CN1894337A - Polyester molding composition - Google Patents
Polyester molding composition Download PDFInfo
- Publication number
- CN1894337A CN1894337A CN 200480037661 CN200480037661A CN1894337A CN 1894337 A CN1894337 A CN 1894337A CN 200480037661 CN200480037661 CN 200480037661 CN 200480037661 A CN200480037661 A CN 200480037661A CN 1894337 A CN1894337 A CN 1894337A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic resin
- resin composition
- acid
- polyester
- blend
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 229920000728 polyester Polymers 0.000 title claims abstract description 32
- 238000000465 moulding Methods 0.000 title claims description 7
- 239000004417 polycarbonate Substances 0.000 claims abstract description 28
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229920001634 Copolyester Polymers 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- 229920003232 aliphatic polyester Polymers 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 abstract description 10
- 239000004609 Impact Modifier Substances 0.000 abstract description 2
- -1 alkane diol Chemical class 0.000 description 25
- 238000012360 testing method Methods 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 229920002633 Kraton (polymer) Polymers 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000013100 final test Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical class CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 150000007520 diprotic acids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 229920003251 poly(α-methylstyrene) Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 239000002426 superphosphate Substances 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (1R)-1,3-butanediol Natural products CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- VSKSUBSGORDMQX-UHFFFAOYSA-N 1,2-dichloro-3-phenoxybenzene Chemical compound ClC1=CC=CC(OC=2C=CC=CC=2)=C1Cl VSKSUBSGORDMQX-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 1
- JHOPNNNTBHXSHY-UHFFFAOYSA-N 2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1O JHOPNNNTBHXSHY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- SYDNSSSQVSOXTN-UHFFFAOYSA-N 2-nitro-p-cresol Chemical compound CC1=CC=C(O)C([N+]([O-])=O)=C1 SYDNSSSQVSOXTN-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- GRBSHVCIKYLDAO-UHFFFAOYSA-N 4-(3,5-diethyl-4-hydroxyphenyl)sulfonyl-2,6-diethylphenol Chemical compound CCC1=C(O)C(CC)=CC(S(=O)(=O)C=2C=C(CC)C(O)=C(CC)C=2)=C1 GRBSHVCIKYLDAO-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QQXDYWHKPKEBJU-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCCCCCCCC[Na] QQXDYWHKPKEBJU-UHFFFAOYSA-N 0.000 description 1
- 241001212143 Cernia Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 description 1
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 1
- ZMISKZOTXULZON-UHFFFAOYSA-N OC1(O)C=CC=CC1C1=CC=CC=C1 Chemical compound OC1(O)C=CC=CC1C1=CC=CC=C1 ZMISKZOTXULZON-UHFFFAOYSA-N 0.000 description 1
- HLSMGGKZHOXWIG-UHFFFAOYSA-N OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)O.OC1=CC=C(C=C1)CCC Chemical compound OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)O.OC1=CC=C(C=C1)CCC HLSMGGKZHOXWIG-UHFFFAOYSA-N 0.000 description 1
- AZMNXWZAJQHTGB-UHFFFAOYSA-N OP(O)=O.CC1=CC=CC=C1C Chemical compound OP(O)=O.CC1=CC=CC=C1C AZMNXWZAJQHTGB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
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- 238000003801 milling Methods 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
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- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical group C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
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- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
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- 239000010456 wollastonite Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A clear thermoplastic resin blend comprises a low viscosity polyester cycloaliphatic resin derived from a cycloaliphatic diol or equivalent thereof and a cycloaliphatic dicarboxylic acid or equivalent thereof, a copolyesterether, an impact modifier and, optionally a polycarbonate wherein the resulting blend has a low flexural modulus with high Shore D hardness.
Description
The cross reference of related application
The application requires the right of priority of the U.S. Provisional Application series 60/530590 of submission on December 18th, 2003, and it is incorporated herein by reference in full at this.
Invention field
The present invention relates to the blend of polycarbonate and vibrin.
