CN1258325A - 由长支化链间规乙烯基芳香聚合物制成的纤维 - Google Patents

由长支化链间规乙烯基芳香聚合物制成的纤维 Download PDF

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CN1258325A
CN1258325A CN98805592A CN98805592A CN1258325A CN 1258325 A CN1258325 A CN 1258325A CN 98805592 A CN98805592 A CN 98805592A CN 98805592 A CN98805592 A CN 98805592A CN 1258325 A CN1258325 A CN 1258325A
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C·E·彼得森
黄仪彬
R·H·沃森
P·J·小摩西
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Abstract

包含长支化链间规乙烯基芳香聚合物的组合物可以制成的高强度和小直径的纤维。由于纤维的强度增加,在加工过程中,单根纤维断裂的情况较少,这增加了加工生产率和产量。

Description

由长支化链间规乙烯基芳香聚合物制成的纤维
本发明涉及间规乙烯基芳香聚合物纤维及其应用。
间规乙烯基芳香聚合物如间规聚苯乙烯(SPS)是有用的聚合物，这些聚合物有高熔点和高结晶速度以及优异的耐热、耐化学腐蚀性能。但是，在一些应用如浇铸一拉幅机膜和纤维中，加工温度下的熔体强度不足以得到所希望的性质。
有优异耐热、耐化学腐蚀性的间规共聚物业已开发出来。Funaki等人的美国专利US-A-5 202 402利用双官能单体与苯乙烯形成间规共聚物，但是，该聚合物在高温时完全交联形成热固体而不能进行熔融加工。
以前，如Jezic的美国专利5,145,631和5,021,288所述，由线型间规乙烯基芳香聚合物制成纤维。但是，由于熔体强度的局限，这些纤维受其直径和强度的限制。
因此，由在高温下保持良好熔体强度和熔融可加工性的间规乙烯基芳香聚合物得到直径较小、强度增加和可加工性改进的纤维是十分有用的。
本发明针对由含长支化链间规乙烯基芳香(LCB-SVA)聚合物的组合物制成的纤维及其制品。
与由线性间规乙烯基芳香聚合物制成的纤维相比，长支化链间规乙烯基芳香聚合物可在高温进行熔融加工，同时保持良好的熔体强度，而且，由它制成的纤维有更小的直径和增加的强度。另外，由于纤维强度的增加，在加工时单根纤维断裂的情况较少，这增加了加工生产率和产量。
在一个实施方案中，本发明涉及由含长支化链间规乙烯基芳香(LCB-SVA)聚合物的组合物制成的纤维。
此处所用的术语“间规”指的是有规立构结构的聚合物，由13C核磁共振光谱测定，有规立构结构为间规度高于90％、优选高于99％的间规外消旋三元组。
间规乙烯基芳香聚合物是乙烯基芳香单体(即化学结构同时含不饱和部分和芳香基部分的单体)的均聚物和共聚物。优选的乙烯基芳香单体的分子式为：
       H2C＝CR-Ar；
