CN107406672A - 耐漏电起痕组合物、由其形成的制品及其制造方法 - Google Patents
耐漏电起痕组合物、由其形成的制品及其制造方法 Download PDFInfo
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- CN107406672A CN107406672A CN201680010650.1A CN201680010650A CN107406672A CN 107406672 A CN107406672 A CN 107406672A CN 201680010650 A CN201680010650 A CN 201680010650A CN 107406672 A CN107406672 A CN 107406672A
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- polyetherimide
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种组合物，基于该组合物的总重量，包含45wt％至75wt％的聚醚酰亚胺；和20wt％至45wt％的滑石；以及5wt％至15wt％的氟化聚合物；其中，该组合物具有根据ASTM D‑3638‑85的大于或等于50滴的250伏特下至漏电起痕的滴数。
Description
技术领域
本公开涉及聚醚酰亚胺组合物，以及具体涉及耐漏电起痕的聚醚酰亚胺组合物、由其形成的制品及其制造方法。
背景技术
聚醚酰亚胺是已知的突出的高性能材料，具有高玻璃化转变温度(Tg)、高模量、和升高的温度下的强度以及优异的耐化学性。它们可用于制造用于各种各样应用的制品和组件。因为它们的用途广泛，特别是在电气和电子工业中，所以期望提供具有良好的耐漏电性的聚醚酰亚胺。漏电起痕是在一定条件下以及在一定电压下在聚合物的表面上形成导电通路。聚合物的漏电起痕可能是火的部分起源，因此耐漏电起痕经常是对用于某些电气应用的材料的重要的安全要求。报告聚合物的耐漏电起痕性的常用方法是通过其相对漏电起痕指数等级(CTI)。目前已知的聚醚酰亚胺可以具有100至175伏特的CTI。然而，一些应用可能要求具有更高的CTI的材料。
因此本领域仍存在对于具有优异的漏电起痕耐性的聚醚酰亚胺组合物的需要。如果在不显著不利地影响材料成本、可加工性和机械性能中的一种或多种的情况下可以使组合物耐漏电起痕，这将是进一步的优势。
发明内容
本领域的上述和其他不足由包含以下的聚醚酰亚胺组合物满足：基于组合物的总重量，45wt％至75wt％的聚醚酰亚胺；和20wt％至45wt％的滑石；以及5wt％至15wt％的氟化聚合物；其中，组合物具有根据ASTM D-3638-85的大于或等于50滴的250伏特下的至漏电起痕的滴数。
在另一个实施方式中，制造方法包括组合上述的组分以形成聚醚酰亚胺组合物。
在又一个实施方式中，制品包含以上描述的聚醚酰亚胺组合物。
在再一个实施方式中，制品的制造方法包括将以上描述的聚醚酰亚胺组合物模制、挤出或成型为制品。
通过以下附图、详细描述、实施例和权利要求举例说明上述的及其他特征。
具体实施方式
发明人已经发现，向聚醚酰亚胺添加20wt％至45wt％的滑石、和5至25wt％的氟化聚合物会导致聚醚酰亚胺的耐漏电起痕性的显着改善。
本发明人还发现，向聚醚酰亚胺添加20wt％至45wt％的滑石和5至25wt％的氟化聚合物会提供具有平衡的机械性能的组合物。
聚醚酰亚胺包含大于1、例如2至1000、或5至500、或10至100个的式(1)的结构单元：
其中，每个R独立地相同或不同，并且是取代或未取代的二价有机基团，如取代或未取代的C6-20芳香族烃基团、取代或未取代的直链或支链C2-20亚烷基基团、取代或未取代的C3-8亚环烷基基团，特别是上述中的任一种的卤代衍生物。在一些实施方式中，R是下式(2)中的一种或多种的二价基团：
其中，Q1是-O-、-S-、-C(O)-、-SO2-、-SO-、-CyH2y-，其中y是1至5的整数，或它们的卤代衍生物(包括全氟亚烷基基团)、或-(C6H10)z-，其中z是1至4的整数。在一些实施方式中，R是间亚苯基、对亚苯基或二亚芳砜，特别是双(4,4’-亚苯基)砜、双(3,4’-亚苯基)砜、双(3,3’-亚苯基砜)或包含上述中的至少一种的组合。在一些实施方式中，至少10摩尔百分数的R基团包含砜基团，以及在其他实施方式中，R基团不包含砜基团。
