CN1256385C - 由增容聚酰胺树脂获得的热塑性硅氧烷弹性体 - Google Patents
由增容聚酰胺树脂获得的热塑性硅氧烷弹性体 Download PDFInfo
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- CN1256385C CN1256385C CNB028206630A CN02820663A CN1256385C CN 1256385 C CN1256385 C CN 1256385C CN B028206630 A CNB028206630 A CN B028206630A CN 02820663 A CN02820663 A CN 02820663A CN 1256385 C CN1256385 C CN 1256385C
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- Prior art keywords
- methyl
- nylon
- acid
- glycidyl
- ethylene
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 26
- 229920002379 silicone rubber Polymers 0.000 title description 13
- 229920001169 thermoplastic Polymers 0.000 title description 11
- 239000004416 thermosoftening plastic Substances 0.000 title description 11
- -1 glycidyl ester Chemical class 0.000 claims abstract description 98
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 11
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 83
- 150000002148 esters Chemical class 0.000 claims description 27
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- 150000001408 amides Chemical class 0.000 claims description 21
- 238000004073 vulcanization Methods 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 17
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- 229920000098 polyolefin Polymers 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229920000299 Nylon 12 Polymers 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
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- 229920001519 homopolymer Polymers 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
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- 239000002253 acid Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
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- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 claims description 3
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- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 claims description 2
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- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
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- 239000000203 mixture Substances 0.000 description 45
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 19
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 125000000217 alkyl group Chemical group 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 150000001721 carbon Chemical group 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
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- 239000004677 Nylon Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 13
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
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- 229910052697 platinum Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
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- 239000003292 glue Substances 0.000 description 9
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- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 6
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004902 Softening Agent Substances 0.000 description 5
- 208000014117 bile duct papillary neoplasm Diseases 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
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- 125000003944 tolyl group Chemical group 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HOPKHJSQWOIIQO-UHFFFAOYSA-N C[SiH2]C.[O] Chemical compound C[SiH2]C.[O] HOPKHJSQWOIIQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 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 3