其中，R为氢或含1至4个碳原子的烷基，Ar是含6至10个碳原子的芳香基。这样的乙烯基芳香单体的实例是苯乙烯、α-甲基苯乙烯、邻甲基苯乙烯、间甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、对叔丁基苯乙烯和乙烯基萘；溴代苯乙烯、尤其是对乙烯基甲苯和环上溴化或二溴化苯乙烯。溴化苯乙烯在制备耐燃性间规乙烯基芳香聚合物中特别有用。换句话说，耐燃LCB-SVA可由溴化LCB-SVA制成。代表性的间规共聚物包括苯乙烯-对甲基苯乙烯、苯乙烯-对叔丁基苯乙烯和苯乙烯-乙烯基甲苯共聚物。间规乙烯基芳香聚合物和用于其制备的单体已在专利US-A-4680353、US-A-4959435、US-A-4950724和US-A-4774301中有所报道。间规聚苯乙烯是目前优选的间规乙烯基芳香聚合物。
长支化链可在少量多官能团单体的存在下、在足以产生间规乙烯基芳香聚合物的条件下通过乙烯基芳香单体聚合得到。多官能团单体为任何含一个以上烯键的化合物，烯键可在聚合条件下与乙烯基芳香单体反应。典型地，多官能团单体含有2-4个烯键，可由分子式(I)表示：
Figure A9880559200041
其中R为乙烯基或含2至20个碳原子并包括乙烯端基的基团，其中含2至20个碳原子的基团可以是烷基、链烯基、环烷基或芳香基，其中环烷基含至少5个碳原子、芳香基含至少6个碳原子，n是1至3的整数，R基团在分子式(I)中处于乙烯基间或对位上，并且当n大于1时，R可以相同或不同。R优选为乙烯基团。
优选的多官能团单体含有两个乙烯端基基团(其中n＝1)。典型地，这样的单体包括双官能乙烯基芳香单体如二乙烯基苯或二苯乙烯基乙烷。
多官能团单体的量将依赖于待制备的聚合物的重均分子量(Mw)，但以乙烯基芳香单体的量为基准，典型地从10、优选从50、更优选从75、最优选从100ppm至1000、优选至800、更优选至500、最优选至650ppm。
多官能团单体可以任何允许多官能团单体与乙烯基芳香单体反应产生LCB-SVA聚合物的方法引入聚合过程。例如，可在聚合前先将多官能团单体溶解于乙烯基芳香单体或在聚合前或聚合过程中单独地引入聚合反应器。另外，可将多官能团单体溶解于聚合所使用的惰性溶剂如甲苯或乙苯中。
只要聚合过程中额外存在多官能团单体，则生产间规乙烯基芳香聚合物的任何聚合方法均可用于生产本发明中的LCB-SVA聚合物。生产间规乙烯基芳香聚合物的典型聚合方法已为本领域熟知，并在US-A-4680353、US-A-5066741、US-A-5206197和US-A-5294685中有所报道。
典型地，LCB-SVA聚合物的重均分子量为从50,000、优选从100,000、更优选从125,000、最优选从150,000至3,000,000、优选至1,000,000、更优选至500,000、最优选至350,000。当由含LCB-SVA聚合物的组合物制备纤维时，分子量优选在100,000至350,000。
支化间规乙烯基芳香聚合物含有与聚合物主链连接的间规乙烯基芳香聚合物的伸展链。长支化链间规乙烯基芳香聚合物典型地含有具有至少10个、优选至少100个、更优选至少300个、最优选至少500个单体重复单元的伸展链。
典型地，本发明的纤维由不含其它聚合物的LCB-SVA聚合物的组合物制成。但是，纤维也可由包含LCB-SVA聚合物和其它聚合物的其它组分的组合物制成。用于制成纤维的组合物内LCB-SVA聚合物的量依赖于最终的应用，在一些情况下，仅仅少量即可获得优势。一般而言，用于制成纤维的组合物内使用至少5wt.％，典型地为至少20％，优选为至少40％，更优选为至少70％，最优选为100％的LCB-SVA聚合物。