CN1216560A - 基于间同结构的乙烯基芳族聚合物、低粘度聚酰胺和极性基团改性的聚亚苯基醚的热塑性模塑组合物 - Google Patents
基于间同结构的乙烯基芳族聚合物、低粘度聚酰胺和极性基团改性的聚亚苯基醚的热塑性模塑组合物 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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Abstract
含有以下组分的热塑性模塑组合物:A)5—97.9%(重量)的间同结构的乙烯基芳族聚合物,B)2—90%(重量)的粘度值VN为50—150ml/g的低粘度聚酰胺,和C)0.1—50%(重量)极性基团改性的聚亚苯基醚。
Description
本发明涉及含有以下组分的热塑性模塑组合物:
A)5-97.9%(重量)的间同结构的乙烯基芳族聚合物,
B)2-90%(重量)的粘度值VN为50-150ml/g的低粘度聚酰胺,和
C)0.1-50%(重量)极性基团改性的的聚亚苯基醚。
本发明还涉及应用热塑性模塑组合物生产纤维、膜和模制品,以及由此得到的纤维、膜和模制品。
欧洲专利申请314 146已公开了一些由间同聚苯乙烯(s-PS)和聚亚苯基醚(PPE)组成的配合物。这里,得到的聚合物体系是多相的,而且虽然它们的耐热性好,但是它们非常脆,而且流动性不令人满意。
欧洲专利申请546 497描述了一种s-PS、无机填料和改性PPE的配合物。但是,该材料也是脆的。
本发明的一个目的是克服上述的缺点,并且提供具有流动性好、吸水性低、尺寸稳定性好和耐水解性提高的热塑性模塑组合物。
我们已经发现,应用本文开头所定义的热塑性模塑组合物可以达到这个目的。
此外,已发现热塑性模塑组合物在制备纤维、膜和模制品上的应用,以及由此得到的纤维、膜和模制品。
新的热塑性模塑组合物含有,如组分A),5-97.9%(重量),优选为15-89.8%(重量),特别是30-79.5%(重量)的具有间同结构的乙烯基芳族聚合物。这里的术语“具有间同结构”是指聚合物基本上是间同的,也即是,用13C-NMR确定的间同部分大于50%,优选大于60%。组分A)优选由式Ⅰ的化合物构成其中:R1是氢或C1-C4-烷基,R2-R6彼此独立的为氢、C1-C12-烷基、C6-C18-芳基,或卤素,或其中两个邻近的基团相连形成一个4-15个碳原子的环基。
优选使用的式Ⅰ的乙烯基芳族化合物,其中
R1是氢和
R2-R6是氢、C1-C4-烷基、氯、苯基、联苯基萘基或蒽基、或其中两个邻近的基团相连形成一个4-12个碳原子的环基,所以,得到的式Ⅰ的化合物是,例如,萘衍生物或蒽衍生物。
这些优选化合物的例子是:
苯乙烯、对甲基苯乙烯、对氯苯乙烯、2,4-二甲基苯乙烯、间,对-二乙烯基苯、4-乙烯基联苯、乙烯基萘或乙烯基蒽。
也可以使用不同的乙烯基芳族化合物的混合物,但优选仅使用一种乙烯基芳族化合物。
特别优选的乙烯基芳族化合物是苯乙烯、对甲基苯乙烯和间,对-二乙烯基苯。
组分A)也可是不同的具有间同结构的乙烯基芳族聚合物的混合物,但是优选仅使用一种乙烯基芳族聚合物,特别是s-PS。
具有间同结构的乙烯基芳族聚合物以及其制备方法本身是已知的,可参见,例如,欧洲专利申请535 582所述。它们优选通过在茂金属络合物的存在下使通式Ⅰ的化合物反应的方法制备。所用的茂金属络合物特别是
三氯化五甲基环戊二烯基钛,
五甲基环戊二烯基三甲基钛,和
五甲基环戊二烯基三甲醇钛。
具有间同结构的乙烯基芳族聚合物,通常其分子量Mw(重均)为5000-10,000,000,特别是10,000-2,000,000。分子量分布Mw/Mn(Mn=数均)通常为1.1-30,优选为1.4-10。
热塑性模塑组合物含有,如组分B),2-90%(重量),优选为10-80%(重量),特别是20-65%(重量)的粘度值VN为50-150ml/g,优选60-150ml/g,特别是70-150ml/g的低粘度聚酰胺。
粘度值VN是用含量0.5%(重量)的96%浓度硫酸溶液于25℃下测定。
聚酰胺是缩聚物,也即是由可解离出低分子量化合物的单体制备的聚合物。
这种方法本领域的技术人员是已知的,并已在文献中描述多次,所以这里就没有必要对这个题目提供更详细的信息。
