfactorY in practice.
10 SUMMARY OF THE INVENTION:
An object of primary importance of the invention is to provide a polyphenylene sulfide resin composition that is significantly improved in the impact resistance and toughness properties and is substantially freed from the problems and difficulties experienced with the above-discussed prior art.
Accordingly, the present invention relates to a resin composition comprising a thermally cured, specific polyphenylene sulfide material modified by inclusion of amino groups in the molecule and which has a viscosity in a specified range before curing and another specified viscosity after curing, in conjunction with a modified polyethylene material on to which 0.5 - 10% by weight of at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymeri~ed. In the composition, the modified polyethylene material exhibits an enhanced adhesion or bonding at the interface between the polyphenylene sulfide and polyethylene materials and permits formation of a homogeneous dlspersion.
Accordingly, the invention provides a polyphenylene sulfide resin composition which comprises (A) 60 - 99.5% by weight of a thermally cured polyphenylene sulfide material having a melt viscosity of 500 - 30,000 poises and which has been derived, by thermally curing, from a polyphenylene sulfide having a melt viscosity of 400 poises or higher and containing 0.05 - S mol% of amino groups on the basis of the phenylene sulfide repeating units, and 3f~
~4-(B) 40 - 0.5% by weight of a modified polyethylene material comprising at least one polyethylene onto which at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymerized in a proportion of 0.1 - 10%
by weight of the total weight of said modified polyethylene material.
DETAILED DESCRIPTION OF THE INVENTION:
The invention will be described in more detail.
Preferably, the amino-containing polYphenylene sulfide material which is used in the present invention has an amino-group content of 0.05 - 5 mol% and, particularly, o-f 0.1 - 3 mol%. If the amino-group content is-less than 0.05 mol%, there is little advantage achieved by the inclusion of amino groups. If the amino-group content is greater than 5 mol%, then the advantageous effect by the inclusion of amino groups is undesirably offset by deterioration of the mechanical strength properties.
The amino-containing polyphenylene sulfide material which is used in the inventi.on should have a melt viscosity of not less than 400 poises, preferably not less than 500 poises before curing, as measured in a KOHKA type flow tester at 300C using an orifice of a 0.5 mm diameter and a 2 mm length under a load of 10 kg, and should have a melt viscosity in the range of from 500 to 30,000 poises, 25 preferably from 1,000 to 20,000 poi.ses after curing as measured simi.larly. If the polyphenylene sulride material has a melt viscosity of less than 400 poises before curing or a melt viscosity less than 500 poises af-ter curing, the intended improvement in the toughness properties of the composition is achieved only to an unsa-tisfactory extent. If the cured polyphenylene sulfide material has a melt viscosity of greater than 30,000 poises, then the moldability of the composition becomes unacceptably deteriorated.
The method for preparing the amino-containing polyphenylene sulfide materials to be used in the present invention is not limited to any specific one. Ilowever, a preferred example of the methods for this purpose comprises 2~60~07 conducting a polymerization by reacting an alkali metal sulfide with a dihalobenzene in an organic amide solvent in the presence of an amino-containing aromatic halide compound. Especially, it is preferred that the amino groups are introduced at ends of the molecule of polyphenylene sulfide.
Examples of the alkali metal sulfides which may be used include lithium, sodium, potassium, rubidium and cesium sulfide and mixtures thereof. These may be in hydrated form. The alkali metal sulfide may be prepared by reacting an alkali metal hydrosulfide with an alkali metal base. The alkali metal sulfide may be formed in situ prior to introduction of the dihalobenzene reactant into the polymerization system, or may be prepared out the polymerization system before use.
The amino-containing polyphenylene sulfide material should preferably comprises at least 70 mol% and more preferably at least 90 mol% of structural unit represented by:
~ S -The polyphenylene sulfide material may comprise less than 30 mol%, preferably less than 10 mol%, of one or more comonomer.