可包含于这样的组合物的其它聚合物包括，但不局限于：线性间规聚苯乙烯，聚苯乙烯，聚苯醚，溴化聚苯醚如聚二溴苯醚，聚烯烃如聚丙烯、聚乙烯、聚(4-甲基戊烯)，乙-丙共聚物，乙烯-丁烯-丙烯共聚物，尼龙如尼龙-6、尼龙-6，6，聚酯如聚(乙二醇-对苯二甲酸酯)、聚(丁二醇-对苯二甲酸酯)，及其共聚物或共混物。也可向LCB-SVA聚合物组合物、纤维或由其制备的制品内添加其它材料或添加剂，包括抗氧剂，抗结剂如细颗粒的氧化铝、氧化硅、硅铝酸盐、碳酸钙、磷酸钙和硅树脂，冲击改进剂，耐燃剂，偶联剂如马来酸化的聚合物，包括马来酸酐改性的聚苯醚或马来酸酐改性的间规乙烯基芳香聚合物，改进基体纤维湿强度的粘合剂，阻燃剂，包括溴化聚苯乙烯、溴化间规乙烯基芳香聚合物、三氧化锑和聚四氟乙烯。
本发明中的纤维可采用多种形状，包括芯包层或相似构型的双组分纤维、中空、星形或球形。典型地，纤维的长度和直径将依赖于最终的应用，可在无限长至约0.1毫米或更小的范围内变化，本发明的纤维也可有不同的直径，有优势地，LCB-SVA聚合物可制成直径非常低如1微米或更小的纤维。典型地，纤维的直径在从约0.3微米、优选从约0.5微米、更优选从约0.8微米、最优选从约1微米至约10微米、优选至约8微米、更优选至约5微米、最优选至约3微米之间变化。已令人吃惊地发现，与线型间规乙烯基芳香聚合物相比，由LCB-SVA聚合物制成的纤维具有改进的熔体强度和较小的直径。
典型地，可将纤维制成多种不同的形状，可将其成型为网、簇(mats)无纺织物，如无纺纤维工业协会1992年出版的“The Nonwoven FabricHandbook(无纺纤维手册)”中第vii页和由Clemson大学E.A.Vaughn所著，由INDA，无纺工业协会1992年出版的Nonwoven Fabric Primerand Reference Sampler(无纺纤维入门和参考集锦)中的第1-2页所述形状；瞬时纺成的半成品、针刺毡、湿法成网半成品和干法成网半成品，或其它纤维状中间制品。中间制品的种类包括，但不局限于，通过热粘合、压延、层压、缝编、树脂粘合、溶剂粘合、机械粘合、射流喷网法、喷射成网法(jetlacing)、水剌法、化学粘合、乳液粘合、粉末粘合、印花粘合、饱和浸渍粘合法、喷洒粘合法、泡沫粘合、发泡、超声波粘合、和针刺形成的熔喷法网，热粘合网，SMS(纺粘、熔喷、纺粘)层压网，交叉铺网的或针刺网，带静电或带氢电荷(hydrocharged)网，多密度网，粘合网及其结合物。另外，其它聚合物网可与含本发明LCB-SVA纤维的纤维网结合使用，制成对于制造过滤用品尤其有用的多层网。
本发明的另一方面是针对由LCB-SVA聚合物、纤维和中间簇网制成的制品，包括(但不局限于)过滤介质、织物、纺品、挤出网织品及由此制成的物品。其它制品包括，但不局限于：双组分复合物，纺粘中间体；线绕过滤介质，带静电或带氢电荷介质，涡轮电过滤介质，滤器或滤器组件如液体或气体的过滤器、聚结器、带静电的过滤器、带氢电荷过滤器和涡轮电过滤器；用于电解池的分离器，电池分离器，表面膜，高温管材包皮，电缆包皮，隔音和绝热材料，止血带，个人护理纤维，造纸过滤网和支撑纸网，电绝缘纤维，屋顶用毡，医疗用品如防护衣、用于无菌医疗包扎的保护带、检查服、无菌滤网或过滤器、外科用品等，热固或热塑聚合物用的增强剂，拉制成型制品，层压制品如印刷线路板，或与热固性树脂如环氧树脂联合使用形成印刷线路板层压结构的纺织或无纺网，及将薄膜与本发明纤维结合使用的各种制品。
