CN1429254A - 耐天候老化聚合物共混物 - Google Patents
耐天候老化聚合物共混物 Download PDFInfo
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- CN1429254A CN1429254A CN01809735A CN01809735A CN1429254A CN 1429254 A CN1429254 A CN 1429254A CN 01809735 A CN01809735 A CN 01809735A CN 01809735 A CN01809735 A CN 01809735A CN 1429254 A CN1429254 A CN 1429254A
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- 239000000203 mixture Substances 0.000 title claims description 59
- 229920000642 polymer Polymers 0.000 title claims description 35
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- 239000005060 rubber Substances 0.000 claims abstract description 26
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 8
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims abstract 4
- 229920002647 polyamide Polymers 0.000 claims abstract 4
- 239000000178 monomer Substances 0.000 claims description 51
- 229920002379 silicone rubber Polymers 0.000 claims description 31
- -1 stablizer Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 150000001408 amides Chemical class 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
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- 239000006185 dispersion Substances 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 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 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 238000002360 preparation method Methods 0.000 description 11
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- 238000010559 graft polymerization reaction Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
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- 125000000962 organic group Chemical group 0.000 description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 3
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
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- 125000000129 anionic group Chemical group 0.000 description 2
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
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- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- MRERMGPPCLQIPD-NBVRZTHBSA-N (3beta,5alpha,9alpha,22E,24R)-3,5,9-Trihydroxy-23-methylergosta-7,22-dien-6-one Chemical compound C1C(O)CCC2(C)C(CCC3(C(C(C)/C=C(\C)C(C)C(C)C)CCC33)C)(O)C3=CC(=O)C21O MRERMGPPCLQIPD-NBVRZTHBSA-N 0.000 description 1
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- CKDSFRWKHBYHHT-UHFFFAOYSA-N 4-bicyclo[2.2.1]heptanylmethanamine Chemical class C1CC2CCC1(CN)C2 CKDSFRWKHBYHHT-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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Abstract