-6- 2~0907 ~- S -m-phenylene sulfide, S
o-phenylene sulfide, S ~ SO2 - phenylene sulfide sulfone, ~ S ~ CO - phenylene sulfide ketone, 5 ~ S ~ O - phenylene sulfide ether, 0~ S - dlphenylene sulfide.
The amino-containing aromatic halide reactants which may be used in the synthesis of the amino-containing polyphenylene sulfide material according to the invention are of the general ~ormula:
X ~ (~)n where X is a halogen, Y is hydrogen, -NH2 or a halogen, each R is a hydrocarbyl group containing 1 - 12 carbon atoms, and n is an integer of O - 4.
.
.. . .. .
~7~ 2~907 Typical examples of the halide reactants include m-fluoroaniline, m-chloroaniline, 3,5-dichloroaniline1 3,5-diaminochlorobenzene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline and m-iodoaniline and mixtures thereof. Especially preferred is 3,5-diaminochlorobenzene.
Examples of the dihalobenzene reactants include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene and the like.
The molar ratio of the alkali metal sulfide reactant to the total of the dihalobenzene and amino-containing aromatic halide reactants is preferably in the range of from 1.00:0.90 to 1.00:1.10.
As the polymerization medium, a polar solvent, in particular an organic amide solvent that is aprotic and is stable agains~ alkali at raised temperatures is preferred.
Typical examples of suitable organic amide solvents include N,N-dimethyl acetamide, N,N-dimethyl formamide, hexamethyl phosphoramide, N-methyl-E-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethyl-sulfoxide, sulfolane, tetramethylurea and the like and mixtures thereof.
The organic amide solvent may be used in an amount of 150 - 3500%, preferably 250 - 1500%, by weight of the welght of polymer to be produced by the polymerization.
The polymerization is effected with stirring at a temperature of 200 - 300C, preferablY 220 - 280C, for a period of 0.5 - 30 hours, preferablY l - 15 hours.
The polymerization degree of the product polymer produced by the above method may be enhance by heating the product polymer in an oxygen-containing atmosphere, e.g. air or by adding, for example, a peroxide to the polymer and then heating the mixture so as to cure the polymer. Such a thermal curing treatment may be effected, for example, at temperatures in the range of 200 - 280C for 1 - 12 hours.
-8- 2~6~07 Especially, in order to obtain a composition of excellent impact resistance and toughness properties, preferably, the amino-containing polyphenylene sulfide is cured by heating it in a nonoxidizing, inert gas at a temperature in the range of about 200 - about 280C for a period of 1 - 24 hours. Examples of the nonoxidizing, inert gases which may be used include helium, argon, nitrogen, carbon dioxide, steam and the like and mixtures thereof. For an economical operation, nitrogen is preferablY used.
The modified polyethylene material used in the invention is a polyethylene on to which 0.1 - 10% by weight of an unsaturated carboxylic acid and/or derivative is graft-copolymerized.
The term "polYethylene" as used herein is intended to refer at lease one, such as high density polyethylene, low density polyethylene, linear low density polyethylene and the like, with high density polyethylene most pre*erred.
The modified polyethylene material used in the invention has a content of unsaturated carboxylic acid and/or derivative ranging from 0.1 to 10%, preferablY from 1 to 5%, by weight. If the content is less than 0.1 wt.%, the advantageous effect achieved by modification with the acid component is not significant. On the other hand, if the content is greater than 10 wt.%, then the mechanical strength properties become seriously deteriorated.
Examples of the unsaturated carboxylic acids and/or derivatives thereof which may be used include acrylic, methacrylic, maleic, fumaric, itaconic and citraconic acids and derivatives thereof. Such an acid or derivative will be referred to as "monomer" hereinafter.