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- 238000005984 hydrogenation reaction Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 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
- UAIFZYSPVVBOPN-UHFFFAOYSA-N trimethyl(prop-1-en-2-yloxy)silane Chemical group CC(=C)O[Si](C)(C)C UAIFZYSPVVBOPN-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
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Abstract
本发明披露了一种热塑性弹性体的制备方法,所述方法包括:(I)混合下述组分:(A)熔点或玻璃化转变温度为25-275℃的流变稳定的聚酰胺树脂,(B)硅氧烷基料,包含:(B′)100重量份二有机聚硅氧烷胶料,其可塑度至少为30并且分子中平均有至少两个链烯基,和非必需地(B″)5-200重量份增强填料,所述硅氧烷基料与所述聚酰胺树脂的重量比从35∶65至85∶15,(C)选自缩水甘油酯聚合物或有机官能接枝聚烯烃的增容剂,(D)有机氢化硅化合物,其分子中平均包含至少两个与硅连接的氢,和(E)硅氢化催化剂,组分(D)和(E)的含量为足以使所述二有机聚硅氧烷(B’)固化的量;(II)使所述二有机聚硅氧烷(B’)动态硫化。
Description
本发明涉及热塑性弹性体组合物,其中,将聚硅氧烷基料与聚酰胺树脂和选自缩水甘油酯聚合物或有机官能接枝聚烯烃的增容剂混合,并且在混合过程中使包含在基料中的硅氧烷胶料动态硫化。
热塑性弹性体(TPEs)是不仅有塑性而且有弹性性能的聚合物材料。他们具有弹性体的机械性能,但与常规热固性橡胶不同,他们能够在高温下进行再加工。由于所述聚合物材料能够使制造的部件回收利用并大大减少边角料,因此再加工性能是TPEs优于化学交联橡胶的主要优点。
通常,已知有两种主要的热塑性弹性体。嵌段共聚物热塑性弹性体包含:熔点或玻璃化转变温度在室温以上的“硬”塑性链段,以及玻璃化转变温度或熔点大大低于室温的“软”聚合物链段。在这些体系中,硬链段聚集形成各别的微相并起使软相物理交联的作用,由此,在室温下赋予橡胶状特性。在高温下,硬链段将熔化或软化并使该共聚物能够流动,并象普通热塑性树脂一样进行加工处理。
另外,称为简单混合物(物理混合物)的热塑性弹性体可通过将弹性体组分与热塑性树脂均匀地混合而获得。当在混合期间弹性体组分也进行交联时,将获得在本领域中称为热塑性硫化橡胶(TPV)的热塑性弹性体。由于TPV的交联弹性体相在高温下是不溶的和不可流动的,因此,相对于简单混合物,TPVs通常显示出改善的耐油性和耐溶剂性以及减少的压缩变定。
典型地,TPV由称为动态硫化的方法形成,其中,将弹性体和热塑性基质混合,并在混合过程中借助交联剂和/或催化剂使弹性体固化。许多这类TPVs在本领域是已知的,包括其中交联弹性体组分可为硅氧烷聚合物而热塑性组分为有机非硅氧烷聚合物的那些(即热塑性硅氧烷橡胶或TPSiV)。在这样的材料中,弹性体组分可通过各种各样的机理进行固化,但业已证明,利用非特定的自由基引发剂,如有机过氧化物,也能够使热塑性树脂本身至少部分固化,由此降低或完全破坏了所述组合物的再加工能力(即不再是热塑性的)。在其它情况下,过氧化物可使热塑性树脂部分降解。为解决这些问题,可使用弹性体-特定的交联剂,如有机氢化硅化合物来固化烯基官能的硅氧烷弹性体。
Arkles在US4,500,688中披露了半互穿网络(半IPN),其中,粘度为500-100,000cS的含乙烯基硅氧烷液体分散于常规的热塑性树脂中。Arkles仅说明了在硅氧烷相对少量时的这些IPNs。根据使用含氢化硅的硅氧烷组分的链伸长或交联机理,含乙烯基的硅氧烷在熔融混合期间在热塑性塑料中硫化。该专利指出:当含乙烯基的硅氧烷有2-4个乙烯基时且含氢化物的硅氧烷有1-2倍当量的乙烯基官能度时,链伸长将产生热塑性组合物。另一方面,当含乙烯基的硅氧烷有2-30个乙烯基且含氢化物的硅氧烷有2-10倍当量的乙烯基官能度时,主要进行交联反应的硅氧烷将形成热固性组合物。所提及的典型的热塑性塑料包括聚酰胺,聚氨酯,苯乙烯,聚缩醛和聚碳酸酯。该专利被Arkles的US4,714,739所扩展,从而包括利用混合硅氧烷,其包含不饱和基团并且通过含氢化物的硅氧烷与具有不饱和官能度的有机聚合物的反应而制备。尽管Arkles披露了硅氧烷液体含量为1-40%重量(在4714739专利中为1-60%),但没有建议这些比例的临界值,或者所述有机树脂的特定性质。
有关改进弹性体体系的WO96/01291披露了具有改善耐油性和耐压缩变定的热塑性弹性体。这些体系是通过首先形成硫化橡胶浓缩物而制备的,其中,将可固化弹性体共聚物分散于与其不溶混的聚合物载体中,所述可固化共聚物在该混合物混合时将动态硫化。将所得橡胶浓缩物反过来与工程热塑性塑料混合,以提供希望的TPE。硅橡胶被披露作为可能的弹性体组分,但没有提供利用所述硅氧烷的实施例。另外,该出版物特别指出:聚合物载体必须不与可固化共聚物用的固化剂反应。
Crosby等人在US4,695,602中教导了其中将通过硅氢化反应硫化的硅氧烷半IPN分散于具有高挠曲模量的纤维增强热塑性树脂中的复合材料。所用硅氧烷是上面引用的Arkles所教导的类型,并且据说该复合材料相对于没有IPN的体系而言,具有改善的收缩率和挠曲特性。
Ward等人在US4,831,071中披露了改善高模量热塑性树脂熔融完整性和强度的方法,以便当改性树脂进行熔融拉伸时提供光滑表面的、高公差的型材。当在上面引用的Arkles等人所披露的情况下,在分散于树脂中之后通过硅氢化反应使硅氧烷混合物固化,从而形成半IPN,然后对得到的组合物进行挤出和熔融拉伸。
欧洲专利申请0651009A1(Sumitomo Bakelite Co.,1995年5月3日出版)披露了热塑性弹性体组合物,它是通过动态加热如下混合物而制备的,所述混合物包含不饱和有机(即非硅氧烷)橡胶,热塑性树脂,含SiH的交联剂,硅氢化催化剂和增容剂。
US6,013,715(Gornowicz等人)教导了TPSiV弹性体的制备,其中,将硅氧烷胶料(或填充硅氧烷胶料)分散于聚烯烃中或聚对苯二甲酸丁二酯树脂中,然后,通过硅氢化硫化体系,使该胶料在其中进行动态硫化。所得弹性体显示出至少25%断裂极限伸长率,并且与其中胶料不固化的树脂和硅氧烷胶料的相应的简单混合物(即物理混合物)相比具有明显改善的机械性能。这显然在商业上意义重大,因为如果在不使用固化剂的情况下能够获得基本相同机械性能的话,硫化步骤和为此所需的固化剂(所述固化剂将增加制备和硫化的复杂性以及费用)在许多应用中可以避免。
US6,281,286(Chorvath等人)披露聚酯和聚酰胺树脂的耐冲击性可通过由其制备热塑性硅氧烷橡胶而大大增加,其中弹性体组分是硅橡胶基料,该基料包含硅氧烷胶料和二氧化硅填料且基料与树脂的重量比从10∶90至35∶65。尽管所得热塑性材料具有改进耐冲击性,但它们没有用作弹性体的足够低的模量。
US6,362,287披露了将受阻酚化合物掺入基于特定尼龙的TPSiV中,其中相对于未改性的组合物,所述酚化合物赋予了改善的机械性能。
US6,417,293披露了热塑性弹性体组合物,其中,硅氧烷胶料和稳定剂分散于聚酯树脂中,并且硅氧烷胶料在得到的混合物中动态硫化。
共同待批的美国专利申请SN09/843,906和SN09/845,971披露了利用过氧化物硫化技术制备TPSiV的方法。SN09/843,906教导了聚烯烃TPSiV,而SN09/845,971教导了聚酰胺和聚酯基的TPSiV。
US6,362,288披露了将增容剂掺入基于特定尼龙的TPSiV弹性体中,所述增容剂选自(i)偶联剂,(ii)官能二有机聚硅氧烷或(iii)包含至少一个二有机聚硅氧烷嵌段和至少一个选自聚酰胺,聚醚,聚氨酯,聚脲,聚碳酸酯或聚丙烯酸酯的嵌段的共聚物;其中,与不含增容剂的类似TPSiV弹性体相比,将所选增容剂包括在配方中将改善拉伸强度或伸长率。