本发明涉及一种耐天候老化聚合物共混物,它包含:A)聚酰胺;B)至少一种选自硅氧烷-、EP(D)M-和丙烯酸酯-橡胶作为接枝主链的橡胶弹性接枝聚合物;C)至少一种含至少一种带有极性基团的热塑性聚合物的相容性介质和D)任选地,至少一种乙烯基(共)聚合物。
Description
本发明涉及聚合物共混物,它基于聚酰胺和以选自硅橡胶、EP(D)M橡胶和丙烯酸酯橡胶作为其接枝基体的接枝聚合物,具有非常好的机械性能,如抗张强度和耐天候老化。
EP-A-202 214描述了聚酰胺/ABS共混物,它另外包含具有能与该聚酰胺的胺或酸端基起反应的官能团的相容剂(Vertrglichkeitsvermittler)。
DE-A-39 38 421描述了热塑性聚酰胺模塑组合物,它采用经某种氧化还原聚合方法后生成并在其外壳内包含丙烯酸叔丁酯的接枝聚合物。
最后,EP-A-785 234描述了聚合物组合物,它包含:芳族乙烯基单体和得自(甲基)丙烯酸烷基酯或丙烯腈的单体在橡胶上的接枝聚合物,作为第一组分;含极性基团热塑性聚合物,作为第二组分;和相容剂,作为第三组分。
本发明的目的是提供具有优异机械性能,如抗张强度和耐天候老化的聚合物共混物。
现已发现,基于聚酰胺和选自硅橡胶、EP(D)M橡胶和丙烯酸酯橡胶的接枝聚合物、包含相容剂的聚合物共混物具有所要求的性能。
因此,本发明提供聚合物共混物,它包含
A)聚酰胺,
B)至少一种橡胶弹性接枝聚合物,其以选自硅橡胶、EP(D)M橡胶和丙烯酸酯橡胶作为其接枝基体,
C)至少一种相容剂,它包含至少一种具有极性基团的热塑性聚合物和,
D)任选地,至少一种乙烯基(共)聚合物。
本发明优选提供这样的聚合物共混物,它包含
-10~98,优选15~70,尤其优选20~60重量份的聚酰胺A,
-0.5~80,优选10~70,尤其优选20~65重量份由组分B和任选的D组成的混合物,或者
-0.5~50,优选1~30,尤其优选2~10重量份包含至少一种具有极性基团的热塑性聚合物的相容剂。组分A
适合本发明的聚酰胺是已知的均聚酰胺、共聚酰胺和所述聚酰胺的混合物。它们可以是部分结晶和/或无定形的聚酰胺。作为部分结晶聚酰胺,合适的是聚酰胺6、聚酰胺-6,6、所述组分的混合物和相应共聚物。再有,可考虑的是部分结晶聚酰胺,其酸组分完全或部分地由对苯二甲酸和/或间苯二甲酸和/或辛二酸和/或癸二酸和/或壬二酸和/或己二酸和/或环己烷二羧酸组成,其二胺组分完全或部分地由间-和/或对-二甲苯二胺和/或六亚甲基二胺和/或2,2,4-三甲基六亚甲基二胺和/或2,4,4-三甲基六亚甲基二胺和/或异佛尔酮二胺组成,和其组成原则上是已知的。
另外,可举出这样的聚酰胺,它可完全或部分地由环中具有7~12个碳原子的内酰胺,任选地再共同使用一种或多种上面提到的原料组分来制备。
尤其优选的部分结晶聚酰胺是聚酰胺-6和聚酰胺-6,6和其混合物。已知的产物可用作无定形聚酰胺。它们通过以下物质的缩聚制取:二胺,例如乙二胺、六亚甲基二胺、1,10-癸二胺、2,2,4-和/或2,4,4-三甲基六亚甲基二胺、间-和/或对-二甲苯二胺、双(4-氨基环己基)甲烷、双(4-氨基环己基)丙烷、3,3’-二甲基-4,4’-二氨基二环己基甲烷、3-氨甲基-3,5,5-三甲基环己基胺、2,5-和/或2,6-双(氨甲基)降冰片烷和/或1,4-二氨甲基环己烷,与二羧酸,如草酸、己二酸、壬二酸、癸烷二羧酸、十七烷二羧酸、2,2,4-和/或2,4,4-三甲基己二酸、间苯二甲酸和对苯二甲酸。
由多种单体的缩聚制取的共聚物也适合,同样适合的还有通过加入氨基酸,如ε-氨基己酸、ω-氨基十一烷酸或ω-氨基月桂酸或它们的内酰胺制备的共聚物。
尤其合适的无定形聚酰胺是由下列各组物质制备的聚酰胺:间苯二甲酸、六亚甲基二胺和另一些二胺如4,4-二氨基二环己基甲烷、异佛尔酮二胺、2,2,4-和/或2,4,4-三甲基六亚甲基二胺、2,5-和/或2,6-双(氨甲基)降冰片烯;或者间苯二甲酸、4,4’-二氨基二环己基甲烷和ε-己内酰胺;或者间苯二甲酸、3,3’-二甲基-4,4’-二氨基-二环己基甲烷和月桂内酰胺;或者对苯二甲酸和2,2,4-和/或2,4,4-三甲基六亚甲基二胺的异构混合物。
不用纯4,4’-二氨基二环己基甲烷,也可使用位置异构体二氨基二环己基甲烷的混合物,其组成如下:
70~99mol%4,4’-二氨基异构体,
1~30mol%2,4’-二氨基异构体,
0~2mol%2,2’-二氨基异构体,
任选地,通过工业级品质的二氨基二苯甲烷的氢化获得的对应地较高级缩合二胺。最高30%间苯二甲酸可由对苯二甲酸替代。
该聚酰胺优选具有2.0~5.0,尤其优选2.5~4.0的相对粘度(在25℃对1wt%在间甲酚中的溶液测定)。组分B
组分B包含一种或多种选自硅橡胶、丙烯酸酯橡胶和EP(D)M橡胶作为其接枝基体的橡胶弹性接枝聚合物。
优选的是,组分B包含一种或多种如下形成的接枝聚合物:
B.15~95,优选20~80,尤其是30~80wt%至少一种乙烯基单体,接枝在
B.295~5,优选80~20,尤其是70~20wt%一种或多种玻璃化转变温度小于10℃,优选小于0℃,尤其优选小于-20℃,选自硅橡胶、丙烯酸酯橡胶和EP(D)M橡胶的接枝基体上。
接枝基体B.2一般具有0.05~5μm,优选0.10~0.5μm,尤其优选0.20~0.40μm的平均粒度(d50值)。