Examples of acid derivatives include anhydrides, esters, amides, imides and metal salts. Particular examples include maleic, citraconic and itaconic anhydrides; methyl-, ethyl- and butyl-acrylates and methacrylates; glycidyl acrylate; mono- and di-ethyl malates; mono- and di-me~hyl fumarates; mono- and di-ethyl itaconates; acryl and _9_ methacryl amides; maleic m.ono- and di-amides; maleic-N-rnonoethyl amide, maleic-N,N-diethyl amide, maleic-N-monobutyl amide, maleic-N,N-dibutyl amide, fumaric mono-and di-amides, fumaric-~-monoethyl amide, fumaric-N,N-S diethyl amide, fumaric-N-monobutyl amide, fumaric-~,N-dibutyl amide, maleimide, N-butyl maleimide, N--phenyl maleimide, sodium acrylate and methacrylate, potassium acrylate and methacrylate, and the like. Tllese monorners may be used singly or in combination. Maleic anhydride is most preferred.
An example of the techniques for graft-copolymerizing the monomer acid on to a polyethylene substrate is a process comprising mixing the polyethylene substrate with the monomer and a radical generator, for example, a peroxide and subjecting the mixture to melt-extrusion operation under copolymeri%ation conditions. An alternative process is to suspend or dissolve a polYethylene substrate in an appropriate solvent and add a monomer and a radical generator to the suspension or solution, which is then heated so as to cause the graft-polymerization to proceed.
The peroxides used for modification in the melt-extrusion process are preferably organic peroxides. Any known organic peroxide may be used. Exampl.es of the peroxides include:
2,5-dimethy]-2,5-di(tert.-bIl~y:I. pcroxy)hexyrIe-3;
2,5-dimethyl-2,5-di(tert.-buI;y:l peroxy)hexaIle;
2,2-bis(tert.-butyl peroxy)-p-diiso-propyl ben%ene dicumyl peroxide;
di(tert.-butyl peroxide;
tert.-butyl peroxy benzoate;
1,1-bis(tart.-butyl peroxy)-3,3,5--trimethyl cyclohexane;
2,4-dich]orobenzoyl peroxi.de;
benzoyl peroxide;
p-chlorobenzoyl peroxide;
a%obisisobutyroni.trile; and the li.ke.
Preferably, 2,5-dime~hyl-2,5-di(~ert.-butyl peroxy)hexane or 2,5-di.mei;hyl-2,5-di.(tert~-butyl peroxy)hexyne-3 i.s used.
2~09~
The amount of organic peroxide added ranges from O.G05% to 2%, preferably from 0.1% to 1%, by weight of the weight of polyethylene substrate.
The present resin composition comprises 60 - 99.5%, preferably 80 - 97% by weight of the cured, amino-containing polyphenylene sulfide material; and 40 - 0.5%, preferablY
20 - 3%, by weight of the modified polyethylene material having 0.5 - 10 wt.% of an unsaturated carboxylic acid and/or derivative thereof graft-copolymerized thereonto.
If the modified polyethylene material is used in a proportion of less than 0.5% by weight, the intended improvement cannot be achieved satisfactorily. If the modified polyethylene material in a proportion exceeding 40%
by weight, then the desirable high-temperature resistance, chemical resistance and rigidity properties possessed by the polyphenylene sulfide are seriouslY damaged and the moldability of the composition tends to largely decline.
The composition according to the invention may be prepared by various known methods. The starting material amino-containing polyphen~lene sulfide is thermally cured before use. The cured polyphenylene sulfide may be mixed -with the modified polYethylene material having the acid . and/or derivative graft-polymerized thereonto, in a mixer, such as tumbler mixer, Henschel mixer, ball mill, ribbon blender and the like. The mixture in powder or pelletized form may be fed into a melt-mixing or blending machine to give a resin composition according to the invention.
Alternatively, the cured polyphenylene sulfide and modified polyethylene materials may be fed to a melt-mixing or blending machine and combined into a composition according to the invention. Melt-blending may be effected at a temperature of 250 - 350C in a suitable machine, such as kneader, Banbury mixer, extruder or the like. ~or ease of operation, an extruder may be desirably employed for 3s this purpose.