Background of invention
People's such as Scott United States Patent (USP) 5,942,585 relates to the blend of polycarbonate and polyester, and wherein polyester comprises based on 1, the unitary dicarboxylic acid component of 4-cyclohexane dicarboxylic acid and comprise 2,2,4,4-tetramethyl--1, the diol component of 3-tetramethylene diol units.Can be described in a Free Volume approach to the MechanicalBehaviour of Miscible Polycarbonate Blends by miscible polycarbonate polyester blends, people such as A.J.Hill, J.Phys.Condens.Matter, 8,3811-3827 (1996) and Dynamic Mechanical andDielectric Relaxation Study of Aliphatic Polyester Based Blends, people such as Stack, J.M.Polym.Mater.Sci.Eng. (1993), 69,4-5, EastmanChemical Company, Kingsport, TN 37662.People's such as Light United States Patent (USP) 4,879,355 relates to the blend polymer that comprises following material: have the glycol copolyesters from the repeating unit of 1,4 cyclohexane dimethanol, terephthalic acid and aklylene glycol; Polycarbonate resin; With the aromatic polyester that has from the repeating unit of terephthalic acid, m-phthalic acid and dihydroxyphenyl propane.People's such as Allen United States Patent (USP) 4,786,692 relates to the blend of aromatic polycarbonate and multipolymer, and this multipolymer is derived from the glycol moiety that comprises 1,4 cyclohexane dimethanol and ethylene glycol.
People's such as Borman United States Patent (USP) 5,399,661 relates to polyester composition, and said composition comprises the reaction product of following material: at least a straight chain, branching or cyclic aliphatic C
2-C
10The mixture of alkane diol or chemical equivalents and at least two kinds of cyclic aliphatic diprotic acid.The diprotic acid mixture mainly comprises trans-isomer(ide) and at least a aromatic diacid.As on 5 hurdles, described in 41-45 is capable, " reaction is adopted the excess glycol component usually and is carried out in the presence of suitable catalyst ".People's such as Borman United States Patent (USP) 5,486,562 described in addition be used for ' 661 patents described in impact-resistance modified dose of type of composition.
The United States Patent (USP) 4,188,314 of Fox has been described and will have been joined derived from the polyester polymers of the cyclohexanedimethanol and the mixture of m-phthalic acid and terephthalic acid in the aromatic carbonate polymers to strengthen the solvent resistance of comparing with polycarbonate article.
Other reference comprises patent 6,043,322; 6,037,424; 6,011,124; 6,005,059; 5,942,585; 5,194,523; With 5,017,659 and GB 1,559,230A.
The blend of polycarbonate and polyester typically has attractive performance such as toughness and chemical resistance.Need to form the blend of this type, this blend keeps these required performances but the desired properties that has low modulus in flexure and high rigidity in addition.
Summary of the invention
According to embodiment, polycarbonate polyester blends has low-down modulus in flexure and high Shore D hardness.Typically in most of blends, these two kinds of performances are directly related.For example, when blend had low modulus in flexure, hardness also significantly reduces and vice versa.According to embodiment, polycarbonate polyester blends by injection moulding processing, strengthens their adaptability for many application easily thus.Low modulus in flexure of performance and high rigidity are converted into the blend polymer with excellent bending fatigue resistance, tear strength and hysteresis quality.According to embodiment, material is suitable for golf spherical shell type application unexpectedly, wherein with above-mentioned performance prevent kernel undermined be important.
The performance specification of various blends is in table 2.Embodiment 1,3,8,12 and 13 is embodiments of the invention and remaining embodiment is a Comparative Examples.
According to embodiment, thermoplastic resin composition comprises that wherein the blend of Huo Deing has low modulus in flexure and high Shore D hardness derived from low-viscosity polyester cycloaliphatic resin, copolyester ether, ABS resin and/or the impact modifying agent of cycloaliphatic diol or its coordinator and cycloaliphatic dicarboxylic acid or its coordinator and optional polycarbonate.According to embodiment, the modulus in flexure of resin blend is that about 120kpsi of about 45-and Shore D hardness are about 55-about 72.According to embodiment, the weight-average molecular weight of cyclic aliphatic vibrin is about 30, about 150,000 atomic mass units of 000-(amu), and with respect to polystyrene standards, and solvent is 5% hexafluoroisopropanol in chloroform at room temperature.The weight-average molecular weight of these polyester is preferably 65, and 000-is about 85,000amu.According to embodiment, the quantity that the cyclic aliphatic polyester exists is the about 40wt% of about 10-of total resin.According to embodiment, the quantity that copolyester ether exists is the about 55wt% of about 20-of total resin.According to embodiment, the quantity that impact modifying agent exists is the about 50wt% of about 20-of total resin.According to embodiment, optional polycarbonate can comprise every kind of at least two kinds of different polycarbonate with different molecular weight.If present, polycarbonate is the about 25wt% of about 5-of total resin.