可在本发明中作为组分B.1的乙烯基单体是下列单体组成的那些:至少一种选自如下系列的单体:乙烯基芳烃和/或环上取代的乙烯基芳烃(例如,苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯)、(C1~C8)-烷基的甲基丙烯酸酯(例如,甲基丙烯酸甲酯、甲基丙烯酸乙酯)(B.1.1),与至少一种选自如下系列的单体:乙烯基氰类(不饱和腈,如丙烯腈和甲基丙烯腈)、(C1~C8)-烷基的(甲基)丙烯酸酯(如,甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)、不饱和羧酸的衍生物(如,酸酐和酰亚胺)(如马来酸酐和N-苯基马来酰亚胺)(B.1.2)。
优选的是,组分B.1是下列成分的混合物,
-50~99,优选60~80重量份组分B.1.1与
-1~50,优选40~20重量份组分B.1.2。
(C1~C8)-烷基的丙烯酸酯或(C1~C8)-烷基的甲基丙烯酸酯是丙烯酸或甲基丙烯酸与1~8个碳原子的单羟基醇的酯。尤其优选的是甲基丙烯酸甲酯、甲基丙烯酸乙酯和甲基丙烯酸丙酯。甲基丙烯酸甲酯被视为尤其优选的甲基丙烯酸酯。
组成符合组分D的热塑性(共)聚合物可作为制备组分B的接枝聚合过程中的副产物而生成,尤其当大量单体接枝到少量橡胶上时。
就本发明目的而言,接枝聚合物B)应理解为在接枝聚合物期间由已接枝的橡胶和在接枝聚合物期间生成的(共)聚合物所产生的产物。接枝聚合期间必然生成的(共)聚合物的数量取决于,特别是,单体组成以及聚合方法。
鉴于,根据另外单独加入的(共)聚合物D)的数量和必要时的本性将无法把加入的(共)聚合物与接枝聚合物的聚合期间生成的(共)聚合物区别开来,故组分B)与D)之和等价于接枝聚合物与(共)聚合物之和。
尤其优选的乙烯基单体B.1是苯乙烯和丙烯腈和,任选地,甲基丙烯酸甲酯;α-甲基苯乙烯和丙烯腈和,任选地,甲基丙烯酸甲酯;或者苯乙烯、α-甲基苯乙烯和丙烯腈和,任选地,甲基丙烯酸甲酯。
R11和R12可相同或不同,并代表(C1~C6)-烷基或环烷基或者(C6~C12)-芳基和
n代表整数。
优选的硅橡胶B.2为粒状,平均颗粒直径d50为0.09~1μm,优选0.09~0.4μm,且凝胶含量大于70wt%,尤其是73~98wt%,并且可由下列物质制取:
1)二卤代有机硅烷,
2)0~10mol%,相对于1)而言,三卤代硅烷和
3)0~3mol%,相对于1)而言,四卤代硅烷和
4)0~0.5mol%,相对于1)而言,卤代三有机硅烷,
其中化合物1)、2)和4)中的有机基团是
α)(C1~C6)-烷基或环己基,优选甲基或乙基,
β)(C6~C12)-芳基,优选苯基,
γ)(C1~C6)-链烯基,优选乙烯基或烯丙基
δ)巯基(C1~C6)-烷基,优选巯基丙基,
条件是,(γ+δ)之和是2~10mol%,相对于化合物1)、2)和4)的全部有机基团而言,并且摩尔比γ∶δ=3∶1~1∶3,优选2∶1~1∶2。
优选的硅橡胶B.2包含,作为有机基团,至少80mol%甲基基团。端基一般是二有机基-羟基-甲硅烷氧基单元,优选二甲基羟基甲硅烷基单元。
优选的制备硅橡胶B.2用的硅烷1)~4)包含氯作为卤素取代基。
“可制取(=可获得)”是指,硅橡胶B.2不一定必须由卤素化合物1)~4)制备。相同结构的硅橡胶B.2,由含其他可水解基团,如(C1~C6)-烷氧基基团的硅烷,或者由环状硅氧烷低聚物制备的那些,也包括在内。
可举出硅氧烷接枝橡胶作为尤其优选的组分B.2。它们例如可通过一种三阶段法来制备。
在第一阶段,单体,如二甲基二氯硅烷、乙烯基甲基二氯硅烷或具有其他取代基的二氯硅烷起反应(参见“Chemie in unserer Zeit(现代化学)4(1987),121~127),生成容易通过蒸馏提纯的环状低聚物(八甲基环四硅氧烷或四乙烯基四甲基环四硅氧烷)。
在第二阶段,交联的硅橡胶通过所述环状低聚物在加入巯丙基甲基二甲氧基硅烷的情况下的开环阳离子聚合而制成。
在第三阶段,制取的硅橡胶,由于其乙烯基和巯基基团具有接枝活性,故与乙烯基单体(或混合物)进行自由基接枝聚合反应。
优选的是,在第二阶段,环状硅氧烷低聚物,如八甲基环四硅氧烷和四甲基四乙烯基环四硅氧烷的混合物,在乳液中进行开环阳离子聚合。生产出乳液中的颗粒形式的硅橡胶。
尤其优选的是,按照GB-A 1 024 014采用烷基苯磺酸,它既具有催化活性又起到乳化剂的作用。在聚合之后,酸被中和。不用烷基苯磺酸,也可使用n-烷基磺酸。还可以除磺酸之外再使用助乳化剂。
助乳化剂可以是非离子或阴离子的。适合作为阴离子助乳化剂的特别是,n-烷基-或烷基苯磺酸的盐。非离子助乳化剂是脂肪醇与脂肪酸的聚氧乙烯衍生物。例如是POE(3)-月桂醇、POE(20)-油醇、POE(7)-壬醇或POE(10)-硬脂酸酯。(写法POE(数字)……醇是指,有对应于该数目那么多的环氧乙烷单元加在一分子……醇上。POE代表聚(环氧乙烷)。该数字是平均值)。
具有交联和接枝活性的基团(乙烯基和巯基基团,参见,有机基团γ和δ)可利用合适的硅氧烷低聚物插入到硅橡胶中。这些硅氧烷低聚物例如是四甲基四乙烯基环四硅氧烷或γ-巯丙基甲基二甲氧基硅氧烷或者它们的水解产物。
它们可在第二阶段以要求的数量加入到主要低聚物,例如,八甲基环四硅氧烷中。
较长链烷基基团如,乙基、丙基之类的加入,或者苯基基团的加入也可类似地实现。
当基团γ和δ在乳液聚合期间彼此起反应时,甚至可以达到硅橡胶的充分交联,以致不再需要外部交联剂的加入。然而,为提高硅橡胶的交联度,可在第二反应阶段加入交联硅烷。
支化和交联可通过加入例如四乙氧基硅烷或下列通式的硅烷来实现,
y-SiX3,其中
X是可水解基团,尤其是烷氧基和卤素基团,和
y是有机基团。
优选的硅烷y-SiX3是甲基三甲氧基硅烷和苯基三甲氧基硅烷。
凝胶含量在25℃时在丙酮中测定(参见DE-AS 2 521 288,列6,行17~37)。在本发明的硅橡胶中,该数值至少是70wt%,优选73~98wt%。
接枝的硅橡胶B可通过自由基接枝聚合,例如,类似于DE-PS 2 421288那样制备。