Provided that the object of the invention is not significantly spoiled, any conventional fibrous or powdery filler may be incorporated in the present resin composition;
~06~3~
for example, fibers of glass, carbon, silica, alumina, silicon carbide, zirconia, calcium titanate, and calcium sulfate; fibers of aramide and wholly aromatic polyester, powders or particulates of wollastonite, calcium carbonate, magnesium carbonate, talc, mica, clay, silica, alumina, kaolin, zeolites, gypsum, calcium silicate, magnesium silicate, calcium sulfate, titanium oxide, magnesium oxide.
carbon black, graphite, iron oxides, zinc oxide, copper oxide, glass, quartz and quartz glass; glass beads; and glass balloons. These fillers may be used a mixture thereof. If desired, the fillers may be treated with, for example, a silane or titanate coupling agent before use.
Glass fibers, for example, chopped strands of a fiber length 1.5 - 12 mm and a fiber diameter 3 - 24 ~m, milled fibers of a fiber diameter 3 - 8 ~m, glass flakes and powder of less than 325 mesh size may be mentioned as suitable examples.
In addition, provided that the ob;ect of the invention is not significantly spoiled, the present composition may include additives, such as releasing agent, lubricant, heat stabilizer, antioxidant, UV absorber, nucleating agent, blowing agent, rust-proofing agent, ion-trapping agent, flame-retardant, flame-proofing aid, colorant (e.g. dye or pigment), antistatic agent or the like; wax; and a minor proportion of other polymer. These may be present singly or in combination.
Examples of the other polymers which may be optionally incorporated includes various thermoplastic elastomer, such as olefin-, styrene-, urethane-, ester-, fluoride-, amide- and acrylate-based elastomers;
rubbery polymers, such as polybutadlene, polyisoprene, polychloroprene, polybutene, styrene-butadiene rubber and hydrogenates thereof, acrylonitrile-butadiene rubber, ethylene-propylene copolymer and ethylene-propylene-ethylidene-norbornene copolymer; polyamides, such as nylon-6, -6/6, -4/6, -6/10, -ll and -12; polyesters, such as polyethylene terephthalate, polybutylene terephthalate and polyarylates; polYstyrene, poly ~-methylstyrene.
; . . ................... .. . . .
. ,: .
~o~oi~
polyvinyl acetate, polyvinyl chloride, polyacrylates, polymethacrylates, polyacrylonitrile, polyurethanes, polyacetals, polyphenylene oxides, polycarbonates, polysulfones, polyether sulfones, polyaryl sulfones, polyphenylene sulfide sulfones, polyphenYlene sulfide ketones, polyether ketones, polyether ether ketones, polyamide imides, polyimides, silicone resins, phenoxy resins, fluorine resins and the like. Also may be mentioned as example, a class of resins which, when molten, form an anisotropic melt phase and may be melt-processed. The above-listed optional additive polymers may be used in a variety of forms, for example, as a homopolymer or as a random or block graft copolymer. TheY may be used singly or in any suitable combination and may be modified before use, if desired.
Incorporation of the additives into the present composition Inay be effected in any suitable manner.
For example, the additives may be added to component (A) and/or (B) before or during the composition is prepared.
Alternatively, the additive may be incorporated into the composition after the composition is formulated from components (A) and (B), in particular when the composition is molten before use.
ExamPle The invention will be further illustrated with re~erence to the following Examples by which the scope of the invention is not restricted.
PreParation 1 Synthesis of amlno-containin~ Polyphenylene sulfide A 15 liter-capacity autoclave was charged with 5 liters of N-methyl-2-pyrrolidone (referred to as ~MP
hereinafter) and heated to a temperature of 120C. To the heated autoclave, 1.866 g of Na2S-2.8H20 was introduced.