Need low modulus in flexure blend to have the good mechanical property that may lose in addition.Favorable mechanical performance as shown in table 2 keeps in embodiment 1,3,8,12 and 13.
Detailed Description Of The Invention
For for simplicity, the implication of the abbreviation that following table 1 explanation is used in whole specification sheets.
Table 1: abbreviation
| Abbreviation | Title |
| PC | Polycarbonate |
| PCCE | Copolyester ether |
| PCCD | 1, the 4-cyclohexane dicarboxylic acid is with the polymkeric substance (9CI chemical abstracts index-name) of 1,4 cyclohexane dimethanol; I.e. poly-(1,4-cyclohexylidene dimethylene 1,4-cyclohexanedicarboxyester ester) |
| ABS | Acronitrile-butadiene-styrene |
| CHDM | 1,4 cyclohexane dimethanol (trans/cis mixture) |
| t-DMCD | Anti-form-1,4-cyclohexane dicarboxylic acid dimethyl ester |
| MV | Melt viscosity |
| T m | Fusing point |
The preparation method of moulding compound comprises and selects for example blend of component PC (optional), PCCD, PCCE and impact modifying agent.Add impact modifying agent to strengthen required mechanical property.
The cyclic aliphatic vibrin has the repeating unit of general formula I A:
With reference to previously described general formula, R
1Derived from 1,4 cyclohexane dimethanol or chemical equivalents; And A
1It is cyclohexane ring derived from cyclohexanedicarboxyester ester or its chemical equivalents.Favourable PCCD has the cis/trans structural formula.
Preferred cyclic aliphatic polyester is poly-(hexanaphthene-1,4-Dimethylenecyclohexacompound-1,4-dicarboxylic ester), is also referred to as poly-(1,4 cyclohexane dimethanol-1,4-cyclohexanedicarboxyester ester) and (PCCD), has the repeating unit of general formula I B:
In general formula I B, R is H or low alkyl group.
Polyester reaction usually in melt suitable catalyst as four (2-ethylhexyl) titanic acid ester in the presence of, adopt suitable quantity, typically carry out based on the titanium of the about 50-200ppm of final product.
The weight-average molecular weight of preferred cyclic aliphatic polyester (using polystyrene standards to measure by gel permeation chromatography) is about 30, about 150,000 atomic mass units of 000-(amu), be preferably approximately 60,000-is about 100,000amu, more preferably about 65,000-is about 95,000amu.
This also consider to have the about 50wt% of about 1-derived from the unitary above polyester of polymeric aliphatic acid and/or polymeric aliphatic polyvalent alcohol to form copolyesters.Aliphatic polyol comprises glycol, as poly-(ethylene glycol) or poly-(butyleneglycol).Such polyester can be followed for example instruction preparation of United States Patent (USP) 2,465,319 and 3,047,539.
In preferred general formula I B:
R be the alkyl of 1-6 carbon atom or derived from arbitrary monomeric remaining end group and n greater than about 70.Polyester is derived from the transesterification reaction of initial DMCD and initial CHDM.Be preferably greater than about 8 to 1 and be preferably greater than about 1 to 1 derived from the trans-cis ratio of the repeating unit of DMCD derived from the trans-cis ratio of the repeating unit of CHDM.The weight-average molecular weight of these polyester is preferably 65, and 000-is about 85,000amu, and melt temperature is preferably greater than 216 ℃ and acid number preferably less than about 10, is more preferably less than about 6meq/kg.
Linear PCCD polyester can be prepared in the presence of catalyzer by the condensation reaction of CHDM and DMCD, wherein initial DMCD's trans-cis ratio greater than equilibrated trans-cis ratio.The PCCD polyester of the preparation that obtains have derived from the repeating polymer of each initial DMCD unitary trans-cis ratio, its trans-cis ratio equal substantially each initial trans-cis ratio to be to strengthen the degree of crystallinity of the PCCD that obtains.