为在第三阶段制备接枝的硅橡胶,接枝单体在硅橡胶存在下,特别是在40~90℃下进行自由基接枝聚合。接枝聚合反应可在悬浮体、分散体或乳液中进行。优选的是连续或间歇乳液聚合。所述接枝聚合反应采用自由基引发剂实施(例如,过氧化物、偶氮化合物、氢过氧化物、过硫酸盐(Persulfaten)、过磷酸盐(Perphosphaten))并任选地,采用阴离子乳化剂,如Carboxonium盐、磺酸盐或有机硫酸盐。就此而论,接枝聚合物以高接枝率形成,即,大部分接枝单体的聚合物化学地键合到硅橡胶上。该硅橡胶具有接枝活性基团,因此加强接枝的特殊措施是多余的。
接枝的硅橡胶可通过5~95重量份,优选20~80重量份乙烯基单体或乙烯基单体混合物接枝聚合到5~95,优选20~80重量份硅橡胶上制成。
尤其优选的乙烯基单体是苯乙烯或甲基丙烯酸甲酯。合适的乙烯基单体混合物一方面由50~95重量份苯乙烯、α-甲基苯乙烯(或其他烷基或卤素-环取代的苯乙烯)或者甲基丙烯酸甲酯和另一方面由5~50重量份丙烯腈、甲基丙烯腈、(C1~C18)-烷基的丙烯酸酯、(C1~C16)-烷基的甲基丙烯酸酯、马来酸酐或取代的马来酰亚胺组成。作为进一步的乙烯基单体,另外还可少量存在伯或仲脂族(C2~C10)-醇的丙烯酸酯,优选丙烯酸正丁酯或丙烯酸叔丁酯或甲基丙烯酸叔丁酯,优选丙烯酸叔丁酯。特别优选的单体混合物是30~40重量份α-甲基苯乙烯、52~62重量份甲基丙烯酸甲酯和4~14重量份丙烯腈。
按此种方式接枝的硅橡胶可按已知方式进行后加工,例如,胶乳以电解质(盐、酸或其混合物)进行凝聚,然后提纯和干燥。
接枝硅橡胶的制备期间,除了实际的接枝共聚物之外,一般还生成一定数量形成接枝外壳的接枝单体的游离聚合物或共聚物。这里,接枝的硅橡胶指的是接枝单体在硅橡胶存在下聚合获得的产物,因此严格地说,通常是接枝共聚物和接枝单体的游离(共)聚合物的混合物。
丙烯酸酯为基础的接枝聚合物优选具有下列组成,
a)20~90wt%,相对于接枝聚合物而言,玻璃化转变温度低于-20℃的丙烯酸酯橡胶,作为接枝基体,和
b)10~80wt%,相对于接枝聚合物而言,至少一种可聚合烯键不饱和单体(参见,B.1)作为接枝单体。
丙烯酸酯橡胶(a)优选是丙烯酸烷基酯,任选地与最高40wt%,相对于(a)而言的其他可聚合烯键不饱和单体的聚合物。该优选的可聚合丙烯酸酯包括(C1~C8)-烷基酯,例如甲基,乙基,丁基,正辛基和2-乙基己基酯;卤代烷基酯,优选卤代(C1~C8)-烷基酯,例如,丙烯酸氯乙基酯,和所述单体的混合物。
为实现交联,可用具有一个以上可聚合双键的单体进行共聚。优选的交联单体的例子是3~8个碳原子的不饱和单羧酸与3~12个碳原子的不饱和单羟基醇,或者与含2~4个羟基基团和2~20个碳原子的饱和多元醇的酯,例如,乙二醇二甲基丙烯酸酯、甲基丙烯酸烯丙基酯;多不饱和杂环化合物,例如,三乙烯基和三烯丙基氰脲酸酯;多官能乙烯基化合物,例如二-和三乙烯基苯;还有磷酸三烯丙基酯和邻苯二甲酸二烯丙基酯。
优选的交联单体是甲基丙烯酸烯丙基酯、乙二醇二甲基丙烯酸酯、邻苯二甲酸二烯丙基酯和具有至少3个烯键不饱和基团的杂环化合物。
特别优选的交联单体是环状单体三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、三丙烯酰六氢-s-三嗪、三烯丙基苯。
交联单体的用量优选为0.02~5,尤其是0.05~2wt%,相对于橡胶基体而言。
在包含至少3个烯键不饱和基团的环状交联单体的情况下,有利的是其用量限制在低于橡胶基体的1wt%。
优选的、除了丙烯酸酯之外还可任选用来制备接枝基体B.2的“其他”可聚合、烯键不饱和单体,例如是丙烯腈、苯乙烯、α-甲基苯乙烯、丙烯酰胺、乙烯基(C1~C6)-烷基醚、甲基丙烯酸甲酯、丁二烯。优选作为接枝基体B.2使用的丙烯酸酯橡胶是凝胶含量至少是60wt%的乳液聚合物。
丙烯酸酯为基础的聚合物是普遍已知的,并可按已知方法(例如,EP-A 244 857)制备,或者是市售产品。
接枝基体的凝胶含量是在25℃、合适的溶剂中测定的(M.Hoffmann,H.Krmer,R.Kuhn,《Polymeranalytik(聚合物分析)I和II》,Georg Thieme-出版社,斯图加特1977)。
平均粒度d50是这样的直径,大于和小于该直径的颗粒各占50wt%。它可通过超离心测定来确定(W.Scholtan,H.Lange,《Kolloid,Z und Z.Polymere(胶体与聚合物杂志)》,250(1972)。782~796)。
至少一种仅具有少量双键的含乙烯和丙烯的共聚物或三元共聚物被用作EP(D)M橡胶接枝基体(参见,EP-A 163 411、EP-A 244 857)。
作为EP(D)M橡胶使用的是玻璃化转变温度在-60~-40℃的那些。该橡胶仅具有少量双键,即,少于20个双键/1000个碳原子,尤其是3~10个双键/1000个碳原子。此种橡胶的例子是由乙烯-丙烯组成的共聚物,和乙烯-丙烯三元共聚物。后者是通过至少30wt%乙烯、至少30wt%丙烯与0.5~15wt%非共轭二烯组分的聚合制备的。作为三组分(Terkomponente)使用的通常是至少5个碳原子的二烯,例如,5-亚乙基降冰片烯、二环戊二烯、2,2,1-二环戊二烯和1,4-己二烯。合适的还有,Polyalkylenamere,例如,Polypentenamer、Polyoctenamer、Polydodecanamer或者所述物质的混合物。另外,合适的还有所含残余双键中至少70%已被氢化的部分氢化聚丁二烯橡胶。以上提到的橡胶当中,特别可使用的是乙烯-丙烯共聚物和乙烯-丙烯三元共聚物(EPDM橡胶)。一般而言,EPDM橡胶具有25~120的门尼粘度ML1-4(100℃)。它们有市售供应。