很普通,在制备这类聚合物时,分子量(因而粘度)可以用不同的方法控制。
一个可能的方法是在较短的反应时间后终止缩聚反应,这种方法通过冷却反应混合物最容易进行。
另一个可能的方法是添加分子量调节剂;这些通常是可终止缩聚反应的单官能的化合物,因为它们一旦被进入分子链中,链端就没有任何可延续缩聚反应的官能基。已知的分子链调节剂的例子是通常用于制备聚酰胺的一元羧酸或一元醇和一元胺。
缩聚反应时调节分子量的最后一个方法是控制起始单体的摩尔比。已知缩聚反应中可达到的最大分子量取决于在有低分子量化合物解离的缩合时相互反应的基团的摩尔比。
由上可见,本领域的技术人员是熟悉低粘度聚酰胺的制备方法的。
一种制备这类聚酰胺的特别有利的合适方法见述于欧洲专利申请129 195和欧洲专利申请129 196。
优选的聚酰胺是聚-ε-己内酰胺(尼龙-6)、聚六亚甲基己二酰胺(尼龙-6,6)、它们的共聚物以及描述于,例如,欧洲专利申请299 444中的基于对苯二甲酸,和如果需要,间苯二甲酸、己二酸、六亚甲基二胺和ε-己内酰胺的部分芳族共聚酰胺。
优选的聚酰胺是带有大约等摩尔比的两个相应的端基的聚酰胺。
也可以使用上述聚酰胺的混合物。
新的热塑性模塑组合物含有,如组分C),0.1-50%(重量),优选为0.2-40%(重量),特别是0.5-20%(重量)的极性基团改性的聚亚苯基醚。
这种极性基团改性的聚亚苯基醚以及它们的制备方法,本身是已知的,和见述于,例如,欧洲专利申请41 29 499。
组分C)的极性基团改性的聚亚苯基醚优选由以下成分构成:
c1)70-99.95%(重量)的聚亚苯基醚,
c2)0-25%(重量)的乙烯基芳族聚合物,和
c3)0.05-5%(重量)的至少一种化合物,该化合物含有至少一个双键或三键和至少一个选自羧酸、羧酸酯、羧酸酐、羧酰胺、环氧化物、噁唑啉和氨基甲酸酯官能基。
聚亚苯基醚c1)的;例子是
聚(2,6-二月桂基-1,4-亚苯基醚),
聚(2,6-二苯基-1,4-亚苯基醚),
聚(2,6-二甲氧基-1,4-亚苯基醚),
聚(2,6-二乙氧基-1,4-亚苯基醚),
聚(2-甲氧基-6-乙氧基-1,4-亚苯基醚),
聚(2-乙基-6-硬脂酰氧-1,4-亚苯基醚),
聚(2,6-二氯-1,4-亚苯基醚),
聚(2-甲基-6-苯基-1,4-亚苯基醚),
聚(2,6-二苄基-1,4-亚苯基醚),
聚(2-乙氧基-1,4-亚苯基醚),
聚(2-氯-1,4-亚苯基醚),和
聚(2,5-二溴-1,4-亚苯基醚)。
优选使用的聚亚苯基醚是其中取代基为1-4个碳原子的烷基的聚亚苯基醚,如聚(2,6-二甲基-1,4-亚苯基醚),
聚(2,6-二乙基-1,4-亚苯基醚),
聚(2-甲基-6-乙基-1,4-亚苯基醚),
聚(2-甲基-6-丙基-1,4-亚苯基醚),
聚(2,6-二丙基-1,4-亚苯基醚),
聚(2-乙基-6-丙基-1,4-亚苯基醚)。
优选的乙烯基芳族聚合物c2)的例子见述于Olabisi的专著,224-230和245页。这里可提及的,也即是代表性的聚合物,是苯乙烯、氯代苯乙烯、α-甲基苯乙烯和对甲基苯乙烯的乙烯基芳族聚合物;结构中也可以含有比例不高的(优选不大于20%(重量),特别是不大于8%(重量))共聚单体,如(甲基)丙烯腈或(甲基)丙烯酸酯。特别优选的乙烯基芳族聚合物是聚苯乙烯和冲击改性的聚苯乙烯。这些聚合物的混合物当然也可应用。制备方法优选是欧洲专利申请302 485所述的方法。
适合的改性剂c3)的例子是马来酸、甲基马来酸、衣康酸、四氢化邻苯二甲酸、相应的酐和酰亚胺、富马酸、这些酸的单酯和双酯,例如C1和C2-C8的链烷醇的酯、这些酸的单酰胺或二酰胺,如N-丙基马来酰亚胺和马来肼。其他的例子是N-乙烯基吡咯烷酮和(甲基)丙烯酰己内酰胺。
另一组改性剂包括,例如,偏苯三酸酐的酰氯、苯-1,2-二羧酸酐-4-羧酸乙酸酐、1,2,4,5-苯四酸二酐、氯乙酰基丁二醛、氯甲酰基丁二醛、柠檬酸和羟基丁二酸。
在新的模塑组合物中特别优选的极性基团改性的聚亚苯基醚C)可用马来酸、马来酐或富马酸改性得到。这类聚亚苯基醚优选具有的分子量(重均分子量Mw)为10,000-80,000,优选为20,000-60,000。
这相应于比浓粘度ηred为0.2-0.9dl/g,优选为0.35-0.8dl/g,特别是0.45-0.6dl/g,在25℃的1%(重量)浓度的氯仿溶液中,根据DIN 53 726的方法测定。