The mixture was heated slowly to 205C over a period of about 2 hours with stirring so as to dis~ill 407 g of water off the autoclave. After the reaction system was cooled down to 140C, 2080 g of p-dichlorobenzene was added. The autoclave was sealed and the reaction mixture was heated 2~3~0~3r7 to 225C and allowed to polymerize for 3 hours at this temperature. Then the temperature of the reaction was raised up to 250C. When 250C was attained, a solution of 3,5-diaminochlorobenzene 20.2 g (corresponding to about 1 mol% of the p-chloroben~ene used hereinabove) in 50 mQ NMP
was injected into the reaction system, which was allowed to be polymerized at 250C for a further period of 3 hours Upon completion of the polymerization, the reaction system was cooled to room temperature. A sample of the resulting slurry mixture was taken and filtered to give a filtrate. The proportion of unconverted 3,5-diaminochloro-benzene remaining in the filtrate was determined using a gas chromatograph apparatus (GC-12A manufactured by Shimadzu Seisakusho Ltd.). It was found that 38% of the 3,5-diaminochlorobenzene was converted.
The slurry from the above polymerization was poured into a mass of water so as to precipitate the product polymer, which was then filtered off, washed with pure water, and hot-vacuum dried overnight. The thus isolated PPS had a melt viscosity of 500 poises as measured in a KOHKA type flow tester at 300C using an orifice of a 0.5 mm diameter and a 2 mm length under a load of 10 kg.
The polymer was thermally cured at 235C for a further period of 2 hours in air to give a cured polymer product having an lncreased melt viscositY of 8,000 poises as measured by the above-specified method. The thus resulting cured, amino-containing polYphenylene sulfide material will be referred to as PPS-I.
Preparation 2 Curing of PPS under a non-oxidizing inert atmosphere The procedure of Preparation 1 was repeated to give an uncured PPS, which was then heated to 230C for 10 hours under a nitrogen atmosphere. The thus thermally cured amino-containing polyphenylene sulfide had a melt viscosity of 1,500 poises. This product will be referred to as PPS-II.
2~907 PreParation 3 Synthesis of amino-containing polyPhenylene sulfide The general procedure of the preceding Preparation 1 was repeated except that 2009 g p-dichlorobenzene and 19.0 g 3,5-diaminochlorobenzene (corresponding to about 1 mol% of the p-dichlorobenzene used herein) were used in Preparation 3 and that the temperature of the reaction mixture was slowly raised to 250C over a period of one hour and 20 minutes and allowed to polymerize at 250C for a further 3 hours so as to give an amino-containing polyphenylene sulfide having a melt viscosity of 110 poises. The proportion of unconverted 3,5-diaminochlorobenzene remaining in the filtrate was determined by gas chromatography technique using Shimadzu GC-12A. It was found that 36% of the supplied 3,5-diaminochlorobenzene was converted. This polymer was thermally cured in air at 235C for a further 2 hours to attain an increased melt viscosity of 8,000 poises.
The thus resulting cured, amino-containing polyphenylene sulfide material will be referred to as PPS-III.
PreParation 4 Synthesis of PolyPhenylene sulfide free of amino grouPs The general procedure of Preparation 1 was repeated except that 2080 g p-dichlorobenzene was used with omitting the amino-containing aromatic halide, i.e. 3,5-diamino-chlorobenzene.
The resulting polYmer had a melt viscosity of 550 poises. Then the polymer was thermally cured in air at 235C for 2 hours to attain an increased melt viscosity of 8000 poises. The thus resulting cured polyphenylene sulfide material will be referred to as PPS-IV.
PrePa-ration 5 Synthesis of amino-containinF PolyPhenylene sulfide An amino-containing polyphenYlene sulfide resin was prepared by repeating the general procedure of the preceding Preparation 1 except that 2080 g p-dichlorobenzene and 18.4 g 2-chloroaniline (corresponding to about 1 mol% of the p-dichlorobenzene) were employed in this Preparation 5, 2~0907 and that the temperature of the reaction mixture was slowly raised to 250C over a period of one hour and 20 minutes and then the mixture was allowed to polymerize at 250C
for a further 3 hours. The resulting amino-containing polyphenylene sulfide had a melt viscosity of 480 poises.
Analysis of the unconverted 2-chloroaniline remaining in the filtrate by gas chromatography (using Shimadzu GC-12A
gas chromatograph apparatus) revealed a 2-chloroaniline conversion of 35%.