It is about 6 to 1 that trans-cis ratio of initial DMCD is typically greater than, and is preferably greater than 9 to 1 and even more preferably greater than 19 to 1.In the PCCD that obtains,, and be more preferably less than about 5% initial trans DMCD and between the reaction period of CHDM and DMCD, change into cis-isomeride to produce PCCD preferably less than about 10% initial trans DMCD.CHDM's is trans: cis ratio is preferably greater than 1 to 1 and more preferably greater than about 2 to 1.
The quantity that preferred catalyst exists is less than about 200ppm.Typically, the catalyzer scope that can exist is the about 300ppm of about 20-.Most preferred material is a blend, and wherein polyester contains cyclic aliphatic diprotic acid and cycloaliphatic diol component, is specially poly-cyclohexanedimethanol cyclohexyl dicarboxylic acid ester (PCCD).
Being used for polyester ether of the present invention can be prepared by routine techniques, as at United States Patent (USP) 4,349, described in 469.A kind of such preferred polyester ether can be from Eastman Chemicals with ECDEL
Resin is buied.Other preferred polyester ether comprises NEOSTAR
Elastomerics is as FN005, FN006 and FN007 available from Eastman Chemical Company.The dicarboxylic acid component of polyester ether can be at least 70% by trans-isomer content substantially, preferably at least 80% and most preferably at least 85% 1, and the 4-cyclohexane dicarboxylic acid is formed.1,4-cyclohexane dicarboxylic acid and 1,4 cyclohexane dimethanol can be by known technology preparations and commercially available." Man-Madefibers:Science and Technology ", Vol.III, Mark, Atlas and Cernia compile, and Interscience Publishers publishes, and has described 1 at 85 pages, the preparation of 4-cyclohexane dicarboxylic acid and 1,4 cyclohexane dimethanol.Poly-(oxygen tetramethylene) diol component of polyester ether is commercially available, and is prepared by technique known.The molecular weight of poly-(oxygen tetramethylene) glycol is the about 1100amu of about 500amu-, preferably about 1000amu (weight average).Polyester ether can comprise that further about at the most 1.5mol% has the polyvalent alcohol branching agent of at least three COOH or OH functional group and 3-60 carbon atom, based on acid or diol component.Also can use the ester of many this acid or polyvalent alcohol.Suitable branching agent comprises 1,2,4-benzenetricarboxylic acid or acid anhydrides, 1,3,5-benzenetricarboxylic acid, trimethylolethane, TriMethylolPropane(TMP) and tripolymer acid.
Should be appreciated that total acid reaction should be 100mol% and the total diol reactant should be 100mol%.Although acid reaction it is said " substantially by 1, the 4-cyclohexane dicarboxylic acid is formed " that if branching agent is polyprotonic acid or acid anhydrides, it is calculated as the part of 100mol% acid.Equally, diol reactant it is said " being made up of 1,4 cyclohexane dimethanol and poly-(oxygen tetramethylene) glycol substantially " that if branching agent is a polyvalent alcohol, it is calculated as the part of 100mol% glycol.
Also can adopt ABS resin.These resins contain vinyl cyanide, divinyl and cinnamic unit.It is the about 50wt% of about 20-of resin blend when existing.
Preferred impact modifying agent contains the polymer unit that reduced TG changes the polymer unit of rubbery component and derived from ethylene base aromatic substance, acrylic compound, acrylic acid alkyl ester compound or derivatives thereof.The preferred impact modifying agent quantity that adopts is the about 20wt% of about 5-, based on the gross weight of resin molding compositions.
For making moulding resin under about-10 ℃ temperature, keep ductility, preferred impact modifying agent is the hud typed impact modifying agent that has as the lower section: comprise derived from butadiene or n-butyl acrylate polymkeric substance rubbery state nuclear and comprise the shell of the polymkeric substance of derived from ethylene base aromatic substance, vinyl cyanide compound or alkyl methacrylate compound, preferred shell derived from independent or with vinylbenzene bonded methacrylic ester.Particularly preferred graftomer is available from Rohm ﹠amp; The core-shell type polymkeric substance of Haas, for example ParaloidEXL3691.What also exist in the fs is that cross-linking monomer is connected monomer with grafting.The example of cross-linking monomer comprises diacrylate 1,3 butylene glycol ester, Vinylstyrene and tetramethylene dimethacrylate.It is allyl acrylate, allyl methacrylate(AMA) and diallyl maleate that grafting connects monomeric example.