新的热塑性模塑组合物可另外含有0-50%(重量),优选为0-15%(重量),特别是0-12%(重量)的添加剂或加工助剂或其混合物。
这些添加剂的例子是成核剂,如羧酸、有机磺酸或有机磷酸的盐,优选为苯甲酸钠、三(对叔丁基苯甲酸)铝、三苯甲酸铝、三(对羧甲基苯甲酸)铝和三己酸铝;抗氧剂,如酚类抗氧剂、亚磷酸酯或膦酸酯,特别是亚磷酸三壬基苯基酯;稳定剂,如空间受阻酚类和氢醌。也可能用润滑剂和脱模剂、染料、颜料和增塑剂。
新的热塑性模塑组合物还可含有0-20%(重量),优选为0-18%(重量),特别是0-15%(重量)的阻燃剂。
可用的阻燃剂是有机磷化合物,如磷酸酯或氧化膦。
氧化膦的例子是三苯基氧化膦、三甲苯基氧化膦、三壬基苯基氧化膦、三环己基氧化膦、三(正丁基)氧化膦、三-(正己基)氧化膦、三(正辛基)氧化膦、三(氰乙基)氧化膦、苄基双(环己基)氧化膦、苄基双苯基氧化膦和苯基双(正己基)氧化膦。特别优选使用的是三苯基氧化膦、三环己基氧化膦、三(正辛基)氧化膦或(氰乙基)氧化膦。
可用的磷酸酯特别是烷基和芳基取代的磷酸酯。它们的例子是磷酸苯基双十二烷基酯、磷酸苯基双新戊基酯、磷酸氢苯乙酯、磷酸苯基双(3,5,5-三甲基己基)酯、磷酸乙基二苯基酯、磷酸双(2-乙基己基)对甲苯基酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、磷酸三基酯、磷酸双(2-乙基己基)苯基酯、磷酸三(壬基苯基)酯、磷酸双(十二烷基)对(甲苯基)酯、磷酸三羟甲苯基酯、磷酸三苯酯、磷酸二丁基苯基酯、磷酸对甲苯基双(2,5,5-三甲基己基)酯和磷酸2-乙基己基二苯基酯。特别适合的化合物是每个R是芳基的磷化合物。磷酸三苯酯、磷酸三(二甲苯)酯以及磷酸三基酯是本发明非常特别适合的。也可以用环状的磷酸酯。二磷酸二苯基季戊四醇酯是本发明特别适合的。二磷酸间苯二酚酯也是优选的。
也可以使用不同磷化合物的混合物。
新的热塑性模塑组合物可另外含有0-50%(重量),优选为0-30%(重量),特别是0-20%(重量)的弹性体聚合物。
这些弹性体聚合物以及它们的制备方法本身是已知的,并见述于,例如,欧洲专利申请41 29 499。
仅可作例子提及的是带有交联的弹性体的芯和聚苯乙烯、EP橡胶、EPDM橡胶、嵌段共聚物和热塑性聚酯弹性体的接枝壳的接枝橡胶。
相应的产物也可从市售产品得到,例如牌号为Vestenamer(Huls公司)的聚辛烯,以及许多具有至少一个乙烯基芳族嵌段和一个弹性体嵌段的适合的嵌段共聚物。其例子可以提及的是CariflexTR牌号(Shell公司)、KratonG牌号(Shell公司)、Finaprene牌号(Fina公司)和EuropreneSOL牌号(Enichem公司)。
优选使用嵌段共聚物。
新的热塑性模塑组合物可另外含有0-50%(重量),优选为0-40%(重量),特别是0-35%(重量)的纤维或颗粒填料或其混合物。
它们的例子是碳纤维、玻璃纤维、玻璃毡、玻璃纤维粗纱和玻璃珠,以及钛酸钾晶须和芳酰胺纤维,优选为玻璃纤维。这些玻璃纤维既可以以短玻璃纤维的形式,也可以以连续的多股线(粗纱)的形式加入。优选玻璃纤维含有氨基硅烷偶联剂。
也可以使用无定形硅石、碳酸镁、石英粉、云母、滑石粉、长石或硅酸钙。
在每种情况下所用组分的总量都是100%(重量)。
新的热塑性模塑组合物可以通过在270-350℃下混合各种组分得到,混合是在常规的混合设备中进行,如捏合机、Banbury混合器或单螺杆挤出机,但是优选使用双螺杆挤出机。为了得到非常均匀的模塑组合物,必须要进行完全、充分的混合。组分混合的顺序可以变化,所以,可以预混合两种,或如果需要三种组分,或同时一起混合所有的组分。
新的热塑性模塑组合物具有高的流动性、低吸水性,因而改进了耐水解性,以及较好的尺寸稳定性。它们适合生产纤维、膜或模制品。
实施例
使用下列的组分:
组分A)
Mw=240,200、Mw/Mn=1.41和13C-NMR测定的间同分数>96%的s-PS,q制法如下:
将2.0mol苯乙烯(208.3g)加入园底烧瓶,其中已用氮气形成了惰性气氛,加热到70℃,与来自Witco公司的1.1ml甲基铝氧烷(MAO)溶液(1.53摩尔在甲苯中)混合。混合物然后与46.04mg(16.67×10-5mol)五甲基环戊二烯基三甲醇钛混合。然后再加入9.8ml上述MAO溶液。内部温度控制在70℃,使聚合进行1小时。然后加入甲醇终止聚合反应。得到的聚合物用甲醇洗并在50℃和减压下干燥。用高温GPC(凝胶渗透色谱)在135℃测定分子量分布,以1,2,4-三氯苯作溶剂。用窄分布的聚苯乙烯标准物标定。
分子量Mw用GPC在120℃测定,以1,2,4-三氯苯作溶剂。
组分B)
B1)粘度值VN为150ml/g的聚六亚甲基己二酰胺(尼龙6,6)(来自BASF的UltramidA3)。
B2)粘度值VN为125ml/g的聚--E--己内酰胺(尼龙6)(来自BASF的UltramidB25)。
B3)粘度值VN为75ml/g的聚六亚甲基己二酰胺(尼龙6,6)(来自BASF的UltramidA15)。
组分B1)、B2)和B3)的粘度值VN各自在96%浓度硫酸的0.5%(重量)溶液中于25℃测定。
组分C)
在300℃和双螺杆挤出机中通过使下列成分反应制备的改性聚亚苯基醚:
c1)99%(重量)的ηred=0.48dl/g(在1%(重量)浓度的氯仿溶液于25℃下测定)的聚(2,6-二甲基-1,4-亚苯基醚)和
c3)1%(重量)的富马酸。
熔体进行脱气、挤出、通过水浴和切粒。
实施例1-3:热塑性模塑组合物的制备
将组分A)、B)和C)在双螺杆挤出机(ZSK 30,Werner & Pfleiderer)中于285℃混合、挤出、在水浴中冷却和切粒。
然后将干的颗粒在290℃加工成园片(厚2mm,直径60mm)、测试平片(127mm×12.7mm×1.6mm)和标准小试样(50mm×6mm×4mm),进行测试。
比较例1c-4c:
如实施例1-3同样的方法进行操作。
为了测定吸水性,将方形试样(10mm×10mm×1mm)放入蒸馏水中,在特定的时间后取出、干燥和称重。算出基于未处理试样重量的相对重量增加〔%〕。
粘度〔泊〕在290℃测定,L/D毛细管比例为30∶1(L=30mm,D=1mm),剪切速率为581/秒。
模塑组合物的配方和其性能列于下表。
实施例 | 配方〔重量%〕 | 吸水性〔%〕 | 粘度〔泊〕 | |||||||
A) | B1) | B2) | B3) | C) | 1天后 | 3天后 | 5天后 | 10天后 | ||
1 | 55 | 43 | - | - | 2 | 0.12 | 0.52 | 0.81 | 0.99 | 630 |
2 | 55 | - | 43 | - | 2 | 0.18 | 0.73 | 0.84 | 1.15 | 490 |
3 | 55 | - | - | 43 | 2 | 0.09 | 0.69 | 0.93 | 1.02 | 280 |
1c | 100 | - | - | - | - | 0.05 | 0.17 | 0.14 | 0.18 | 920 |
2c | - | 100 | - | - | - | 1.18 | 2.40 | 3.10 | 4.70 | 250 |
3c | - | - | 100 | - | 1.52 | 2.81 | 3.86 | 5.25 | 190 | |
4c | - | - | - | 100 | - | 1.73 | 3.42 | 4.01 | 5.77 | 110 |
Claims (6)
1.一种含有以下组分的热塑性模塑组合物:
A)5-97.9%(重量)的间同结构的乙烯基芳族聚合物,
B)2-90%(重量)的粘度值VN为50-150ml/g的低粘度聚酰胺,
和
C)0.1-50%(重量)极性基团改性的的聚亚苯基醚。
2.权利要求1的热塑性模塑组合物,该组合物含有
量为15-89.8%(重量)的组分A),
量为10-80%(重量)的组分B)和
量为0.2-40%(重量)的组分C)。
4.权利要求1-3任何一项的热塑性模塑组合物,其中组分C)由以下成分构成:
c1)70-99.95%(重量)的聚亚苯基醚,
c2)0-25%(重量)的乙烯基芳族聚合物,和
c3)0.05-5%(重量)的至少一种化合物,该化合物含有至少一个双键或三键和至少一个选自羧酸、羧酸酯、羧酸酐、羧酰胺、环氧化物、噁唑啉和氨基甲酸酯的官能基。
5.应用权利要求1-4中任一项的热塑性模塑组合物生产纤维、膜和模制品。