本发明的制品可由100％的LCB-SVA聚合物纤维、混合纤维、LCB-SVA聚合物与其它聚合物的混合物或共混物制成，或由纤维的混合物制成。例如，其它纤维可与本发明的纤维混合使用，这些纤维包括玻璃纤维、碳纤维、聚醚酮纤维、聚醚醚酮纤维、聚酯酰亚胺纤维、聚酰亚胺纤维、全芳烃聚酯纤维、聚苯硫纤维、芳香聚酰胺纤维、芳族聚酰胺纤维和陶瓷纤维，它们可以任何传统方法与本发明的纤维混合，这些方法包括，例如，在湿法成网方法中将连续纤维束共混合或将短纤维混合。
制造纤维、网、垫、纤维质材料和由其所制成的制品的方法已为本领域熟知，其包括，但不局限于：由Clemson大学E.A.Vaughn所著，由INDA，无纺工业协会1992年出版的Nonwoven Fabric Primerand Reference Sampler(无纺纤维入门和参考集锦)中的第4-6页和无纺纤维工业协会1992年出版的“The Nonwoven Fabric Handbook(无纺纤维手册)”中第45-46页中定义的方法，旋纺，熔喷，纺粘，粗疏，气流成网，湿法成网，薄膜打孔，薄膜原纤维化，瞬时纺制，针刺，热粘合，压延，层压成型，缝编，树脂粘合，溶剂粘合，机械粘合，射流喷网，喷射成网，水刺法，化学粘合，乳液粘合，粉末粘合，印花粘合，饱合浸渍粘合，喷洒粘合，泡沫粘合，发泡，超声波粘合，片材挤出，型材挤出，管材挤出，网材挤出，镶装注射成型，拉制成型，加压成型，热成型，层压，缠绕，浇铸，树脂压铸，片状成型料(SMC)法，预制整体模塑料(BMC)法以及真空树脂压铸。
或可选择地，本发明的纤维、网、垫或制品可经多种本领域熟知的精加工技术改性。这些技术包括无纺纤维手册中第72-76页所述的技术，磺化作用，使用润滑剂、脂肪酸酯、聚氧乙烯、表面活性剂、阻燃剂、抗静电剂、亲水或憎水润湿剂和软化剂的纺丝给油处理。
LCB-SVA聚合物可用于其它非纤维应用，包括管材挤出或型材挤出、粉末涂层如平面碳钢或其它强度高但化学稳定性差材料的粉末涂层。本发明的纤维也可用于经过粒子尺寸减小工艺后的粉末涂层。
在本发明的一个实施方案中，LCB-SVA聚合物纤维用于形成包含LCB-SVA聚合纤维的纤维基质材料和包含浸于基质材料中的热固性树脂的树脂组合物的预浸料坯。将LCB-SVA纤维成型为基质材料，其可以是纺织织物、编织织物、无纺织物或纸状薄片。由于与以较低定向性纤维为基质的织物相比，湿法成网或干法成网和纺粘织物中的纤维的定向性和结晶度提高，因此优选后者。可将这样的织物进行压延处理，改进热固性树脂组合物的孔隙度和可浸渍性。纤维内可含有润湿剂改进其在湿法成网中的分散能力。或可选择地，可将纤维分散在环氧树脂组合物以及挤出的印刷电路板内，或浇铸入所希望的、任选层压或混合成型的制品内。
除LCB-SVA纤维外，纤维基质材料可以含有其它纤维质材料。优选的纤维基质材料包括2.5-100wt.％，优选为5-100wt.％的LCB-SVA纤维和97.5-0wt.％，优选为95-0wt.％的至少一种其它类型的纤维。例如，其它纤维可选自玻璃纤维、碳纤维、聚醚酮纤维、聚醚醚酮纤维、聚酯酰亚胺纤维、聚酰亚胺纤维、全芳烃聚酯纤维、聚苯硫纤维、芳香聚酰胺纤维、芳族聚酰胺纤维和陶瓷纤维。可在基质材料成型的湿法成网过程中，通过将不间断纤维束共混或短纤维混合等方式将这样的纤维与LCB-SVA纤维混合。在优选的实施方案中，可通过共连续纺制纤维或使用湿法成网或干法成网技术、用玻璃纤维或芳族聚酰胺纤维与LCB-SVA纤维的混合物制备织物。还可使用改进纤维和/或热固性基体之间粘合性的其它组分，如偶联剂，例如，马来酸化的聚合物，包括马来酸酐改性的聚苯醚或马来酸酐改性的间规乙烯基芳香聚合物，或改进基质织物湿强度的粘合剂。添加剂如阻燃剂，包括溴化聚苯乙烯、溴化间规乙烯基芳香聚合物、三氧化锑和聚四氟乙烯可加入纤维基质材料和热固性树脂组合物内。