基于EP(D)M橡胶的接枝聚合物可通过各种各样方法制备。优选的是,制备EP(D)M橡胶弹性体(橡胶)在单体混合物和(任选地)惰性溶剂中的溶液,并通过自由基引发剂如偶氮化合物或过氧化物,在较高的温度进行接枝反应。作为例子,可举出DE-AS 23 02 014和DE-A 25 33991的方法。也可在悬浮体中实施,如描述在US-A 4 202 948中。组分C
按照本发明,具有极性基团的热塑性聚合物优选作为相容剂使用。
按照本发明,优选使用这样的聚合物,它包含,
C.1 乙烯基芳族单体,
C.2 至少一种选自C2-~C12-烷基的甲基丙烯酸酯、C2-~C12-烷基的丙烯酸酯、甲基丙烯腈和丙烯腈的单体,和
C.3包含α,β-不饱和成分的二羧酸酐。
苯乙烯尤其优选作为乙烯基芳族单体C.1。
丙烯腈尤其优选作为组分C.2。
尤其优选的包含α-,β-不饱和成分的二羧酸酐C.3是马来酸酐。
优选的是,用所述单体的三元共聚物作为组分C.1、C.2和C.3使用。因此,苯乙烯、丙烯腈和马来酸酐的三元共聚物是优选使用的。所述三元共聚物尤其对机械性能如抗张强度和耐天候老化的改善做出贡献。马来酸酐在三元共聚物中的含量可在宽范围内变化。优选的是,该含量为0.2~5mol%。尤其优选的是,为0.5~1.5mol%的数量存在于组分C.1中。在该范围内,达到了尤其好的涉及抗张强度和耐天候老化的机械性能。
三元共聚物可按本身已知的方式制备。合适的方法是,将三元共聚物的单体组分,例如苯乙烯、马来酸酐和丙烯腈溶解在合适的溶剂中,例如在丁酮(MEK)中。一种,或者任选地,多种化学引发剂加入到该溶液中。合适的引发剂,例如是过氧化物。然后,混合物在提高的温度下聚合几个小时。随后,溶剂和未反应单体按本身已知的方式被除去。
组分C.1(乙烯基芳族单体)与组分C.2,例如,丙烯腈单体,在三元共聚物中的比例优选为80∶20~50∶50。为改善三元共聚物与接枝共聚物B之间的混溶性,乙烯基-芳族单体C.1的数量优选地选择为对应于接枝共聚物B中的乙烯基单体B.1的数量。
本发明聚合物共混物中的组分C的含量为0.5~50wt%,优选为1~30wt%,尤其优选2~10wt%。高度优选的为5~7wt%的含量。
此类聚合物例如描述在EP-A-785 234和EP-A-202 214中。按照本发明,EP-A-202 214中提到的聚合物特别优选。组分D
组分D包含一种或多种热塑性乙烯基(共)聚合物。
适合作为乙烯基(共)聚合物D的是至少一种选自乙烯基芳烃、乙烯基氰(不饱和腈)、(C1~C8)-烷基的(甲基)丙烯酸酯、不饱和羧酸和不饱和羧酸的衍生物(例如,酸酐和酰亚胺)的单体的聚合物。尤其合适的是下列成分的(共)聚合物,
D.1 50~99,优选60~80重量份乙烯基芳烃和/或环上取代的乙烯基芳烃,例如,苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯和/或(C1~C8)-烷基的甲基丙烯酸酯,例如,甲基丙烯酸甲酯、甲基丙烯酸乙酯,和
D.21~50,优选20~40重量份乙烯基氰(不饱和腈),例如丙烯腈和甲基丙烯腈和/或(C1~C8)-烷基的(甲基)丙烯酸酯(例如,甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和/或不饱和羧酸(例如,马来酸)和/或不饱和羧酸的衍生物(例如,酸酐和酰亚胺)(例如,马来酐和N-苯基马来酰亚胺)。
(共)聚合物D是树脂类、热塑性和不含橡胶的。
尤其优选的是D.1苯乙烯和D.2丙烯腈的共聚物。
符合D的(共)聚合物是已知的,并可通过自由基聚合,特别是通过乳液、悬浮体、溶液或本体聚合来制备。(共)聚合物优选具有15,000~200,000的分子量
Mw(重均,由光散射或沉降来确定)。
符合组分D的(共)聚合物通常是作为组分B接枝聚合期间的副产物生成的,尤其当大量单体B.1接枝到少量橡胶B.2上时。组分E
本发明聚合物共混物可包含传统添加剂,如阻燃剂、防滴剂、精细分散的无机化合物、润滑剂和脱模剂、成核剂、抗静电剂、稳定剂、填料和增强物质,和染料和颜料。
本发明聚合物共混物通常可包含0.01~20wt%的阻燃剂,相对于整个模塑组合物。作为例子,可举出有机卤化合物如十溴联苯醚、四溴双酚,无机卤化合物,如溴化铵,氮化合物如三聚氰胺、蜜胺-甲醛树脂、无机氢氧化物,如Mg-Al氢氧化物,无机化合物如氧化铝、二氧化钛、氧化锑、偏硼酸钡、羟配锑酸盐(Hydroxoantimonat)、氧化锆、氢氧化锆、氧化钼、钼酸铵、硼酸锡、硼酸铵、偏硼酸钡和氧化锡和硅氧烷化合物作为阻燃剂。
还有,磷化合物,例如描述在EP-A-363 608、EP-A-345 522或EP-A-640 655中的那些,也可用作阻燃化合物。
可用的无机化合物包含一种或多种周期表主族1~5和副族1~8的,优选和主族2~5和副族4~8的,尤其是主族3~5和副族4~8的金属与元素氧、硫、硼、磷、碳、氮、氢和/或硅的化合物。
此种化合物的例子是氧化物、氢氧化物、含水氧化物、硫酸盐、亚硫酸盐、硫化物、碳酸盐、碳化物、硝酸盐、亚硝酸盐、氮化物、硼酸盐、硅酸盐、磷酸盐、氢化物、亚磷酸盐或膦酸盐。这些包括,例如,TiN、TiO2、SnO2、WC、ZnO、Al2O3、AlO(OH)、ZrO2、Sb2O3、SiO2、氧化铁、NaSO4、BaSO4、氧化钒、硼酸锌、硅酸盐如硅酸铝、硅酸镁、一-、二-和三-维硅酸盐,混合物和掺杂化合物也可使用。再有,这些纳米级颗粒是用有机分子表面改性的,以便达到与聚合物更好的相容。这样,可生成疏水或亲水表面。
平均颗粒直径小于或等于200nm,优选小于或等于150nm,特别是1~100nm。
粒度和颗粒直径总是指按照W.Scholtan等人,《胶体与聚合物杂志》,250(1972),pp.782~796的超离心测定法确定的平均颗粒直径d50。
无机化合物可以是粉末、糊料、溶胶、分散体或悬浮体形式。粉末可通过从分散体、溶胶或悬浮体中沉淀来制取。