因此,仍然需要确定起用于聚酰胺基TPSiV弹性体的增容剂作用的物质。特别是,需要确定能够提供与US6,362,288中教导的相当配方的增容剂,并且对于许多市场应用还具有巨大的商业利用价值。
通过将增容剂掺入配方中,本发明提供了聚酰胺TPSiV弹性体,所述增容剂选自缩水甘油酯聚合物或有机官能的接枝聚烯烃。在此所披露的弹性体通常具有良好的外观,具有至少25%的伸长率,并且具有比其中二有机聚硅氧烷不固化的相应的简单(物理)混合物大至少25%的抗张强度和/或伸长率。
因此,本发明涉及热塑性弹性体,其通过下述步骤制备:
(I)混合下述物质:
(A)熔点或玻璃化转变温度为25-275℃的流变稳定的聚酰胺树脂,
(B)硅氧烷基料,包含:
(B′)100重量份二有机聚硅氧烷胶料,其可塑度为至少30并且其分子中平均有至少两个链烯基,和非必需地
(B″)5-200重量份增强填料,
所述硅氧烷基料与所述聚酰胺树脂的重量比为35∶65至85∶15,
(C)选自缩水甘油酯聚合物或有机官能接枝聚烯烃的增容剂,
(D)有机氢化硅化合物,其分子中平均包含至少两个与硅连接的氢,和
(E)硅氢化催化剂,
组分(D)和(E)的含量为足以使所述二有机聚硅氧烷(B’)固化;和
(II)使所述二有机聚硅氧烷动态硫化。
在本发明优选的实施方案中,稳定剂(F)包括在所述配方中。稳定剂(F)是选自如下的至少一种有机化合物:受阻酚;硫代酸酯;受阻胺;2,2-(14-亚苯基)二(4H-3,1-苯并噁嗪-4-酮);或3,5-二叔丁基-4-羟基苯甲酸十六烷基酯。
另外,本发明还涉及通过上述方法制备的热塑性弹性体。
本发明方法的第一步包括将下列物质混合:
(A)熔点或玻璃化转变温度为25-275℃的流变稳定的聚酰胺树脂,
(B)硅氧烷基料,包含:
(B′)100重量份二有机聚硅氧烷胶料,其可塑度至少为30并且其分子中平均有至少两个链烯基,和非必需地
(B″)5-200重量份增强填料,
所述硅氧烷基料与所述聚酰胺树脂的重量比为35∶65至85∶15,
(C)选自缩水甘油酯聚合物或有机官能接枝聚烯烃的增容剂,
(D)有机氢化硅化合物,其分子中平均包含至少两个与硅连接的氢,和
(E)硅氢化催化剂,
组分(D)和(E)的含量为足以使所述二有机聚硅氧烷(B′)固化。
本发明的组分(A)是热塑性聚酰胺树脂。这些树脂是大家所熟知的通用术语″尼龙″,并且是沿聚合物主链包含酰胺(即-C(O)-NH-)键的长链合成聚合物。对于本发明,如果聚酰胺是无定形的,那么所述聚酰胺树脂的熔点(m.p.)或玻璃化转变温度(Tg)为室温(即25℃)至275℃。由具有更高熔点的聚酰胺(例如尼龙4/6)制备TPSiV弹性体的尝试导致差的物理性能,这样的产物的极限伸长率将低于本发明所要求的25%。此外,对于本发明,优选的是,在高温下使干燥惰性气体通过树脂粒或粉末而对聚酰胺树脂进行干燥。符合可接受的性能和加工的干燥程度取决于特定的聚酰胺,并且其值通常被制造商所推荐,或者可以通过一些简单的实验来确定。通常优选的是,聚酰胺树脂包含不多于约0.1%重量的水。最后,在如下所述制备TPSiV弹性体所需的混合条件下,聚酰胺还必须是流变稳定的。在适当的加工温度,对纯树脂评价该稳定性,并且在制备相应TPSiVs通常所需的时间内(例如在滚筒混合机中为10-30分钟),熔体粘度改变超过20%(混合扭矩)表明该树脂在本发明范围之外。因此,例如,在约210-220℃,在氮气吹洗下,于滚筒混合机中,对熔点为198℃的干燥尼龙11试样混合约15分钟,所观察到的混合扭矩将增加约200%。这样的聚酰胺树脂不是本发明方法合适的选择物。
除了上述的限制以外,树脂(A)可是在聚合物链之内有重复酰胺单元的任何热塑性结晶或无定形高分子量固体均聚物、二元共聚物或三元共聚物。在二元共聚物和三元共聚物体系中超过50%摩尔的重复单元是含酰胺的单元。合适聚酰胺的例子是聚内酰胺,如尼龙6,聚庚内酰胺(尼龙7),聚辛内酰胺(尼龙8),聚月桂内酰胺(尼龙12)等等;氨基酸的均聚物,如聚吡咯烷酮(尼龙4);二羧酸和二胺的共聚酰胺,如尼龙6/6,尼龙66,聚六亚甲基壬二酰胺(尼龙6/9),聚六亚甲基-癸二酰胺(尼龙6/10),聚六亚甲基间苯二甲酰胺(尼龙6,I),聚六亚甲基十二酸(尼龙6/12)等等;芳族和部分芳族的聚酰胺;共聚酰胺,如己内酰胺和六亚甲基己二酰二胺的共聚物(尼龙6,6/6),或三元共聚酰胺(如尼龙6,6/6,6);嵌段共聚物,如聚醚聚酰胺;或其混合物。优选的聚酰胺树脂是尼龙6,尼龙12,尼龙6/12和尼龙6/6。
另外还可以预期的是,组分(A)可与非聚酰胺、饱和的热塑性树脂混合,以致使聚酰胺树脂(A)占混合物体积的大于50%。优选的是,该非必需树脂的玻璃化转变温度应为25-275℃。
硅氧烷基料(B)是二有机聚硅氧烷胶料(B′)的均匀混合物,或者非必需地是该胶料与增强填料(B″)的均匀混合物。
二有机聚硅氧烷(B′)是高稠度(胶质)聚合物或共聚物,其分子中包含至少两个具有2-20个碳原子的链烯基。该链烯基的具体例子是乙烯基,烯丙基,丁烯基,戊烯基,己烯基和癸烯基。链烯基官能度的位置并不重要,它可以连接在分子链末端、在分子链上非末端位置或在这两个位置上。优选的是,链烯基是乙烯基或己烯基,并且该基团在二有机聚硅氧烷胶料中的含量为0.001-3%重量,优选在0.01-1%重量。
在组分(B′)中余下的(即非链烯基)与硅连接的有机基团独立地选自:不包含脂族不饱和度的烃或卤代烃基团。具体地,这些基团例如是具有1-20碳原子的烷基,如甲基,乙基,丙基,丁基,戊基和己基;环烷基,如环己基和环庚基;具有6-12碳原子的芳基基团,如苯基,甲苯基和二甲苯基;具有7-20碳原子的芳烷基,如苄基和苯乙基;和具有1-20碳原子的卤化烷基,如3,3,3-三氟丙基和氯甲基。当然,应当理解的是,应当这样来选择这些基团,以致使二有机聚硅氧烷胶料(B′)的玻璃化转变温度(或熔点)低于室温,并因此所述胶料是弹性体的。在组分(B′)中,甲基优选占非不饱和与硅连接的有机基团的至少50%、更优选至少90%摩尔。
因此,聚二有机硅氧烷(B′)可为包含所述有机基团的均聚物或共聚物。其例子包括:含二甲基甲硅烷氧基单元和苯甲基甲硅烷氧基单元;二甲基甲硅烷氧基单元和二苯基甲硅烷氧基单元;以及二甲基甲硅烷氧基单元,二苯基甲硅烷氧基单元和苯甲基甲硅氧基单元的胶料。另外,分子结构也不是重要的,优选的是例如直链和部分支化的直链、线型结构。
二有机聚硅氧烷(B′)的具体例子包括:三甲基甲硅烷氧基封端的二甲基硅氧烷-甲基己烯基硅氧烷共聚物;二甲基己烯基甲硅烷氧基封端的二甲基硅氧烷-甲基己烯基硅氧烷共聚物;三甲基甲硅烷氧基封端的二甲基硅氧烷-甲基乙烯基硅氧烷共聚物;三甲基甲硅烷氧基封端的甲苯基硅氧烷-二甲基硅氧烷-甲基乙烯基硅氧烷共聚物;二甲基乙烯基甲硅烷氧基封端的二甲聚硅氧烷;二甲基乙烯基甲硅烷氧基封端的二甲基硅氧烷-甲基乙烯基硅氧烷共聚物;二甲基乙烯基甲硅烷氧基封端的甲苯基聚硅氧烷;二甲基乙烯基甲硅烷氧基封端的甲苯基硅氧烷-二甲基硅氧烷-甲基乙烯基硅氧烷共聚物;和其中至少一个端基是二甲基羟基甲硅烷氧基的类似的共聚物。用于低温应用的优选体系包括:甲苯基硅氧烷-二甲基硅氧烷-甲基乙烯基硅氧烷共聚物和二苯基硅氧烷-二甲基硅氧烷-甲基乙烯基硅氧烷共聚物,特别是其中二甲基硅氧烷单元的摩尔含量约为93%。
组分(B′)还可以由两种或更多种有机聚硅氧烷组成。最优选的是,组分(B′)是分子的每一端用乙烯基封端的聚二甲硅氧烷均聚物,或者是沿其主链还包含至少一个乙烯基的该类均聚物。
对于本发明,当通过American Society For Testing andMaterials(ASTM)测试法926进行测量时,所述二有机聚硅氧烷胶料的分子量足以赋予至少约30的威廉姆斯可塑度。本文所用的可塑度定义为:2立方厘米体积且高约10毫米的圆柱状试样在25℃经受49牛顿压缩载荷三分钟之后的厚度(毫米)×100。当该组分的可塑度小于约30时,如在上面引用的Arkles所采用的低粘度液体硅氧烷的情况下,根据本发明方法的动态硫化所制备的TPSiVs显示出差的均匀性,以致使在高硅氧烷含量(例如50-75%重量)时,有主要仅仅是硅氧烷的区域和主要仅仅是热塑性树脂的区域,并且该混合物是弱且脆的。本发明的胶料与现有技术中使用的硅氧烷液体相比明显更粘。例如,上面引用的Arkles所预期的硅氧烷具有100,000cS(0.1m2/s)的粘度上限,并且尽管所述低粘度液体的可塑度不易通过ASTM D926方法来测量,但可以确定的是,这相当于约24的可塑度。尽管组分(B′)的可塑度没有绝对的上限,但在常规混合设备中对加工性能的实际考虑通常将对该值进行限制。优选的是,可塑度应当约为100-200,最优选约为120-185。