6.由用作主要组分的权利要求1-4中任一项的热塑性模塑组合物得到的纤维、膜或模制品。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19616075.8 | 1996-04-23 | ||
DE19616075A DE19616075A1 (de) | 1996-04-23 | 1996-04-23 | Thermoplastische Formmassen auf der Basis von vinylaromatischen Polymeren mit syndiotaktischer Struktur, niederviskosen Polyamiden und mit polaren Gruppen modifizierten Polyphenylenethern |
Publications (1)
Publication Number | Publication Date |
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CN1216560A true CN1216560A (zh) | 1999-05-12 |
Family
ID=7792140
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Application Number | Title | Priority Date | Filing Date |
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CN97194065A Pending CN1216560A (zh) | 1996-04-23 | 1997-04-07 | 基于间同结构的乙烯基芳族聚合物、低粘度聚酰胺和极性基团改性的聚亚苯基醚的热塑性模塑组合物 |
Country Status (6)
Country | Link |
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US (1) | US6093771A (zh) |
EP (1) | EP0895525A1 (zh) |
JP (1) | JP2000508697A (zh) |
CN (1) | CN1216560A (zh) |
DE (1) | DE19616075A1 (zh) |
WO (1) | WO1997040097A1 (zh) |
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DE19933279A1 (de) | 1999-07-14 | 2001-03-01 | Biotronik Mess & Therapieg | Polymerwerkstoff |
US20040054082A1 (en) * | 2001-12-03 | 2004-03-18 | Bank David H | Toughened polymer blends with improved surface properties |
US6894102B2 (en) * | 2002-05-20 | 2005-05-17 | General Electric | Syndiotactic polystyrene blends |
EP2031004A1 (en) * | 2007-09-03 | 2009-03-04 | Cytec Surface Specialties Austria GmbH | Polyester hybrid resins |
BRPI0911051A2 (pt) * | 2008-04-15 | 2015-12-29 | Denki Kagaku Kogyo Kk | composição de resina termoplástica. |
WO2010074417A2 (ko) * | 2008-12-24 | 2010-07-01 | 제일모직 주식회사 | 나일론계 얼로이 수지 조성물 및 이를 이용한 LED(발광다이오드) 반사체(reflector) |