该粉末可通过传统方法,例如,通过模塑组合物的组分与精细分散的无机粉末直接混炼或挤塑,而结合到热塑性塑料中。优选的方法是制备母料,例如,在组分A中的以阻燃添加剂、其他添加剂、单体、溶剂的形式,或者组分B或C的分散体与精细分散的无机材料的分散体、悬浮体、糊料或溶胶进行共沉淀形成的。
例如,玻璃纤维,任选地切断或磨碎的,玻璃珠、玻璃球、小片型增强材料,如高岭土、滑石、云母(Glimmer)、硅酸盐、石英、滑石、二氧化钛、硅灰石、云母(Mika)、碳纤维或者它们的混合物,可以以填料或增强剂的形式存在。优选的是,用切断或磨碎的玻璃纤维作为增强材料。优选的填料,同时也具有增强作用的是玻璃球、云母、硅酸盐、石英、滑石、二氧化碳和硅灰石。
本发明聚合物共混物可用于制备任何种类的模塑件。特别是,模塑件可通过注塑生产。可生产的模塑件的例子是:各种外壳零件,例如,家用电器,如水果压榨器、咖啡机和混合机,或者办公机器,例如,计算机、打印机和监视器,或者建筑业用的面板以及机动车行业的零件。
特别合适的是用于生产在耐天候老化、抗张强度和抗应力龟裂等方面要求特别高的模塑件的聚合物共混物。
本发明还涉及该聚合物共混物用于制备模塑件的应用以及可由它制取的模塑件。
下面,将结合某些实施例更详细地说明本发明。
实施例
1、使用的组分A 聚酰胺(DURETHAN B30,拜尔AG公司(Leverkusen,德国)供应B1 接枝聚合物,由40重量份73∶27苯乙烯与丙烯腈的共聚物接枝到
60重量份以颗粒形式交联的聚丁二烯橡胶(平均颗粒直径
d50=0.28微米)上形成,采用乳液聚合制备B2 丙烯腈-乙烯-苯乙烯共聚物(AES)与约70wt%比例的EPDM,例如
Bendex WX270,通用电气供应B3 丙烯酸酯-苯乙烯-丙烯腈共聚物(ASA)与约60wt%含量的橡胶,
例如Bendex WX160,通用电气供应B4 硅氧烷丙烯酸酯橡胶,具有由丙烯酸酯芯和室温下G’模量为约110
MPA的硅外壳组成的芯-壳结构:
(1)Metablen S2001(Metablen公司,B.V.Vlissingen,荷兰);
(2)Metablen SKR200(Metablen公司,B.V.Vlissingen,荷兰)。C 相容剂:苯乙烯和丙烯腈(2.2∶1重量比)并含有1mol%马来酸酐的
三元共聚物D 苯乙烯/丙烯腈共聚物,其中苯乙烯/丙烯腈比例=72∶28,特性粘
度为0.75dl/g(在20℃、二甲基甲酰胺中测定)E 无机填料,按照US-A 5 714 537
(1)Tremin 939-300 EST(滑石)
(2)Burgess 2211(硅酸铝)
(3)Wicroll 40PA(硅灰石)
(4)Finntalc M30SL(Finntalc)F 添加剂
2、聚合物共混物的制备
本发明聚合物共混物通过各组分按已知方式掺混并在200~300℃的温度在传统机设备中,例如在密炼机、挤出机和双螺杆挤出机熔融混炼或熔融挤出而制成,其中氟化聚烯烃优选以上面已经提到的凝聚混合物形式使用。
各个组分可按已知方式,或者先后或者同时地掺混,具体地说,在约20℃(室温)或者在提高的温度进行。
3、耐天候老化橡胶(ASA、AES、硅氧烷丙烯酸酯代替ABS)
a)用ASA+AES
对比例,按照EP-A 202 214 | 实施例1 | 实施例2 | ||
A | 重量份 | 44 | 44 | 44 |
B1 | 重量份 | 17 | - | - |
B2 | 重量份 | - | 27 | - |
B3 | 重量份 | - | - | 30 |
C | 重量份 | 6 | 6 | 6 |
D | 重量份 | 33 | 23 | 26 |
F | 重量份 | 1.5 | 1.5 | 1.5 |
Vicat A | ℃ | 186 | 191 | 188 |
HDT A | ℃ | 65 | 67 | 72 |
熔体体积流速 | cm3/10min. | 4 | 6 | 14 |
天候老化 | (Xe-WOM1000h) | - | + | + |
弹性模量 | MPA | 1850 | 2000 | 1980 |
断裂伸长 | % | 90 | 100 | 130 |
b)用硅丙烯酸酯
根据Vicat A和B的耐热性是按照DIN 53 460(ISO 306)测定的。热畸变温度A(HDT A)是按照ISO75在1.8MPa下测定的。熔体体积流速是按照ISO 527测定的。天候老化是按照SAE J 1885测定的;仪器Uerit:Xe WO11喷洒周期:102=18曝光时间:1000h辐照能量:1260KJ/m2辐照:144.9MJ/m2弹性模量按照DIN 534 57/ISO 527测定。断裂伸长按照ISO 527测定。
对比例,按照EP-A 202 214 | 实施例3 | 实施例4 | ||
A | 重量份 | 44 | 44 | 44 |
B1 | 重量份 | 33 | 33 | 33 |
B4 | 重量份 | - | 17(1) | 17(2) |
C | 重量份 | 6 | 6 | 6 |
D | 重量份 | 17 | - | - |
F | 重量份 | 1.5 | 1.5 | 1.5 |
Vicat B | ℃ | 103 | 106 | 107 |
熔体体积流速 | cm3/10min. | 4 | 4.9 | 6.7 |
弹性模量 | MPA | 1850 | 1840 | 1950 |
断裂伸长 | % | 90 | 140 | 110 |
Claims (14)
1.聚合物共混物,它包含
A)聚酰胺,
B)至少一种橡胶弹性接枝聚合物,其以选自硅橡胶、EP(D)M橡胶和丙烯酸酯橡胶作为其接枝基体,
C)至少一种相容剂,它包含至少一种具有极性基团的热塑性聚合物和任选地,
D)至少一种乙烯基(共)聚合物。
2.权利要求1的耐天候老化聚合物共混物,它包含