The polymer was thermally cured in air at 235C
for a further 2 hours to give a cured amino-containing polyphenylene sulfide having a melt viscosity of 8,000 poises. This cured polymer will be referred to as PPS-V.
Preparation 6 Synthesis of amino-containinF Polyphenylene sulfide An amino-containing polyphenylene sulfide resin was prepared by repeating the general procedure of the preceding Preparation 1 except that 1789 g p-dichlorobenzene, and 310 g 3,5-diaminochlorobenzene (corresponding to about 15 mol% of the total amount of the p-dichlorobenzene and 3,5-diaminochlorobenzene present) were employed in this Preparation 6, and that the temperature of the reaction mixture was slowly raised to 250C over a period of one hour and 20 minutes and then the mixture was allowed to polymerize at 250C for a further 3 hours. The resulting amino-containing polYphenylene sulfide had a melt viscosity that was too low to be determined by the above-specified flow tester method. Analysis of the unconverted 3,5-diaminochlorobenzene remaining in the filtrate by gas chromatography (using Shimadzu GC-12A gas chromatograph apparatus) revéaled a 3,5-diaminochlorobenzene conversion of 38%.
The polymer was thermally cured in a.ir at 235C for a further 10 hours to give a cured amino-containing polyphenylene sulfide having an increased melt viscosity of 6,600 poises. This cured polYmer will be referred to as PPS-VI.
-16- 2~6~907 PreParation 7 Graft copolymerization of Polyethylene with acid - A high densitY polyethylene 97.5 weight % was premixed with maleic anhydride 2 weight % and 2,5-dimethyl-2,5-di(tert.-butyl peroxy)hexane 0.5 weight %. The premix was fed to an extruder machine with a cylinder maintained at a temperature of 210C. During passage through the extruder, the premix was kneaded and allowed to react.
By this procedure, pellets of a graft copolymerized, high - 10 density polyethYlene were prepared.
PreParation 8 PreParation of carboxylic ~roup-containinF olefinic coPolymer An ethylene-butene-1 copolymer (commercially avail-able under trade mark TAFMER A4090) 100 parts by weight waspremixed with maleic anhydride 1 part by weight and 1,3-bis(tert.-butyl peroxy propyl) benzene 0.5 parts by weight.
The premix was fed to an extruder machine with a cylinder maintained at 220G. During passage through the extruder, the premix was kneaded and allowed to react. By this procedure, pellets of a carboxylic group-containing olefinic copolymer were prepared.
By IR spectrography, the quantity of maleic anhydride grafted on to the ethylene-butene-l copolymer substrate was confirmed to be 0.75 parts by weight of maleic anhydride per 100 parts by weight of ethylene-butene-1 copolymer. This graft copolymer will be referred to as "modifled P0".
ExamPle PPS-I from Preparation 1 and the graft copolymerized polyethylene from Preparation 7 were mixed in relative proportions of 90% and 10% by weight and fed to a vent-type vacuum twin-screw extruder which had a venting pressure of 30 Torrs at the vent. In the extruder, the mixture was kneaded at 300C to produce pellets thereof. A sample of the pellets was in~ection molded at a temperature of 300C
to prepare various test specimens to be sub~ected to tests of:
-17- 2~6~07 Izod Impact Strength; notched, according to ASTM D-256 Tensile Elongation; according to ASTM D638, at 5 mm/minute Heat Distortion Temperature; according to ASTM D648, with a load of 18.6 kg/cm2 In addition, a 1/8 inch thick test specimen prepared for the heat distortion temperature test was subjected to a solvent resistance test, where the specimen was immersed in a gasohol mixture comprising gasoline and methanol in a weight ratio of 80:20, at a temperature of 125C for 8 hours. The weight of the specimen was measured before and after the immersion test. The solvent resistance performance was rated by the difference of the two weights.
The results are set forth in Table 1.
Example 2 PPS-II from Preparation 2 and the graft copolymerized polyethylene from Preparation 7 were mixed in relative proportions of 90% and lO~o by weight. The mixture was processed and tested as in Example 1.
The results are set forth in Table 1.