The preparation method of nuclear-shell copolymer, nuclear-shell copolymer and the purposes that combines with polycarbonate as the nuclear-shell copolymer of impact modifying agent are described in United States Patent (USP) 3,864,428 and 4,264,487.
Suitable nuclear-shell copolymer is to comprise as those of lower section: second-order transition temperature (" Tg ") is less than-30 ℃ approximately, preferably less than-40 ℃, and comprise derived from one or more single ethylenically unsaturated monomers such as acrylate monomer, as butyl acrylate, and conjugated diene monomer,, and comprise more than or equal to about 40 ℃ as the rubbery state " nuclear " of the repeating unit of divinyl and Tg, as the rigidity " shell " of the repeating unit of methyl methacrylate derived from single ethylenically unsaturated monomers.
The preferred impact modifying agent of unitary another kind that comprises derived from butadiene and vinyl aromatic compounds comprises the ABA triblock copolymer, particularly comprises those of styrenic block and divinyl or isoprene block.Compare with the core-shell impact modifiers of previous discussion, the segmented copolymer impact modifying agent lacks the low temperature ductility performance.Conjugated diene block is hydrogenation partially or completely, so they can be expressed as ethylene-propylene block etc. and have performance similar in appearance to olefin block copolymers.The example of this type triblock copolymer is polystyrene-poly divinyl-polystyrene (SBS), hydrogenated polystyrene-polyhutadiene-polystyrene (SEBS), polystyrene-poly isoprene-polystyrene (SIS), poly-(alpha-methyl styrene)-polyhutadiene-poly-(alpha-methyl styrene) and poly-(alpha-methyl styrene)-polyisoprene-poly-(alpha-methyl styrene).
Particularly preferred triblock copolymer can Kraton D and KRATON G available from Shell.The KRATON polymkeric substance constitutes KRATON D series (styrene-butadiene-styrene with the compound that contains the unsaturated rubber mid-block, SBS and styrene-isoprene-phenylethene, SIS), and contain saturated mid-block those form KRATON G series (styrene-ethylene/butylene-styrene, SEBS and styrene-ethylene/propylene-styrene, SEPS).D-and G-series polymer all are elasticity and flexible.KRATION G-series polymer is because the scale resistance that increases is preferred for weathering resistance.
The polycarbonate resin that is used to prepare blend of the present invention is aromatic polycarbonate resin normally.Preferred polycarbonate comprises the unit of bis-phenol that BPA, SBI bis-phenol, aryl replace, cyclic aliphatic bis-phenol and composition thereof.
Typically these prepare by making dihydric phenol and carbonate precursor such as phosgene, haloformate or carbonate reaction.Generally speaking, such carbonate polymer can typically have general formula :-O-Ar-O-(CO)-repeated structural unit, wherein Ar is the divalent aromatic radical derived from the dihydric phenol that is used for polymer production reaction.
Preferably, be used for providing the intrinsic viscosity (as measuring down at 25 ℃) of the carbonate polymer of resin compound of the present invention to be the about 1.00dl/g of about 0.30-at methylene dichloride.
Can be used for the dihydric phenol of this aromatic carbonate polymers is provided is monokaryon or the multi-nucleus aromatic compound that comprises as two hydroxyls of functional group, and each hydroxyl is directly connected on the carbon atom of aromatic kernel.Typical dihydric phenol is: 2, two (4-hydroxyphenyl) propane of 2-, Resorcinol, Resorcinol, 2, two (4-hydroxyphenyl) pentanes of 2-, 2,4 '-(dihydroxyl phenylbenzene) methane, two (2-hydroxyphenyl) methane, two (4-hydroxyphenyl) methane, two (4-hydroxyl-5-nitrophenyl) methane, 1, two (4-hydroxyphenyl) ethane of 1-, 3, two (4-hydroxyphenyl) pentanes of 3-, 2,2-dihydroxyl phenylbenzene, 2, the 6-dihydroxy naphthlene, two (4-hydroxy diphenyl) sulfone, two (3,5-diethyl-4-hydroxyphenyl) sulfone, 2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane, 2,4 '-dihydroxy-diphenyl sulfone, 5 '-chloro-2,4 '-dihydroxy-diphenyl sulfone, two-(4-hydroxyphenyl) sulfobenzide, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-the dichloro diphenyl ether, 4,4-dihydroxyl-2,5-dihydroxydiphenyl ether etc.