10~98重量份聚酰胺A,
0.5~80重量份组分B,
0.5~50重量份组分C和任选地,
0.5~80重量份乙烯基(共)聚合物D。
3.权利要求1的耐天候老化聚合物共混物,它包含
15~70重量份聚酰胺A,
10~70重量份组分B与任选的D的混合物,和
1~30重量份组分C。
4.权利要求1的聚合物共混物,它包含
20~60重量份聚酰胺A,
20~65重量份组分B与任选的D的混合物和
2~10重量份组分C。
5.权利要求1~4的聚合物共混物,其中组分B)包含一种或多种如下形成的接枝聚合物,
B.1 5~95wt%至少一种乙烯基单体接枝在
B.2 95~5wt%一种或多种玻璃化转变温度小于10℃、选自硅橡胶、丙烯酸酯橡胶和EP(D)M橡胶的接枝基体上。
6.权利要求5的聚合物共混物,其中乙烯基单体B.1选自:
B.1.1 50~99重量份乙烯基芳烃和/或环上取代的乙烯基芳烃和/或(C1~C8)-烷基的甲基丙烯酸酯和
B.1.2. 1~50重量份乙烯基氰、(C1~C8)-烷基的(甲基)丙烯酸酯和/或不饱和羧酸的衍生物。
7.权利要求6的聚合物共混物,其中单体B)
B.1.1选自单体苯乙烯、α-甲基苯乙烯和甲基丙烯酸甲酯当中的至少一种,和
B.1.2选自单体丙烯腈、马来酸酐和甲基丙烯酸甲酯当中的至少一种。
8.权利要求1~4的聚合物共混物,其中组分D是至少一种选自乙烯基芳烃、乙烯基氰、(C1~C8)-烷基的(甲基)丙烯酸酯、不饱和羧酸和不饱和羧酸的衍生物的单体的乙烯基(共)聚合物。
9.权利要求1~4的聚合物共混物,其特征在于,组分C包含:乙烯基芳族单体(C.1),至少一种选自(C2~C12)-烷基的(甲基)丙烯酸酯、甲基丙烯腈和丙烯腈的单体(C.2),和含α,β-不饱和成分的二羧酸酐。
10.以上权利要求之一的聚合物共混物,它包含至少一种添加剂,选自润滑剂、脱模剂、成核剂、抗静电剂、稳定剂、填料和增强物质、防滴剂、精细分散的无机化合物、染料和颜料。
11.以上权利要求之一的聚合物共混物,它包含阻燃剂。
12.权利要求1~11的聚合物共混物用于生产模塑件的应用。
13.模塑件,其特征在于,它们是采用权利要求1~11之一的聚合物共混物生产的。
14.可由权利要求1~11的聚合物共混物制取的外壳零件、面板和机动车行业的零件。
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CN01809788A Pending CN1430647A (zh) | 2000-05-19 | 2001-05-07 | 含有聚酰胺和以本体聚合法制备的橡胶改性聚合物的聚合物掺合物 |
CN01809731A Pending CN1429250A (zh) | 2000-05-19 | 2001-05-07 | 耐冲击一改性聚合物组合物 |
CNB018097359A Expired - Fee Related CN1244636C (zh) | 2000-05-19 | 2001-05-07 | 耐天候老化聚合物共混物 |
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CN01809788A Pending CN1430647A (zh) | 2000-05-19 | 2001-05-07 | 含有聚酰胺和以本体聚合法制备的橡胶改性聚合物的聚合物掺合物 |
CN01809731A Pending CN1429250A (zh) | 2000-05-19 | 2001-05-07 | 耐冲击一改性聚合物组合物 |
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US (3) | US20030153677A1 (zh) |
EP (3) | EP1287067A1 (zh) |
JP (3) | JP2003534429A (zh) |
KR (3) | KR20030001517A (zh) |
CN (3) | CN1430647A (zh) |
AR (3) | AR033369A1 (zh) |
AU (3) | AU2001254829A1 (zh) |
BR (3) | BR0110853A (zh) |
CA (3) | CA2409013A1 (zh) |
MX (3) | MXPA02011394A (zh) |
TW (1) | TWI281484B (zh) |
WO (3) | WO2001090247A1 (zh) |
Cited By (1)
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CN105860512A (zh) * | 2016-04-28 | 2016-08-17 | 苏州新区华士达工程塑胶有限公司 | 一种多功能防老化塑料 |
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US7135520B2 (en) * | 2002-07-01 | 2006-11-14 | Lanxess Corporation | Glass fiber filled thermoplastic compositions with good surface appearance |
DE10231001A1 (de) * | 2002-07-09 | 2004-02-12 | Volkswagen Ag | Aus Kunststoff bestehendes Werkzeug |
DE10233170A1 (de) * | 2002-07-22 | 2004-02-12 | Bayer Ag | Polymerblends auf Basis Polyamid |