US20110152420A1 (en) * | 2009-12-22 | 2011-06-23 | Mark Elkovitch | Poly(arylene ether)/polyamide compositions, methods, and articles |
US8450412B2 (en) * | 2009-12-22 | 2013-05-28 | Sabic Innovative Plastics Ip B.V. | Flame retardant polyamide composition, method, and article |
US8669332B2 (en) | 2011-06-27 | 2014-03-11 | Sabic Innovative Plastics Ip B.V. | Poly(arylene ether)-polysiloxane composition and method |
US9090999B2 (en) | 2011-09-28 | 2015-07-28 | Sabic Global Technologies B.V. | Polyamide/polyphenylene ether fibers and fiber-forming method |
US8722837B2 (en) | 2012-01-31 | 2014-05-13 | Sabic Innovative Plastics Ip B.V. | Poly(phenylene ether)-polysiloxane composition and method |
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US4661922A (en) * | 1982-12-08 | 1987-04-28 | American Telephone And Telegraph Company | Programmed logic array with two-level control timing |
DE3321579A1 (de) * | 1983-06-15 | 1984-12-20 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen herstellung von polyamiden |
EP0299444B2 (de) * | 1987-07-17 | 2007-02-14 | BASF Aktiengesellschaft | Teilaromatische Copolyamide mit verringertem Triamingehalt |
DE3726283A1 (de) * | 1987-08-07 | 1989-02-16 | Basf Ag | Thermoplastische formmassen |
IT1223326B (it) * | 1987-10-28 | 1990-09-19 | Montedipe Spa | Composizioni termoplastiche a base di polimeri sindiotattici dello stirene e polifenileneteri |
AU628651B2 (en) * | 1989-10-13 | 1992-09-17 | Idemitsu Kosan Co. Ltd | Styrene polymer composition |
JP2923383B2 (ja) * | 1991-10-01 | 1999-07-26 | 出光石油化学株式会社 | スチレン系重合体の製造方法 |
DE4129499A1 (de) * | 1991-09-05 | 1993-03-11 | Basf Ag | Thermoplastische polyphenylenether/polyamidformmassen mit duktilem bruchverhalten bei tiefen temperaturen |
EP0546497A3 (en) * | 1991-12-10 | 1993-11-18 | Idemitsu Kosan Co | Thermoplastic resin composition |