Other dihydric phenol that also is applicable to the above polycarbonate of preparation is disclosed in United States Patent (USP) 2,999,835; 3,038,365; 3,334,154; With 4,131, in 575.
These aromatic polycarbonates can be by known method, for example and as mentioned above, by making dihydric phenol and carbonate precursor, as phosgene reaction, according in above citing document and at United States Patent (USP) 4,123, in 436 the explanation method, or by as at United States Patent (USP) 3,153, disclosed ester exchange method in 008, and other method well known by persons skilled in the art and preparing.
Wish to be used to prepare under the situation of polycarbonate blend of the present invention at carbonate copolymer or interpolymer rather than homopolymer, also can adopt two or more different dihydric phenols or dihydric phenol and glycol or with hydroxyl-the acid blocked polyester or with the multipolymer of diprotic acid.The polycarbonate of branching can be useful, as at United States Patent (USP) 4,001, described in 184.Equally, can adopt the blend of linear polycarbonate and branching polycarbonate.In addition, the blend of any above material can be used for implementing the present invention so that aromatic polycarbonate to be provided.
Being used to implement preferred aromatic carbonate of the present invention is homopolymer, and for example derived from 2, the homopolymer of two (4-hydroxyphenyl) propane (bisphenol-A) of 2-is with trade(brand)name LEXAN
TMAvailable from General Electric Company.
Blend polymer comprises about 20-55wt% copolyester ether.The I.V. of typical copolyester ether is about 0.8-1.5dl/g and comprises from the repeating unit as the lower section: a) be at least 70% by trans-isomer content substantially, preferred at least 80% 1, the dicarboxylic acid component that the 4-cyclohexane dicarboxylic acid is formed, b) substantially by 1) the preferred trans-isomer content of about 75-96mol% be at least 60% 1, the 4-cyclohexanedimethanol, with 2) about 25-4mol% (about 15-50wt%, weight based on polyester ether) molecular weight is the diol component of poly-(tetramethylene ether) glycol (PTMG) composition of about 500-1100, and c) the about 1.5mol% of 0-has at least three functional groups that are made up of COOH and/or OH and the branching agent with 3-60 carbon atom, based on the mol% of acid or diol component.
In addition, additive such as oxidation inhibitor, thermo-stabilizer, releasing agent, static inhibitor, whitening agent, tinting material, softening agent, mineral substance such as talcum, clay, mica, barite, wollastonite and include but not limited to UV stablizer such as benzotriazole other stablizer, replenish reinforcing filler such as sheet or the glass of milling etc., fire retardant, pigment, other resin or its combination can join in the composition of the present invention.The different additive that can introduce composition is normally used and is well known by persons skilled in the art.The illustrative of this additive is described visible R.Gachter and H.Muller, Plastics Additives Handbook, the 4th edition, 1993.
The example of thermo-stabilizer comprises triphenyl phosphite, three-(2,6-dimethylbenzene phenyl) phosphorous acid ester, three-(2,4-di-t-butyl-phenyl) phosphorous acid ester, three-(mix single-and two-nonyl phenyl) phosphorous acid ester, dimethyl benzene phosphonic acid ester and trimethyl phosphite 99.The example of oxidation inhibitor comprises octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester and tetramethylolmethane base-four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester].The example of photostabilizer comprises 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl)-benzotriazole and 2-hydroxyl-4-n-octyloxy benzophenone.The example of softening agent comprises dioctyl-4,5-epoxy-hexahydrophthalic acid ester, three-(carbonyl octyloxy ethyl) isocyanuric acid ester, Tristearoylglycerol and epoxidised soybean oil.The example of static inhibitor comprises glyceryl monostearate, stearyl sodium sulfonate and Sodium dodecylbenzene sulfonate.