用于形成预浸料坯的合适的热固性树脂包括那些已知并已用于形成印刷线路板预浸料坯的树脂，特别优选的树脂包括众所周知的环氧树脂、聚酰亚胺树脂、氰酸酯-酯树脂、双马来酰亚胺-三嗪树脂和乙烯基酯树脂。在此使用的合适的环氧树脂的例子包括：
(A)由至少一种选自双酚A和卤化双酚A的成员与3-氯-1，2-环氧丙烷的反应产物组成的二缩水甘油醚化合物(例如，道化学公司生产的D.E.R.TM592 A80)。
(B)由由双酚A与氧化烯在酸或碱催化剂存在下的反应产物组成的多元醇化合物与3-氯-1，2-环氧丙烷的反应产物组成的聚缩水甘油醚化合物(例如，由Asahi-Denka供应的EP-4000)。
(C)苯酚-酚醛清漆树脂环氧化合物(例如，DOW环氧酚醛清漆树脂D.E.N.TM438)。
(D)对甲酚-酚醛清漆树脂环氧化合物(例如，由Yuka-Shell Epoxy供应的Epikote 180S65)。
环氧树脂组合物内含有的固化剂并不是特别重要，但一般而言，可使用至少一种选自二氰肼化合物、芳香多胺、酸酐和酚醛树脂的成分。
固化促进剂可进一步用于本发明中有用的环氧树脂组合物中。优选使用咪唑、咪唑啉和叔膦如三苯基膦。
预浸料坯可用的合适的阻燃性环氧树脂组合物包括四溴双酚A和双酚A和3-氯-1，2-环氧丙烷共聚所产生的溴化双酚A环氧树脂、耐热的对甲酚-酚醛清漆树脂类环氧树脂和二氰肼(作为固化剂)的混合物。优选的环氧树脂具有改进的耐热性和良好的抗金属片剥离能力，其包含
(I)至少一种选自由3-氯-1，2-环氧丙烷与双酚A和甲醛的缩聚产物的反应产物组成的缩水甘油醚化合物，及由3-氯-1，2-环氧丙烷与卤化双酚A和甲醛的缩聚产物的反应产物组成的卤化缩水甘油醚化合物的成分，与
(II)至少一种选自双酚A型和双酚F型缩水甘油醚化合物的成分，以及
(III)至少一种选自双酚A、双酚F和四溴双酚A的成分的反应产物。
为易于施用于基质材料上，热固性树脂组合物可与各种稀释剂结合使用。例如，可使用至少一种选自丙酮、甲基乙基酮、甲苯、二甲苯、甲基异丁基酮、乙酸乙酯、乙二醇单甲醚、N，N’-二甲基甲酰胺、N，N-二甲基乙酰胺、甲醇和乙醇的成分作为稀释剂。可以任何适宜的方式如喷雾、浸渍、浸泡、注射，将树脂组合物浸入基质材料中或者将树脂组合物涂布在基质材料上。
可将预浸料坯成型或在最后固化前进一步以钻孔或成型及加入其它组分如接头、终端或电子组件进行改性。
优选地，纤维基质材料与树脂组合物的重量比在20/80至90/10，优选为30/70至75/25，更优选为35/65至65/35。
热固性树脂可进一步包含一种或多种其它组分，如固化促进剂、润滑剂、阻燃剂、稳定剂、脱模剂、无机或有机填料、含氟聚合物的细粒子、颜料和染料。
预浸料坯可通过将LCB-SVA纤维基质材料用热固性树脂组合物浸渍、干燥的方式制备，或者，若需要，可以通常采用的程序对所得的预浸料坯部分固化。预浸料坯可选地在将预浸料坯进一步形成或成型为所需形状之后，一般通过加热热固性树脂以引发其发生交联或完成交联，形成固化的产品。或可选择地，可将包括纤维和热固性树脂的混合物挤成所需形状并固化，形成所需的固化预浸料坯。
可通过组合预定量的预浸料坯，在预浸料坯或预浸料坯层压制品的表面加上铜箔，及在加压下加热整体固化层压制件，制备印刷线路板。也可通过气相沉积或通过金属层向固化预浸料坯的后序层压作用，并且在金属层上蚀刻或机械加工成所需的电路设计，形成金属电路层。