DE10254877A1 (de) * | 2002-11-25 | 2004-06-03 | Bayer Ag | Schlagzähmodifizierte Polymer-Zusammensetzungen |
WO2004048452A1 (de) * | 2002-11-25 | 2004-06-10 | Lanxess Deutschland Gmbh | Schlagzähmodifizierte polymer-zusammensetzungen |
DE10310693A1 (de) * | 2003-03-12 | 2004-09-23 | Bayer Ag | Schlagzähmodifizierte Polymer-Zusammensetzungen |
EP1678257A1 (en) * | 2003-10-10 | 2006-07-12 | Basf Aktiengesellschaft | Thermoplastic molding compositions |
WO2006004245A1 (en) * | 2004-07-02 | 2006-01-12 | Lg Chem, Ltd. | Nanocomposite thermoplastic resin composition with flame resistance |
JP5221876B2 (ja) * | 2004-11-04 | 2013-06-26 | ライオン株式会社 | 導電性マスターバッチ及びそれを含む樹脂組成物 |
KR100616723B1 (ko) | 2005-04-15 | 2006-08-28 | 주식회사 이폴리머 | 재생 폴리아미드 나노복합체 조성물 |
CN101787205B (zh) * | 2009-10-28 | 2012-07-04 | 上海锦湖日丽塑料有限公司 | 一种改善皮纹制件表面闪光点的pa6/苯乙烯类树脂共混物 |
EP2802620B1 (de) | 2012-01-11 | 2016-05-04 | INEOS Styrolution Europe GmbH | Witterungsstabile thermoplastische formmassen auf basis von styrolcopolymeren und polyamiden mit verbesserter zähigkeit |
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CN107207854B (zh) * | 2015-02-13 | 2020-03-03 | 艾曼斯专利股份公司 | 聚酰胺模塑组合物和由该模塑组合物制成的模制件 |
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-
2001
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- 2001-05-07 EP EP01927943A patent/EP1287067A1/de not_active Withdrawn
- 2001-05-07 BR BR0110853-0A patent/BR0110853A/pt not_active IP Right Cessation
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- 2001-05-07 CN CN01809788A patent/CN1430647A/zh active Pending
- 2001-05-07 KR KR1020027015548A patent/KR20030001519A/ko not_active Application Discontinuation
- 2001-05-07 AU AU2001254829A patent/AU2001254829A1/en not_active Abandoned
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- 2001-05-07 WO PCT/EP2001/005141 patent/WO2001090247A1/de not_active Application Discontinuation
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- 2001-05-07 CA CA002409013A patent/CA2409013A1/en not_active Abandoned
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- 2001-05-07 CN CNB018097359A patent/CN1244636C/zh not_active Expired - Fee Related
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- 2001-05-07 EP EP01931688A patent/EP1287074A1/de not_active Withdrawn
- 2001-05-07 CA CA002409011A patent/CA2409011A1/en not_active Abandoned
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105860512A (zh) * | 2016-04-28 | 2016-08-17 | 苏州新区华士达工程塑胶有限公司 | 一种多功能防老化塑料 |
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