The preferred type stablizer that comprises in the preparaton is a quencher.Typically, this stablizer is using under the level of 0.001-10wt% and under the preferred level at 0.005-2wt%.Favourable stablizer comprises the superphosphate of significant quantity; Have acid, alkyl, the aryl of at least one acidic hydrogen or mix phosphorous acid ester; IB family or IIB family metal phosphate; Phosphorus oxyacid, metal acid pyrophosphate or its mixture.Specific compound with how much quantity of the adaptability of used as stabilizers and stand-by used as stabilizers is determined and can easily be determined by following mode: the influence that the mixture of preparation vibrin component and polycarbonate and determining forms melt viscosity, gas generation or colour stability or interpolymer.Superphosphate comprises SODIUM PHOSPHATE, MONOBASIC, mono phosphoric acid ester zinc, potassium hydrogen phosphate, monocalcium phosphate etc.Phosphorous acid ester can have general formula V:
Wherein R1, R2 and R3 are independently selected from hydrogen, alkyl and aryl, and condition is that at least one of R1, R2 and R3 is hydrogen.
The phosphoric acid salt of IB family or IIB family metal comprises zinc phosphate etc.Phosphorus oxyacid comprises phosphorous acid, phosphoric acid, Tripyrophosphoric acid or Hypophosporous Acid, 50.
The polyacid pyrophosphate salt can have general formula VI:
MzxHyPnO3n+l
Wherein M is a metal, and x is the number of 1-12 and the number that y is 1-12, and n is the number of 2-10, and z is the number of 1-5 and (xz)+y's and equal n+2.Preferred L is alkali or alkaline-earth metal.
Most preferred quencher is the oxygen acid or the acid organo phosphorous compounds of phosphorus.The mineral acid phosphorus compound also can be used as quencher, yet they can cause the loss of optical haze or transparency.Most preferred quencher is phosphoric acid, phosphorous acid or their part ester.
The example of releasing agent comprises pentaerythritol tetrastearate, stearic acid stearyl ester, beeswax, montanin wax and paraffin.The example of other resin includes but not limited to polypropylene, polystyrene, polymethylmethacrylate and polyphenylene oxide.Can use the combination of any above-mentioned additive.Such additive can mix between for the component mixing period that forms composition in the suitable time.
Polyester ether preferably includes phenolic antioxidant, preferred phenolic antioxidant be obstructed with relative nonvolatile.
Preferably four [methylene radical (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate) methane, it is buied with Irganox 1010 oxidation inhibitor from Ciba-Geigy Chemical Company.Preferably, the usage quantity of oxidation inhibitor is about 1.0 for about 0.1-, based on the weight of copolyester ether.
The production of composition can be adopted the known any blend operation of thermoplastics blend, for example blend in kneader such as banbury mixers or forcing machine.Reinforced order is not crucial, but abundant all components of blend.
Be the preparation resin combination, component can be mixed by any known method.Typically, there are two different mixing steps: premix step and melt-mixing step.In the premix step, dry ingredient is mixed.The premix step typically uses tumbler mixer or ribbon mixer to carry out.Yet as needs, pre-composition can use high shear mixer such as Henschel mixing machine or similar high strength device fabrication.Typically be the melt-mixing step after the premix step, wherein with pre-composition fusion and be mixed into melt once more.Perhaps, can omit the premix step, and starting material directly can be added the feed zone of melt-mixing equipment, preferably by many feed systems.In the melt-mixing step, with composition melt kneading in single screw rod or twin screw extruder, banbury mixers, two roller roller refining machine or like device typically.
Can be by various techniques known in the art such as injection moulding, compression moulding, extrude, gas helps blowing or vacuum forming is configured as end article with composition.
Embodiment
In following embodiment and in whole specification sheets and claim, unless otherwise indicated, all quantity is based on the weight percent of total resin weight in the composition.All the components mixed being incorporated in ribbon mixer extruded under 260 ℃ in the Werner-Pleiderer twin screw extruder to form pellet.Then pellet is added injection moulding machine with the moulding disc test strip.Test process is as follows:
From saccharoid, according to ISO 1133 (265 ℃/2.16kg, unless otherwise indicated) with cm
3/ 10min is that melt volume speed (MVR) is measured by unit.
Measure according to ASTMD648 on the bent-strip that heat-drawn wire HDT is thick at 3.2mm, 126mm is long.
Tensile property: drawing process is followed ATSM D638 standard.Test Zwick 1474 (+carry out on HASY).This machine equipment automatic assembling and disassembling system.Use has the I type ASTM tensile bars of following size: width 13mm and thickness 3.2mm.