ExamPle 3 PPS-I from Preparation 1, the grafted polyethylene from Preparation 7, and glass fibers were mixed in relative proportions of 63%, 7% and 30% by weight. The mixture was processed and tested as in Example 1. The results are set forth in Table 1.
ExamPle 4 PPS-V from Preparation 5 and the grafted polyethylene from Preparation 7 were mixed in relative proportions of 90% and 10% by weight. The mixture was processed and tested as in Example 1. The results are set forth in Table 1.
Comparative ExamPles 1 and 2 The procedure of Example 1 was repeated using either PPS-III or PPS-IV as an amino-containing polyphenylene sulfide material. The results are shown in Table 1.
ComParatiVe ExamPles 3 - 6 PPS-I from Preparation 1, the grafted polyethylene from Preparation 7 and glass fiber were mi.xed in various .
3 ~
relative proportions as given in Table 1. Each of the mixtures was processed and tested as in Example l. I`he results are al.so shown in Table l.
Comparative Example 7 PPS-I from Preparation 1 and an unmodified high density polyethylene were mixed in relative proportions of 90% and 10% by weight. The mixture was processed and tested as in Example 1. The results are sho~Yn in Table 1.
Comparative Example 8 PPS-VI from Preparation 6 and the grafted polyethylene from Preparation 7 were mixed in relative proportions of 90% and 10% by weight. The mixture was processed and tested as in Example 1. The results are shown in Table 1.
Comparative ExamPle 9 PPS-I from Preparation ] and the modified P0 from Preparation 8 were mixed in relative proportions of 90% and 10% by weight. The mixtllre was subjected to the process as described in Example 1. However, during the melt-kneading - 20 in the vented twin-screw extruder, part of -the melt was expelled through the vent. This made the extrusion procedure unstable. Further, it was found that the resulting pellets had bubbles caught therein. Furthermore, the moldings showed a poor appearance. The test results are shown in Table 1.
As above-illustrated, according to -I;he invel-ltion, a specially prepared polypherlylelle suJ.f:i(le ma-(;el:ial. contaiJlirlg a speci-fied amount of amino groups is formulated with a specially modified polyethylene material so as to provide a po].yphenylene su].fide resin composition which retains the desired proper-ties, SUC}l as high temperature resistance and chemical resis-tance, possessed originally by the unmodified polyphenylene sul.fide itseli` and is significantly improved in the toughness properties, such as impact strength, and in the tensile elongation properties.
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Claims (18)
1. A polyphenylene sulfide resin composition which comprises (A) 60 - 99.5% by weight of a thermally cured polyphenylene sulfide material having a melt viscosity of 500 - 30,000 poises and which has been derived, by thermally curing, from a polyphenylene sulfide having a melt viscosity of 400 poises or higher and containing 0.05 - 5 mol% of amino groups on the basis of the phenylene sulfide repeating units, and (B) 40 - 0.5% by weight of a modified polyethylene material comprising at least one polyethylene onto which at least one unsaturated carboxylic acid and/or derivative thereof is graft-copolymerized in a proportion of 0.1 - 10%
by weight of the total weight of said modified polyethylene material.
by weight of the total weight of said modified polyethylene material.
2. A resin composition according to Claim 1 wherein component (A) contains 0.1 - 3 mol% amino groups.
3. A resin composition according to Claim 1 or 2 wherein the amino-containing polyphenylene sulfide has a melt viscosity of 500 poises or higher before thermal curing and a melt viscosity of 1,000 - 2,000 poises after thermal curing.
4. A resin composition according to any one of Claims 1 - 3 wherein the amino-containing polyphenylene sulfide is produced by reacting an alkali metal sulfide with a dihalobenzene in the presence of an amino-containing aromatic halide in an organic amide solvent.
5. A resin composition according to any one of Claims 1 - 4 wherein the amino-containing polyphenylene sulfide has the amino groups attached to the ends of its molecule.