JP3533534B2 (ja) * | 1993-06-04 | 2004-05-31 | 出光興産株式会社 | ポリスチレン系樹脂組成物 |
JP3531683B2 (ja) * | 1993-06-04 | 2004-05-31 | 出光興産株式会社 | ポリスチレン系樹脂組成物 |
JP3264462B2 (ja) * | 1993-06-04 | 2002-03-11 | 出光興産株式会社 | ポリスチレン系樹脂組成物 |
JPH08143729A (ja) * | 1994-11-25 | 1996-06-04 | Idemitsu Kosan Co Ltd | ポリスチレン系樹脂組成物 |
JPH08302120A (ja) * | 1995-04-28 | 1996-11-19 | Idemitsu Kosan Co Ltd | 難燃性樹脂組成物 |
JP3516364B2 (ja) * | 1995-05-26 | 2004-04-05 | 出光石油化学株式会社 | ポリスチレン系樹脂組成物及びその成形品 |
JPH08319385A (ja) * | 1995-05-26 | 1996-12-03 | Idemitsu Petrochem Co Ltd | ポリスチレン系樹脂組成物及びその成形品 |
DE19535400A1 (de) * | 1995-09-23 | 1997-03-27 | Basf Ag | Thermoplastische Formmassen auf der Basis von vinylaromatischen Polymeren mit syndiotaktischer Struktur, thermoplastischen Polyamiden und mit polaren Gruppen modifizierten Polyphenylenethern |
DE19535417A1 (de) * | 1995-09-23 | 1997-03-27 | Basf Ag | Thermoplastische Formmassen auf der Basis von vinylaromatischen Polymeren mit syndiotaktischer Struktur, thermoplastischen Polyamiden und mit polaren Gruppen modifiziierten Polyphenylenethern |
-
1996
- 1996-04-23 DE DE19616075A patent/DE19616075A1/de not_active Withdrawn
-
1997
- 1997-04-03 WO PCT/EP1997/001671 patent/WO1997040097A1/de not_active Application Discontinuation
- 1997-04-03 US US09/155,090 patent/US6093771A/en not_active Expired - Fee Related
- 1997-04-03 JP JP9537655A patent/JP2000508697A/ja active Pending
- 1997-04-03 EP EP97916431A patent/EP0895525A1/de not_active Withdrawn
- 1997-04-07 CN CN97194065A patent/CN1216560A/zh active Pending
Also Published As
Publication number | Publication date |
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DE19616075A1 (de) | 1997-10-30 |
WO1997040097A1 (de) | 1997-10-30 |
EP0895525A1 (de) | 1999-02-10 |
US6093771A (en) | 2000-07-25 |
JP2000508697A (ja) | 2000-07-11 |
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