Notched izod intensity: this test process in the case, uses socle girder method E based on ASTM D256 method, obtains notched Izod impact strength by the test notched specimen.Test result is reported according to the energy that the per unit specimen width absorbs, and is taken advantage of a pound per inch to represent (Ft.Lbs./In.) with foot.Typically final testing result is calculated as the testing mean of five test strip.
The Dynatup Impact Test: this test process is based on ASTM D3763 method.The information that this process provides material how to show under the three axial deformation condition.The distortion that applies is puncture at a high speed.The supplier's of this type testing apparatus example is Dynatup.As test result report be so-called total energy (TE) that absorbs, it is expressed as foot and takes advantage of pound (Ft.Lbs.).Final test result calculations is the mean value of the test result of ten testing plate typically.
Melt viscosity: this test process is based on ASTM D1238 method.The equipment that uses is the plasticity machine of extruding of equipment autotimer.The exemplary of this equipment is Tinius OlsonMP987.Before test, that sample is following dry one hour at 150 ℃.Test condition is 266 ℃ of melt temperatures, total load 5,000 grams, 0.0825 inch of the orifice diameter and the residence time 5 minutes.Test result is with unit pool expression.
Modulus in flexure: this test process is based on ASTM D790 method.Typical test strip has following size: 13mm * 126mm and thickness 3.2mm.Final testing result is calculated as the mean value of the test result of five test strip.Test is included in 3 loading systems that adopt center loaded on the simply supported beam.The ratio of the deformation extent that thermometrically produces in standing the material of certain bending force.When applying bending force, low modulus in flexure number means that material has higher distortion.
Instron and Zwick are the exemplary that designs with the apparatus manufacturer that carries out this type test.Modulus in flexure is in elastic limit, and stress is represented to corresponding strained ratio and with pound per square inch (psi).
Shore D hardness is by from Zwick, and the D of USA numeral hardness tester is measured.The hardness tester test is carried out according to ASTM D2240 process.The ability that Shore D hardness measurement material opposing Shore D probe penetrates.Higher hardness number means that material is more endurable.
The performance of the various blends of table 2..Embodiment 1,3,8,12 and 13 is embodiments of the invention and remaining embodiment is a Comparative Examples.
Claims (10)
1. thermoplastic resin composition, comprise polyester cycloaliphatic resin, copolyester ether, ABS resin and/or impact modifying agent and optional polycarbonate derived from cyclic aliphatic dialkanol or its coordinator and cycloaliphatic dicarboxylic acid or its coordinator, wherein the blend of Huo Deing has low modulus in flexure and high Shore D hardness.
2. according to the thermoplastic resin composition of claim 1, the modulus in flexure of wherein said resin is that about 120kpsi of about 45kpsi-and Shore hardness are about 55-about 72.
3. according to the thermoplastic resin composition of claim 1, wherein the weight-average molecular weight of cyclic aliphatic vibrin is 65, and 000-is about 85,000amu.
4. according to the thermoplastic resin composition of claim 1, wherein the quantity of cyclic aliphatic polyester existence is the about 40wt% of about 10-.
5. according to the thermoplastic resin composition of claim 1, wherein the quantity of copolyester ether existence is the about 55wt% of about 20-.
6. according to the thermoplastic resin composition of claim 1, wherein the quantity of ABS resin existence is the about 50wt% of about 20-.
7. according to the thermoplastic resin composition of claim 1, wherein the quantity of impact modifying agent existence is the about 50wt% of about 20-.
8. according to the thermoplastic resin composition of claim 1, wherein optional polycarbonate can comprise every kind of at least two kinds of different polycarbonate resins with different molecular weight.
9. by the moulded products of the blend molding of claim 1.
10. by the moulded products of the blend molding of claim 2.
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| US53059003P | 2003-12-18 | 2003-12-18 | |
| US60/530,590 | 2003-12-18 | ||
| US10/983,775 | 2004-11-08 |
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| CN116790101A (en) * | 2023-04-07 | 2023-09-22 | 江苏科技大学 | PETG high-strength high-toughness transparent wire, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116790101A (en) * | 2023-04-07 | 2023-09-22 | 江苏科技大学 | PETG high-strength high-toughness transparent wire, preparation method and application |
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