高稠度、含不饱和基团的聚二有机硅氧烷的制备方法为大家所熟知,在本说明书中不需要详细讨论它们。例如,链烯基官能聚合物的典型的制备方法包括在类似链烯基官能物质的存在下,环状和/或线型二有机聚硅氧烷的碱催化平衡。
非必需组分(B″)是细碎的填料,其已知用来增强二有机聚硅氧烷(B′)并且优选选自细碎的、热稳定的矿物,如比表面积至少约50m2/g的煅制二氧化硅和沉淀二氧化硅,白炭黑以及二氧化钛。基于其高表面积,煅制形式的二氧化硅是优选的增强填料,其表面积可高达450m2/g;特别优选的是表面积为50-400m2/g,最优选为200-380m2/g的煅制二氧化硅。优选的是,对煅制二氧化硅填料进行处理,以使其表面疏水,如典型地在硅橡胶领域中所进行的。这可通过使二氧化硅与包含硅烷醇基或硅烷醇基的可水解前体的液体有机硅化合物反应而实现。可用作填料处理剂(在硅橡胶领域中,也称为抗蠕变剂或增塑剂)的化合物包括:这样的成分,如低分子量液体羟基-或烷氧基封端的聚二有机硅氧烷,六有机二硅氧烷,环二甲基硅氮烷和六有机二硅氮烷。优选的是,处理化合物是低聚的羟基封端的二有机聚硅氧烷,其平均聚合度(DP)为2至约100,更优选为约2-10,以每100重量份二氧化硅填料计,其用量约为5-50重量份。当组分(B′)为优选的乙烯基官能或己烯基官能的聚二硅氮烷时,所述处理剂优选为羟基封端的聚二甲基硅氧烷。
当组分(B″)用于本发明时,将5-200重量份,优选5-150重量份,最优选20-100重量份的增强填料(B″)均匀地与100重量份胶料(B′)混合,以制备硅氧烷基料(B)。该混合通常利用如在硅橡胶领域中熟知的双辊塑炼机,密炼机或其它合适的装置在室温进行。另外,如下面进一步描述的那样,硅氧烷基料可在胶料动态硫化之前,在混合期间就地形成。在后一情况下,混合温度保持在聚酰胺树脂的软化点或熔点以下,直至增强填料充分分散于二有机聚硅氧烷胶料中为止。
组分(C)是选自缩水甘油酯官能聚合物或有机官能接枝聚烯烃的增容剂。对于本发明,在热塑性弹性体制备中至少包括一种增容剂。
在第一实施方案中,增容剂(C)是缩水甘油酯聚合物。对于本发明,缩水甘油酯聚合物定义为包含衍生于一种或更多种缩水甘油酯单体的重复单元的聚合物。缩水甘油酯聚合物可是均聚物,二元共聚物或三元共聚物。缩水甘油酯单体指的是烯属不饱和羧酸如丙烯酸,甲基丙烯酸,衣康酸的缩水甘油酯,包括例如丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,衣康酸缩水甘油酯。用于本发明的合适的缩水甘油酯聚合物的例子是在US5,981,661中描述的作为缩水甘油酯耐冲击性改进剂的缩水甘油酯,在此将其引入作为参考。优选的是,缩水甘油酯聚合物包含衍生于一种或更多种缩水甘油酯单体的第一重复单元和衍生于一种或更多种α-烯烃单体如乙烯,丙烯,1-丁烯,1-戊烯的第二重复单元。优选的是,缩水甘油酯单体是丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯。
合适的缩水甘油酯聚合物可以非必需地包含少量即至多约50%重量的衍生于一种或更多种其它单烯键不饱和单体的重复单元,所述单烯键不饱和单体可与缩水甘油酯单体共聚合。这里所用的术语“单烯键不饱和”指的是每个分子具有一个烯属不饱和的位置。合适的可共聚单烯键不饱和单体包括:例如乙烯基芳族单体,如苯乙烯和乙烯基甲苯,乙烯基酯,如醋酸乙烯酯和丙酸乙烯酯,以及(甲基)丙烯酸(C1-C20)烷基酯,如丙烯酸丁酯,甲基丙烯酸甲酯,甲基丙烯酸环己酯。这里所用的术语“(C1-C20)烷基”指的是每个基团具有1-20碳原子的直链或支链烷基,如甲基,乙基,癸基,二十烷基,环己基,并且术语“(甲基)丙烯酸酯”指的是丙烯酸酯化合物和甲基丙烯酸酯化合物。
合适的缩水甘油酯共聚物可通过例如常规的自由基引发共聚合来制备。
更优选的是,用作本发明中增容剂的缩水甘油酯聚合物选自烯烃-(甲基)丙烯酸缩水甘油酯聚合物,烯烃-醋酸乙烯酯-(甲基)丙烯酸缩水甘油酯聚合物和烯烃-(甲基)丙烯酸缩水甘油酯-(甲基)丙烯酸烷基酯聚合物。最优选的是,缩水甘油酯聚合物选自无规的乙烯/丙烯酸酯/甲基丙烯酸缩水甘油酯共聚物或三元共聚物,如由Elf Atochem(ElfAtochem,North America,Inc.,Philadelphia,PA)以LOTADERAX8900Resin,LOTADERAX 8930,和LOTADERAX 8840出售的LOTADERGMA产品。
在第二实施方案中,共聚物增容剂选自有机官能的接枝聚烯烃。对于本发明,“有机官能的接枝聚烯烃”是烯烃和有机官能的接枝单体的均聚物,二元共聚物或三元共聚物。合适烯烃的代表性例子包括:乙烯,丙烯,丁烯等等;烯烃例如乙烯,丙烯和二烯的混合物,即所谓的EPDM。另外,烯烃还可选自:C5-C20烃的α-烯烃,醋酸乙烯酯,丙烯酸烷基酯或甲基丙烯酸烷基酯,其中,烷基可为甲基,乙基,丙基,丁基等等。所述α-烯烃的合适例子包括1-己烯,1-辛烯,和1-癸烯。丙烯酸烷基酯的烷基的例子包括甲基,乙基,丙基和丁基。有机官能接枝单体可选自:包含下述有机官能基团的烯属不饱和烃:羧酸,羧酸盐,酰胺,酰亚胺,酯,酸酐,环氧基,烷氧基,和噁唑啉。所述噁唑啉基团具有如下结构:
式中,环可以包含一个或更多个选自1-4个碳原子的烃基的取代基。
包含羧酸和酸酐的烯属不饱和烃的例子是:丙烯酸,甲基丙烯酸,马来酸,富马酸,衣康酸,巴豆酸,衣康酸酐,马来酸酐,和取代的马来酸酐,如二甲基马来酸酐或柠康酸酐,桥亚甲基四氢化邻苯二甲酸酐,桥亚甲基甲基四氢化邻苯二甲酸酐(nadic methyl anhydride),和四氢化邻苯二甲酸酐,其中特别优选的是马来酸酐。不饱和酸衍生物的例子是盐,酰胺,酰亚胺和酯,例如,顺丁烯二酸一钠和二钠,丙烯酰胺,顺丁烯二酰亚胺,甲基丙烯酸缩水甘油酯和富马酸二甲酯。环氧官能单体的例子包括烯丙基缩水甘油醚,1,2-环氧-7-辛烯,1,2-环氧-9-癸烯,1,2-环氧-5-己烯。噁唑啉官能单体的例子是己烯基噁唑啉。用于有机官能接枝聚烯烃增容剂的优选的接枝单体选自马来酸酐和马来酸酐衍生物。
优选的是,有机官能接枝聚烯烃增容剂选自:聚(乙烯-共聚-醋酸乙烯酯)-接枝-马来酸酐,聚丙烯-接枝-马来酸酐,聚乙烯-聚丙烯-接枝-马来酸酐,马来酸酐接枝EPDM橡胶,马来酸酐接枝SEBS(苯乙烯-乙烯/丁烯-苯乙烯三嵌段共聚物)。
最优选的是,有机官能接枝聚烯烃是马来酸酐接枝的EPDM,例如市售的Royaltuf,485-B(Uniroyal Chemical Company,Inc.,Middlebury,CT06749),或马来酸酐接枝的聚丙烯,得自同一公司的Polybone。在接枝聚合物中,这些不饱和接枝单体的含量可为0.1-10%重量,优选的是0.3-4%重量。
可添加至本发明步骤(I)的增容剂的用量优选为所有组分总量的0.1-25%重量,更优选1-15%重量,最优选2-8%重量。
组分(D)的例子如下:低分子的硅氧烷,如PhSi(OSiMe2H)3;三甲基甲硅烷氧基封端的甲基氢化聚硅氧烷;三甲基甲硅烷氧基封端的二甲基硅氧烷-甲基氢化硅氧烷共聚物;二甲基氢化甲硅烷氧基封端的二甲基聚硅氧烷;二甲基氢甲硅烷氧基封端的甲基氢聚硅氧烷;二甲基氢化甲硅烷氧基封端的二甲基硅氧烷-甲基氢化硅氧烷共聚物;环状甲基氢聚硅氧烷;环状二甲基硅氧烷-甲基氢化硅氧烷共聚物;四(二甲基氢甲硅烷氧基)硅烷;由(CH3)2HSiO1/2,(CH3)3SiO1/2,和SiO4/2单元组成的硅氧烷树脂;和由(CH3)2HSiO1/2,(CH3)3SiO1/2,CH3SiO3/2,PhSiO3/2和SiO4/2单元组成的硅氧烷树脂,式中Me和Ph在下文分别表示甲基和苯基。