Claims (14)

1.由包含长支化链间规乙烯基芳香聚合物的组合物制成的纤维。
2.权利要求1的纤维，其中乙烯基芳香聚合物为聚苯乙烯。
3.权利要求1的纤维，其中乙烯基芳香聚合物为聚甲基苯乙烯。
4.权利要求1的纤维，其中纤维为双组分纤维。
5.包括权利要求1的纤维的制品。
6.权利要求5的制品，其中制品为带静电的滤器介质。
7.权利要求5的制品，其中制品为滤器介质。
8.权利要求5的制品，其中制品为包括包含LCB-SPS聚合纤维的纤维质基质材料和包含浸于基质材料中的热固性树脂的树脂组合物的预浸料坯。
9.根据权利要求8的预浸料坯，其中热固性树脂包括环氧树脂、聚酰亚胺树脂、氰酸酯-酯树脂、双马来酰亚胺-三嗪树脂或乙烯基酯树脂。
10.根据权利要求9的预浸料坯，其中环氧树脂包括：
(A)包含双酚A或卤化双酚A化合物与3-氯-1，2-环氧丙烷的反应产物的二缩水甘油醚化合物，
(B)包含双酚A或卤化双酚A化合物与氧化烯在酸或碱催化剂存在下反应产生的多元醇化合物与3-氯-1，2-环氧丙烷的反应产物的聚缩水甘油醚化合物，
(C)苯酚-酚醛清漆树脂环氧化合物，或
(D)对甲酚-酚醛清漆树脂环氧化合物。
11.根据权利要求8的预浸料坯，其中纤维质基质材料包括芳族聚酰胺或玻璃纤维和LCB-SPS聚合纤维的混合物。
12.包括一种或多种权利要求8-11的任一项的预浸料坯的复合物。
13.根据权利要求12的固化的复合物。
14.印刷电路板，它包括权利要求13的复合物。
CN98805592A 1997-05-30 1998-03-10 由长支化链间规乙烯基芳香聚合物制成的纤维 Pending CN1258325A (zh)

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CN102317226A (zh) * 2008-12-22 2012-01-11 Ocv智识资本有限责任公司 以直接熔化操作制造高强度玻璃纤维的方法以及由此形成的产品
CN103213352A (zh) * 2013-04-19 2013-07-24 苏州佰家丽新材料科技有限公司 一种复合保温板的制备方法

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US7085302B2 (en) 2002-01-31 2006-08-01 Canon Kabushiki Kaisha Laser apparatus, exposure apparatus and method
CN102317226A (zh) * 2008-12-22 2012-01-11 Ocv智识资本有限责任公司 以直接熔化操作制造高强度玻璃纤维的方法以及由此形成的产品
CN102317226B (zh) * 2008-12-22 2015-01-21 Ocv智识资本有限责任公司 以直接熔化操作制造高强度玻璃纤维的方法以及由此形成的产品
CN103213352A (zh) * 2013-04-19 2013-07-24 苏州佰家丽新材料科技有限公司 一种复合保温板的制备方法

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US6037048A (en) 2000-03-14
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