6. A resin composition according to any one of Claims 1 - 5 wherein the amino-containing polyphenylene sulfide comprises at least 70 mol% of p-phenylene sulfide structural unit represented by:
and remainder of one or more other copolymerized units selected from the group consisting of m-phenylene sulfide, o-phenylene sulfide, phenylene sulfide sulfone, phenylene sulfide ketone, phenylene sulfide ether, and diphenylene sulfide units in addition to the amino-containing units.
and remainder of one or more other copolymerized units selected from the group consisting of m-phenylene sulfide, o-phenylene sulfide, phenylene sulfide sulfone, phenylene sulfide ketone, phenylene sulfide ether, and diphenylene sulfide units in addition to the amino-containing units.
7. A resin composition according to Claim 4 wherein the amino-containing aromatic halide reactant has the general formula:
where X is a halogen, Y is hydrogen, -NH2 or a halogen, each R is a hydrocarbyl group containing 1 - 12 carbon atoms and n is an integer of 0 - 4.
where X is a halogen, Y is hydrogen, -NH2 or a halogen, each R is a hydrocarbyl group containing 1 - 12 carbon atoms and n is an integer of 0 - 4.
8. A resin composition according to any one of Claims 1 - 7 wherein component (A) is prepared by thermally curing the amino-containing polyphenylene sulfide in air at a temperature in the range of 200° to 280°C for a period of from 1 to 12 hours.
9. A resin composition according to any one of Claims 1 - 7 wherein component (A) is prepared by thermally curing the amino-containing polyphenylene sulfide in a nonoxidizing atmosphere at a temperature of about 200° to about 280°C
for a period of from 1 to 24 hours.
for a period of from 1 to 24 hours.
10. A resin composition according to any one of Claims 1 - 9 wherein component (B) modified polyethylene material has 1 - 5% by weight of the unsaturated carboxylic acid and/or derivative thereof grafted thereon.
11. A resin composition according to any one of Claims 1 - 10 wherein the unsaturated carboxylic acid is selected from the group consisting of acrylic, methacrylic, maleic, fumaric, itaconic and citraconic acids and derivatives thereof.
12. A resin composition according to Claim 11 wherein the acid is maleic anhydride.
13. A resin composition according to any one of Claims 1 - 12 wherein component (B) is prepared by mixing a polyethylene, an unsaturated carboxylic acid and/or derivative thereof and a radical generator and melt-extruding the mixture under copolymerization conditions.
14. A resin composition according to Claim 13 wherein the radical generator is an organic peroxide.
15. A resin composition according to any one of Claims 1 - 14 wherein component (B) is prepared by dissolving or suspending a polyethylene in an appropriate solvent, adding an unsaturated carboxylic acid and a radical initiator to the liquor and heating the mixture at a copolymerization temperature.
16. A resin composition according to any one of Claims 1 - 15 which comprises 80 - 97% by weight of component (A) and 20 - 3% by weight of component (B).
17. A resin composition according to any one of Claims 1 - 16 wherein one or more conventional additives or fillers is incorporated at suitable levels.
18. A resin composition according to any one of Claims 1 - 17 wherein component (B) is derived from a high density polyethylene.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP40577/1991 | 1991-02-13 | ||
JP4057791 | 1991-02-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2060907A1 true CA2060907A1 (en) | 1992-08-14 |
Family
ID=12584345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002060907A Abandoned CA2060907A1 (en) | 1991-02-13 | 1992-02-10 | Polyphenylene sulfide resin composition |
Country Status (3)
Country | Link |
---|---|
KR (1) | KR920016555A (en) |
CA (1) | CA2060907A1 (en) |
TW (1) | TW203084B (en) |
-
1992
- 1992-02-10 CA CA002060907A patent/CA2060907A1/en not_active Abandoned
- 1992-02-12 KR KR1019920001978A patent/KR920016555A/en not_active Application Discontinuation
- 1992-02-12 TW TW081100978A patent/TW203084B/zh active
Also Published As
Publication number | Publication date |
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KR920016555A (en) | 1992-09-25 |
TW203084B (en) | 1993-04-01 |
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