特别优选的有机氢化硅化合物是包含用R3SiO1/2或HR2SiO1/2封端的RHSiO单元的均聚物或共聚物,其中R独立地选自具有1-20个碳原子的烷基,苯基或三氟丙基,优选为甲基。另外还优选的是,组分(D)的粘度在25℃时约为0.5-1,000mPa·s,优选为2-500mPa·s。另外,该组分优选有0.5-1.7%重量键合至硅上的氢。特别优选的是,组分(D)选自主要由甲基氢化硅氧烷单元组成的聚合物或主要由聚二甲基硅氧烷单元和甲基氢化硅氧烷单元组成的共聚物,所述聚合物或共聚物具有0.5-1.7%重量键合至硅上的氢并且在25℃时的粘度为2-500mPa·s。应当理解的是,所述特别优选的体系将具有选自三甲基甲硅烷氧基或二甲基氢化甲硅烷氧基的端基。
另外,组分(D)还可以是两种或更多种上述体系的组合。有机氢化硅化合物(D)的用量使得其中的SiH与组分(B′)中Si-链烯基的摩尔比大于1,优选低于约50,更优选3-30,最优选4-20。
这些SiH-官能的材料在本领域是熟知的,并且其中许多可从市场上得到。
硅氢化催化剂(E)是促进本发明组合物中二有机聚硅氧烷(B′)固化的催化剂。该硅氢化催化剂的例子有:铂催化剂,如铂黑,担载在二氧化硅上的铂,担载在碳上的铂,氯铂酸,氯铂酸的醇溶液,铂/烯烃配合物,铂/链烯基硅氧烷配合物,铂/β-二酮配合物,铂/膦配合物等等;铑催化剂,如三氯化铑和三氯化铑/二正丁基硫配合物等等;以及钯催化剂,如担载在碳上的钯,氯化钯等等。组分(E)优选为铂基催化剂,如氯铂酸;二氯化铂;四氯化铂;通过氯铂酸和二乙烯基四甲基二硅氧烷反应而生产的铂配合物催化剂,其中所述二乙烯基四甲基二硅氧烷用二甲基乙烯基甲硅烷氧基封端的聚二甲硅氧烷稀释,根据US3,419,593(Willing)进行制备;以及氯化亚铂和二乙烯基四甲基二硅氧烷的中和配合物,其根据US5,175,325(Brown等人)制备。最优选的是,催化剂(E)是氯化亚铂和二乙烯基四甲基二硅氧烷的中和配合物。
以足以促进组分(B′)和(D)反应的催化量将组分(E)添加至本发明的组合物中,并由此使二有机聚硅氧烷固化而形成弹性体。优选的是,这样来添加催化剂,以基于热塑性弹性体组合物的总重量计,提供约0.1-500ppm的金属原子,更优选为0.25-100ppm。
在本发明的优选实施方案中,稳定剂(F)包括在所述配方中。稳定剂(F)为选自受阻酚;硫代酸酯;受阻胺;2,2-(1,4-亚苯基)二(4H-3,1-苯并噁嗪-4-酮);或3,5-二叔丁基-4-羟基苯甲酸十六烷基酯的至少一种有机化合物。
对于本发明,受阻酚是分子中具有至少一个下式基团的有机化合物:
结构式(i)
其中,Q为具有1-24个碳原子的一价有机基团,选自烃基、非必需地包含选自硫、氮或氧的杂原子的烃基或上述基团的卤素取代物。Q的例子包括:如烷基,芳基,烷芳基,芳烷基,环烷基及其卤素取代物;具有1-24碳原子的烷氧基,如甲氧基或叔丁氧基;和包含杂原子、具有2-24碳原子的烃基(例如,-CH2-S-R″,-CH2-O-R″或-CH2-C(O)OR″,其中R″是具有1-18碳原子的烃基)。另外,尽管在结构式(i)中没有清楚地示出,但也可预料的是,苯环可以另外被上述Q基团中的一个或更多个取代。基团(i)化学结合至其上的有机化合物的剩余部分并不重要,只要它不包含干扰如下描述的动态硫化的部分。例如,该剩余部分可以是适当化合价的烃,取代的烃或包含杂原子的烃基。另外还可以预料的是,结构式(i)的基团可连接至氢上以形成有机酚。优选的是,受阻酚化合物的数均分子量小于约3,000。
优选的受阻酚化合物在其分子中包含至少一个下式的基团:
结构式(ii)
其中,苯环可以非必需地被1-24碳原子的烃基进一步取代。在结构式(ii)中,R为具有1-4碳原子的烷基,并且R′为具有4-8碳原子的烃基。
优选的是,使示于结构式(i)或(ii)中的一至四个基团连接至适当化合价的有机残基上,以致使预期的化合物的分子量(MW)低于约1,500。最优选的是,使四个所述基团存在于组分(C)中,和该化合物的分子量低于约1,200。该一价(或多价)有机残基可包含一个或更多个杂原子,如氧,氮,磷和硫。上式中,可以列举的R′基团为叔-丁基,正-戊基,丁烯基,己烯基,环戊烯基,环己基和苯基。优选的是,R和R′均为叔-丁基。对于本发明,也可将结构式(ii)的基团连接至氢上,以形成二有机基苯酚。
合适受阻酚的非限定性例子包括:1,1,3-三(2′-甲基-4′-羟基-5′-叔丁基苯基)丁烷,N,N′-六亚甲基二(3-(3,5-二-叔丁基-4-羟苯基)丙酰胺),4,4′-硫代二(2-叔丁基-5-甲基苯酚),1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苯甲基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮,N,N′-六亚甲基二(3,5-二叔丁基-4-羟基氢化肉桂酰胺),四(亚甲基(3,5-二叔丁基-4-羟基-氢化肉桂酸酯)甲烷,1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苯甲基)苯,4,4′-亚甲基二(2,6-二叔丁基苯酚),2,2′-硫代二(6-叔丁基-4-甲基苯酚),2,2′-硫代二(4-辛基苯酚),4,4′-硫代二(6-叔丁基-2-甲基苯酚),4,4′-硫代二(3,6-二仲戊基苯酚),2-(4,6-二(2,4-二甲基苯基)-1,3,5,-三嗪-2-基)-5-(辛氧基)苯酚,2,4-二辛基巯基-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯,2-辛基巯基-4,6-二(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-二(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三(3,5-二叔丁基-4-羟苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰基)六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟苄基)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯,2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基氢醌,2,5-二叔戊基氢醌,2,6-二叔丁基氢醌,2,5-二叔丁基-4-羟基苯甲醚,2,6-二苯基-4-十八烷氧基苯酚,3,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟苯基硬脂酸酯,二(3,5-二叔丁基-4-羟苯基)己二酸酯,β-(3,5-二叔丁基-4-羟苯基)丙酸与一元醇或多元醇(例如甲醇,乙醇,正辛醇,三甲基己二醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫代二甘醇,二甘醇,三甘醇,季戊四醇,三羟甲基丙烷,三(羟乙基)异氰脲酸酯,N,N’-二(羟乙基)乙二酰胺,3-硫代十一烷醇,3-硫代十五烷醇,4-羟甲基-1-磷-2,6,7-三噁二环(2.2.2)辛烷)的酯,以及β-(5-叔丁基-4-羟基-3-甲苯基)丙酸与上述一元醇或多元醇的酯。
本发明的硫代酸酯是具有至少一个式G-S-G(iii)基团的化合物,其中,G是-CH2-CH2-C(O)OR并且R是具有1-24碳原子的一价烃基。合适硫代酸酯的具体的非限定性例子包括3,3′-硫代二丙酸二硬脂酯,3,3′-硫代二丙酸二月桂基酯和3,3′-硫代二丙酸二(十三烷基)酯。
本发明的受阻胺是包含至少一个下式的二价基团的低分子量有机化合物或聚合物
结构式(iv)
其中,Me在下文中表示甲基。该组分的主链并不重要,只要其不包含干扰硅氧烷胶料动态硫化的官能度,并且说明性的例子如披露于在此引入作为参考的US4,692,486中的低分子的和聚合的多烷基哌啶。优选的是,上述基团具有如下结构:
结构式(v)
式中,Z选自氢或具有1-24个碳原子的烷基,优选为氢。
合适受阻胺的具体的非限定性例子包括:1,6-己二胺,N,N′-二(2,2,6,6-五甲基-4-哌啶基)-,具有吗啉-2,4,6-三氯-1,3,5-三嗪的聚合物;1,3-苯二甲酰胺,N,N′-二(2,2,6,6-四甲基-4-哌啶基),具有2,4,-二氯代-6-(4-吗啉基)-1,3,5-三嗪的聚合物;二(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯;二(2,2,6,6-四甲基-4-哌啶基)癸二酸酯;具有4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的琥珀酸二甲酯聚合物;和聚甲基(丙基-3-氧-(2′,2′,6′,6′-四甲基-4′-哌啶基)硅氧烷。
本发明优选的稳定剂是四(亚甲基(3,5-二叔丁基-4-羟基-氢化肉桂酸酯))甲烷,N,N′-六亚甲基二(3,5-二叔丁基-4-羟基氢化肉桂酰胺)和1,1,3-三(2′-甲基-4′-羟基-5′-叔丁基苯基)丁烷,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苯甲基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮,以及3,3′-硫代二丙酸二月桂基酯。
组分(F)的具体的非限定性例子包括由Ciba Specialty ChemicalsCorporation以商品名IrganoxTM出售的各种受阻酚。IrganoxTM1076=3,5-二叔丁基-4-羟基氢化肉桂酸十八烷基酯,IrganoxTM1035=二(3,5-二叔丁基-4-羟基氢化肉桂酸)硫代二亚乙基酯,IrganoxTM MD1024=1,2-二(3,5-二叔丁基-4-羟基氢化肉桂酰)肼,IrganoxTM 1330=1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟苄基)苯,IrganoxTM1425WL=二(一乙基(3,5-二叔丁基-4-羟苄基)膦酸)钙以及IrganoxTM3114=1,3,5-三(3,5-二叔丁基-4-羟苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮。优选的受阻酚是IrganoxTM245{三甘醇二(3-(3′-叔丁基-4′-羟基-5′-甲基苯基)丙酸酯)},IrganoxTM1098{N,N′-六亚甲基二(3,5-二叔丁基-4-羟基氢化肉桂酰胺)}和IrganoxTM1010{四(亚甲基(3,5-二-叔丁基-4-羟基-氢化肉桂酸酯))甲烷}。
对于每100重量份聚酰胺(A)和硅氧烷基料(B),优选使用0.01-5重量份稳定剂(F)。对于每100重量份(A)加上(B),优选添加0.1-0.75重量份,更优选0.4-0.6重量份(F)。
除上面提到的组分之外,少量非必需的添加剂(G)可掺入本发明的组合物中。优选的是,以组合物总量计,该非必需组分添加量为0.5-40%重量,更优选为0.5-20%重量。该非必需的添加剂的例子包括但不局限于:用于聚酰胺树脂的增强填料,如玻璃纤维和碳纤维;增量填料,如石英,硫酸钡,碳酸钙,和硅藻土;颜料,如氧化铁和二氧化钛;导电填料,如炭黑和细碎金属;热稳定剂,如水合氧化铈;抗氧化剂;阻燃剂,如卤代烃,三水氧化铝,氢氧化镁和有机磷化合物;及其它防火(FR)材料。优选的FR添加剂是硅酸钙颗粒,优选的是,平均粒度为2-30微米的硅灰石。另外,非必需组分(G)可是用于硅氧烷胶料组分的增塑剂,如聚二甲基硅氧烷油,和/或用于聚酰胺组分的增塑剂。后者的例子包括:邻苯二甲酸酯,如邻苯二甲酸二环己酯,邻苯二甲酸二甲酯,邻苯二甲酸二辛酯,邻苯二甲酸丁基苄酯和邻苯二甲酸苯甲基酯;偏苯三酸酯,如偏苯三酸C1-C9烷基酯;磺酰胺,如N-环己基-对甲苯磺酰胺,N-乙基-邻,对-甲苯磺酰胺和邻-甲苯磺酰胺,和液体低聚物增塑剂。优选的增塑剂是:在聚酰胺通常的熔融温度下增塑剂散发最少的低挥发性液体。
通常,在动态固化之后将上述添加剂添加至最终的热塑性组合物中,但它们也可以在制备过程的任何位置添加,前提条件是,它们不干扰动态硫化机理。当然,上述附加成分仅以不明显减弱最终组合物希望性能的用量使用。
本发明方法的第二步骤是动态硫化二有机聚硅氧烷(B′)。在此所使用的“动态硫化”指的是二有机聚硅氧烷(B′)进行固化过程,即进行固化。因此,根据本发明的方法,通过将硅氧烷基料(B)和增容剂(C)充分地分散于聚酰胺(A)中,并利用有机氢化硅化合物(D)和催化剂(E)在所述基料中使二有机聚硅氧烷动态硫化,而制备热塑性弹性体。对于本发明,硅氧烷基料(B)与聚酰胺树脂(A)的重量比大于35∶65。业已发现,当该重量比为35∶65或更低时,最终的硫化产品通常具有与热塑性弹性体相比更类似于聚酰胺树脂的模量。另一方面,上述重量比不应当大于约85∶15,这是因为在所述重量比以上,所述组合物往往会变弱且类似于固化的硅氧烷弹性体。尽管有该上限,但(B)与(A)的最大比对于任何给定组分的组合而言还将受加工性能的限制,这是因为太高的硅氧烷基料含量将造成部分交联的连续相,后者不再是热塑性的。对于本发明,该实际的极限通过常规试验能容易地确定,并且表示使TPSiV能够进行压塑的组分(B)的最高含量。然而,优选的是,最终的热塑性弹性体还可以用其它常规的塑料操作如注塑和挤塑容易地进行加工处理,并且在这种情况下,(B)与(A)的重量比应当不大于约75∶25。随后进行再加工的所述优选的热塑性弹性体通常具有的抗张强度和伸长率值在原始TPSiV对应值的10%的范围之内(即,通过再加工热塑性弹性体几乎没有改变)。尽管符合上述要求的硅氧烷基料的用量取决于所用具体的聚酰胺树脂及其他组分,但优选的是,组分(B)与(A)的重量比为40∶60至75∶25,更优选为40∶60至70∶30。
在能够将各组分均匀分散于聚酰胺树脂中的任何装置中,如在密炼机或双螺旋挤出机中进行混合,对于工业化制备后者是优选的。优选将温度保持在符合良好混合尽可能低的温度,以便不使树脂降解。取决于特定的体系,混合顺序通常不重要,例如,可在(A)软化点(即熔点或玻璃化温度)以上的温度将组分(A),(C),(D)以及非必需的(F)添加至(B)中,然后引入催化剂(E),以便开始动态硫化。然而,在动态硫化开始之前,必须使组分(B)至(F)充分分散于树脂(A)中。如前所述,另外还设想的是,硅氧烷基料可就地形成。例如,可以在聚酰胺树脂软化点以下的温度将增强填料添加至已包含聚酰胺树脂和二有机聚硅氧烷胶料的混合机中,以使填料充分分散于所述胶料中。然后升温,以使树脂熔融,再添加其它的成分,并进行混合/动态硫化。混合操作的最佳温度,搅拌时间及其他条件取决于特定的树脂和所考虑的其它组分,并且这些因素可以由本领域普通技术人员通过常规的试验来确定。然而,优选的是,在干燥的惰性气氛(即不与各组分进行副反应或其它干扰硅氢化的气氛)下,如干燥氮,氦或氩气氛下,进行混合和动态硫化。
如上所述,为了落入本发明的范围之内,TPSiV弹性体的抗张强度或伸长率或两者必须比相应的简单混合物大至少25%。本发明另外的要求是:当通过下文所述试验方法进行测量时,TPSiV具有至少25%的伸长率。在本文中,术语“简单混合物”(或物理混合物)表示其中树脂(A),基料(B)和增容剂(C)的重量比与TPSiV中的比例相同的组合物,但不使用固化剂(即省略组分(D)或(E),或两者,并因此胶料不固化)。为了确定是否特定的组合物满足上述条件,根据ASTM方法D412,以50mm/min的伸长速率,针对长度为25.4毫米、宽度3.2毫米且典型的厚度为1-2毫米的哑铃试样,测量TPSiV的抗张强度。至少评估三个所述的试样,并在除去由于试样不匀一性(例如空隙,污染物或夹杂物)所致的明显低读数之后对结果取平均值。然后,将这些值与通过简单混合的组合物制备的试样的相应的平均抗张强度和伸长率进行对比。当在抗张强度和伸长率方面不能取得相对简单混合物至少25%的改善时,则动态硫化没有任何益处,并且这样的TPSiVs不在本发明的范围之内。
然后,可通过常规技术,如挤出,真空成型,注塑,吹塑,重叠注塑或压塑,对上述方法制得的热塑性弹性体进行加工处理。此外,这些组合物可进行再加工(循环利用),而几乎没有或没有机械性能的减弱。
本发明新颖的热塑性弹性体可用于制造电线和电缆的绝缘层;振动和声音阻尼部件;电插塞;汽车和设备的部件,如皮带,软管,导气管,保护罩,波纹管,垫片和燃料管部件;家具部件;用于手握装置的“柔软手感”手柄(如工具的把手);建筑的封条;瓶塞;医用器材;体育用品;和一般的橡胶部件。
实施例
列出如下实施例以进一步阐明本发明的组合物和方法,但这并不构成对本发明的限定,本发明由所附的权利要求书限定。在实施例中,除非另有说明,所有份数和百分数均以重量计,所述测量值均在约23℃获得。
材料
为便于参考按字母顺序列出在实施例中使用的下列材料。
BASE(基料)1是由如下所述68.7%PDMS1、25.8%的煅制二氧化硅(表面积约250m2/g(Cab-O-SilMS-75,Cabot Corp.,Tuscola,IL.)、5.4%羟基封端的二有机聚硅氧烷(平均聚合度(DP)约8)和0.02%的碳酸铵制得的硅氧烷橡胶基料。
CATALYST(催化剂)1是1.5%1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷;6%四甲基二乙烯基二硅氧烷;92%二甲基乙烯基封端的聚二甲硅氧烷和0.5%有6个或更多个二甲基硅氧烷单元的二甲基环聚硅氧烷的铂配合物。X-LINKER 1是主要由68.4%MeHSiO单元,28.1%Me2SiO单元和3.5%Me3SiO1/2单元组成的SiH-官能交联剂,并且具有约29mPa.s的粘度。这相当于平均式MD16D′39M,其中M为(CH3)3Si-O-,D是-Si(CH3)2-O-且D′为-Si(H)(CH3)-O-。COMPATIBILIZER 1是AX 8900,它是由Elf Atochem North America,Inc.,2000Market Street,Philadelphia,PA 19103以商品名LOTADERAX 8900出售的乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯三元共聚物(E-MA-GMA)。
COMPATIBILIZER(增容剂)2是AX 8930,它是由Elf AtochemNorth America,Inc.,2000 Market Street,Philadelphia,PA 19103以商品名LOTADERAX 8930出售的乙烯-丙烯酸甲酯-甲基丙烯酸缩水甘油酯三元共聚物(E-MA-GMA)。COMPATIBILIZER 3是LOTADER3410,它是由Elf Atochem North America,Inc.,2000Market Street,Philadelphia,PA19103以商品名LOTADER3410出售的乙烯-丙烯酸正丁酯-马来酸酐三元共聚物。COMPATIBILIZER 4是LOTADER3300,它是由Elf Atochem North America,Inc.,2000Market Street,Philadelphia,PA19103以商品名LOTADER3300出售的乙烯-丙烯酸乙酯-马来酸酐三元共聚物。
COMPATIBILIZER 5是LOTADER6200,它是由Elf AtochemNorth America,Inc.,2000 Market Street,Philadelphia,PA19103以商品名LOTADER6200出售的乙烯-丙烯酸正丁酯-马来酸酐三元共聚物。COMPATIBILIZER 6是ROYALTUF 485-B,它是得自UniroyalChemical Company,Inc.,Middlebury,CT 06749的马来酸酐接枝的EPDM。
COMPATIBILIZER 7是得自Aldrich的马来酸酐接枝的聚丙烯,其马来酸酐含量为0.6%并且熔体流动指数为115。IRGANOxTM1010由Ciba-Geigy出售的受阻酚稳定剂并且描述为四{亚甲基(3,5-二叔丁基-4-羟基-氢化肉桂酸酯)}甲烷。
LOWINOXTM CA22由Great Lake Chemical Corporation出售的受阻酚稳定剂,并且描述为1,1,3-三(2′-甲基-4′-羟基-5′-叔丁基苯基)丁烷。NYLON 12是RILSANTM AMNO,由Elf Atochem NA,Inc.(Philadelphia,PA)出售的尼龙12;m.p.=175℃。
NYLON(尼龙)6是由DU Pont以商品名ZYTELTM7301出售的尼龙6;其熔点为215-225℃。
PDMS 1是由99.81wt%Me2SiO单元,0.16%MeViSiO单元和0.03%Me2ViSiO1/2单元组成的胶料。通过环硅氧烷的钾催化平衡来制备,其中,催化剂用二氧化碳中和。该胶料的可塑度约为150。
设备:
TPSiVs用Polylab Haake混合器制备。该混合器装备有3000系列的滚筒和滚轴转子。对于尼龙6在240℃和对于尼龙12在220℃下操作滚筒。转子转速恒定在60RPM。在操作期间,氮气层设置在滚筒上,其流量为0.5SCFM。
利用装配有West 4100系列温度控制器的Wabash热压机,将粗TPSiV压塑成试验板。对于尼龙6在250℃和对于尼龙12在225℃下操作热压机。在15吨压力下对试样模压3分钟。按照ASTM D412的规格从试验板上切取试样。至少对5个试样进行测试并列出平均结果。
实施例1
下列的一般步骤用来制备尼龙6TPSiVs,示于表1。
在典型试验中,将滚筒加热至操作温度(240℃)或使之保持在操作温度。然后启动操作,并且向滚筒装入120.0克BASE 1。在添加80.0克尼龙6之前对BASE 1混合1分钟。在添加3.21克COMPATIBILIZER 1之前对混合物混合2分钟。(增容剂的浓度以体系中尼龙的重量计。)对COMPATIBILIZER 1混合2分钟,然后添加1.08克LoWinox CA-22稳定剂。在混合2分钟之后,添加3.86克X-LINKER 1。使该交联剂混合4分钟以保证良好的分散作用。然后添加2.28克稀CATALYST 1。在添加催化剂之后,作为硅氧烷基料的固化反应的指示,扭矩开始增加。在扭矩平衡后2分钟,结束操作并从滚筒中取出TPSiV。
表1.PA6TPSiVs的增容作用
操作序号 | 增容剂序号 | 增容剂浓度(相对于尼龙的wt%) | 最大扭矩mg | 拉伸强度MPa | 断裂伸长率% |
1 | 无 | 对照 | 4000 | 15.7 | 132.6 |
2 | 1 | 1 | 4500 | 14.8 | 130.2 |
3 | 1 | 2 | 4900 | 17.4 | 206 |
4 | 1 | 4 | 5500 | 17.38 | 210.5 |
5 | 2 | 1 | 4100 | 16.3 | 147.1 |
6 | 2 | 2 | 4700 | 17.8 | 195.4 |
7 | 2 | 4 | 4800 | 17.2 | 180.8 |
8 | 3 | 1 | 5300 | 17.1 | 150.6 |
9 | 3 | 2 | 5700 | 15.1 | 108.1 |
10 | 3 | 4 | 6100 | 16.9 | 126.1 |
11 | 4 | 1 | 5200 | 17.1 | 155.6 |
12 | 4 | 2 | 5800 | 18.9 | 173.4 |
13 | 4 | 4 | 6100 | 18.4 | 146.3 |
14 | 5 | 1 | 5000 | 16.2 | 145.4 |
15 | 5 | 2 | 5200 | 17.3 | 148.8 |
16 | 5 | 4 | 5400 | 17.7 | 163.1 |
17 | 6 | 1 | 4000 | 17.0 | 140.4 |
18 | 6 | 2 | 4300 | 19.1 | 163.6 |
19 | 6 | 4 | 5000 | 17.6 | 142.9 |
实施例2
下列的一般步骤用来制备尼龙-12TPSiVs,示于表2中。
在典型试验中,将滚筒加热至操作温度(220℃)或使之保持在操作温度。然后启动操作,并且向滚筒装入120.0克BASE 1。在添加80.0克尼龙12和想要量的增容剂之前,对BASE 1混合1分钟。添加增容的尼龙-12/BASE 1(增容剂的浓度以体系中尼龙的重量计)。然后添加1.0克Irganox 1010稳定剂。在混合2分钟之后,添加1.95克X-LINKER 1。在用2.25克CATALYST 1对操作催化之前,对该交联剂混合4分钟,以保证良好的分散作用。在添加催化剂之后,作为硅氧烷基料的固化反应的指示,扭矩开始增加。在扭矩平衡后2分钟,结束操作并从滚筒中取出TPSiV。
表2.PA12TPSiVs的增容作用
操作序号 | 增容剂序号 | 增容剂浓度(相对于尼龙的wt%) | 最大扭矩m.g | 拉伸强度MPa | 断裂伸长率% |
20 | 无 | 对照 | 4000 | 9.6 | 83.4 |
21 | 1 | 1 | 4500 | 14.3 | 208.7 |
22 | 1 | 2 | 5000 | 15.3 | 251.2 |
23 | 1 | 4 | 6200 | 15.7 | 259.2 |
24 | 7 | 2 | 5500 | 12.6 | 157.2 |
Claims (13)
1.一种热塑性弹性体的制备方法,所述方法包括:
(I)混合下述组分:
(A)熔点或玻璃化转变温度为25-275℃的流变稳定的聚酰胺树脂,
(B)硅氧烷基料,包含:
(B′)100重量份二有机聚硅氧烷胶料,其按照ASTM试验方法926测定的可塑料度至少为30并且分子中平均有至少两个链烯基,和非必需地
(B″)5-200重量份增强填料,
所述硅氧烷基料与所述聚酰胺树脂的重量比为35∶65至85∶15,
(C)选自缩水甘油酯聚合物或有机官能接枝聚烯烃的增容剂,
(D)有机氢化硅化合物,其分子中平均包含至少两个与硅连接的氢,和
(E)硅氢化催化剂,
组分(D)和(E)的含量为足以使所述二有机聚硅氧烷(B′)固化;和
(II)使所述二有机聚硅氧烷(B′)动态硫化。
2.根据权利要求1的方法,其中所述聚酰胺选自尼龙6,尼龙6/6,尼龙6/12和尼龙12。
3.根据权利要求1的方法,其中所述的二有机聚硅氧烷(B′)为选自下述的胶料:由二甲基硅氧烷单元和甲基乙烯基硅氧烷单元组成的共聚物和由聚二甲基硅氧烷单元和甲基己烯基硅氧烷单元组成的共聚物,并且存在所述的增强填料(B″)且其为煅制二氧化硅。
4.根据权利要求1的方法,其中,增容剂是包含一种或更多种缩水甘油酯单体的重复单元的缩水甘油酯聚合物。
5.根据权利要求4的方法,其中,所述缩水甘油酯聚合物包含衍生于一种或更多种缩水甘油酯单体的第一重复单元和衍生于一种或更多种α-烯烃单体的第二重复单元。
6.根据权利要求5的方法,其中,缩水甘油酯单体是丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯。
7.根据权利要求4的方法,其中,缩水甘油酯聚合物选自烯烃-(甲基)丙烯酸缩水甘油酯聚合物,烯烃-醋酸乙烯酯-(甲基)丙烯酸缩水甘油酯聚合物和烯烃-(甲基)丙烯酸缩水甘油酯-(甲基)丙烯酸烷基酯聚合物。
8.根据权利要求4的方法,其中,缩水甘油酯聚合物是无规乙烯/丙烯酸酯/甲基丙烯酸缩水甘油酯二元共聚物或三元共聚物。
9.根据权利要求1的方法,其中,增容剂是有机官能的接枝聚烯烃,包括烯烃和有机官能的接枝单体的均聚物、二元共聚物或三元共聚物。
10.根据权利要求9的方法,其中,有机官能接枝单体为包含下列有机官能基团的烯属不饱和烃:羧酸、羧酸盐、酰胺、酰亚胺、酯、酸酐、环氧基、烷氧基和噁唑啉。
11.根据权利要求9的方法,其中,有机官能接枝聚烯烃选自聚(乙烯-共聚-醋酸乙烯酯)-接枝-马来酸酐、聚丙烯-接枝-马来酸酐、聚乙烯-聚丙烯-接枝-马来酸酐、马来酸酐接枝的乙烯-丙烯-二烯橡胶、马来酸酐接枝SEBS(苯乙烯-乙烯/丁烯-苯乙烯三嵌段共聚物)。
12.根据权利要求1的方法,其中,所述有机氢化硅组分(D)选自由甲基氢化硅氧烷单元组成的聚合物和由二甲基硅氧烷单元和甲基氢化硅氧烷单元组成的共聚物,其具有0.5-1.7%重量键合至硅上的氢并且在25℃时的粘度为2-500mPa·s,并且所述催化剂(E)是氯化亚铂和二乙烯基四甲基二硅氧烷的中和配合物。
13.根据权利要求1-12中任一项的方法,其中,相对每100重量份所述聚酰胺加上所述硅氧烷基料加入0.01-5重量份的稳定剂(F)到混合步骤(I)中,所述稳定剂选自受阻酚、硫代酸酯、受阻胺、2,2′-(1,4-亚苯基)二(4H-3,1-苯并噁嗪-4-酮)和3,5-二叔丁基-4-羟基苯甲酸十六烷基酯。
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AT (1) | ATE384103T1 (zh) |
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WO (1) | WO2003035759A1 (zh) |
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CN110234680A (zh) * | 2017-01-31 | 2019-09-13 | 玛尔提贝斯股份有限公司 | 热塑性组合物 |
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2001
- 2001-10-19 US US10/043,907 patent/US6569955B1/en not_active Expired - Lifetime
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2002
- 2002-10-15 CN CNB028206630A patent/CN1256385C/zh not_active Expired - Fee Related
- 2002-10-15 DE DE60224696T patent/DE60224696T2/de not_active Expired - Lifetime
- 2002-10-15 JP JP2003538268A patent/JP2005507020A/ja active Pending
- 2002-10-15 AT AT02786412T patent/ATE384103T1/de not_active IP Right Cessation
- 2002-10-15 KR KR10-2004-7005789A patent/KR20040058211A/ko not_active Application Discontinuation
- 2002-10-15 WO PCT/US2002/032888 patent/WO2003035759A1/en active IP Right Grant
- 2002-10-15 EP EP02786412A patent/EP1440123B1/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110234680A (zh) * | 2017-01-31 | 2019-09-13 | 玛尔提贝斯股份有限公司 | 热塑性组合物 |
Also Published As
Publication number | Publication date |
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KR20040058211A (ko) | 2004-07-03 |
WO2003035759A1 (en) | 2003-05-01 |
US6569955B1 (en) | 2003-05-27 |
DE60224696T2 (de) | 2009-01-22 |
JP2005507020A (ja) | 2005-03-10 |
EP1440123A1 (en) | 2004-07-28 |
EP1440123B1 (en) | 2008-01-16 |
ATE384103T1 (de) | 2008-02-15 |
DE60224696D1 (de) | 2008-03-06 |
CN1571818A (zh) | 2005-01-26 |
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