进一步地，在式(1)中，T是-O-或式-O-Z-O-的基团，其中-O-或-O-Z-O-基团的二价键处于3,3'、3,4'、4,3'或4,4'位置，并且Z是芳香族的，可选地被1至6个C1-8烷基基团、1至8个卤素原子或包含上述中的至少一种的组合取代的C6-24单环或多环部分，条件是不超过Z的化合价。示例性的基团Z包括式(3)的基团：
其中，Ra和Rb各自独立地相同或不同且是例如卤素原子或一价的C1-6烷基基团；p和q各自独立地是0至4的整数；c是0至4；并且Xa是连接羟基取代的芳香族基团的桥连基团，其中每个C6亚芳基基团的桥连基团和羟基取代基彼此排列在C6亚芳基基团上的邻位、间位或对位(特别是对位)。桥连基团Xa可以是单键、-O-、-S-、-S(O)-、-S(O)2-、-C(O)-或C1-18有机桥连基团。C1-18有机桥连基可以是环状或非环状的、芳香族或非芳香族的，并且可以进一步包含杂原子如卤素、氧、氮、硫、硅或磷。可以排列C1-18有机基团，使得与其连接的C6亚芳基基团各自连接至共同的烷叉基碳或连接至C1-18有机桥连基团的不同碳。基团Z的具体实例是式(3a)的二价基团
其中，Q是-O-、-S-、-C(O)-、-SO2-、-SO-或-CyH2y-，其中y是1至5的整数，或它们的卤代衍生物(包括全氟亚烷基基团)。在具体的实施方式中，Z衍生自双酚A，使得在式(3a)中的Q是2,2-异丙叉基。
在一个实施方式中，在式(1)中，R是间亚苯基、对亚苯基或包含上述中的至少一种的组合，以及T是-O-Z-O-，其中Z是式(3a)的二价基团。可替换地，R是间亚苯基、对亚苯基或包含上述中的至少一种的组合，以及T是-O-Z-O，其中Z是式(3a)的二价基团以及Q是2,2-异丙叉基。可替换地，聚醚酰亚胺可以是包含式(1)的另外的结构聚醚酰亚胺单元的共聚物，其中R基团的至少50摩尔百分数(mol％)是双(3,4’-亚苯基)砜、双(3,3’-亚苯基)砜或包含上述中的至少一种的组合，并且剩余的R基团是对亚苯基、间亚苯基或包含上述中的至少一种的组合；并且Z是2,2-(4-亚苯基)异丙叉基，即双酚A部分。
在一些实施方式中，聚醚酰亚胺是可选地包含不是聚醚酰亚胺单元的另外的结构酰亚胺单元，例如式(4)的酰亚胺单元的共聚物：
其中，R是如式(1)中所描述的且每个V相同或不同，并且是取代或未取代的C6-20芳香族烃基团，例如下式的四价连接基：
其中，W是单键、-S-、-C(O)-、-SO2-、-SO-或-CyH2y-，其中y是1至5的整数，或它们的卤代衍生物(其包括全氟亚烷基基团)。这些另外的结构酰亚胺单元优选地占单元总数的小于20mol％，并且更优选地可以以单元总数的0至10mol％、或单元总数的0至5mol％、或单元总数的0至2mol％的量存在。在一些实施方式中，没有另外的酰亚胺单元存在于聚醚酰亚胺中。
聚醚酰亚胺可以由本领域技术人员已知的任何方法制备，包括式(5)的芳香族双(醚酐)或其化学等同物与式(6)的有机二胺的反应：
其中，T和R如上述所定义的。可以使用式(5)的芳香族双(醚酐)和不是双(醚酐)的另外的双(酸酐)，例如均苯四甲酸二酐或双(3,4-二羧酸苯基)砜二酐的组合制造聚醚酰亚胺的共聚物。
芳香族双(醚酐)的示例性实例包括2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(也称为双酚A二酐或BPADA)、3,3-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐；4,4'-双(3,4-二羧基苯氧基)二苯基醚二酐；4,4'-双(3,4-二羧基苯氧基)二苯硫醚二酐；4,4'-双(3,4-二羧基苯氧基)二苯甲酮二酐；4,4'-双(3,4-二羧基苯氧基)二苯基砜二酐；4,4'-双(2,3-二羧基苯氧基)二苯基醚二酐；4,4'-双(2,3-二羧基苯氧基)二苯基硫醚二酐；4,4'-双(2,3-二羧基苯氧基)二苯甲酮二酐；4,4'-双(2,3-二羧基苯氧基)二苯基砜二酐；4-(2,3-二羧基苯氧基)-4'-(3,4-二羧基苯氧基)二苯基-2,2-丙烷二酐；4-(2,3-二羧基苯氧基)-4'-(3,4-二羧基苯氧基)二苯基醚二酐；4-(2,3-二羧基苯氧基)-4'-(3,4-二羧基苯氧基)二苯基硫醚二酐；4-(2,3-二羧基苯氧基)-4'-(3,4-二羧基苯氧基)二苯甲酮二酐；4,4’-(六氟异丙叉基)邻苯二甲酸酐；和4-(2,3-二羧基苯氧基)-4'-(3,4-二羧基苯氧基)二苯基砜二酐。可以使用不同的芳香族双(醚酐)的组合。
有机二胺的实例包括1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,9-壬二胺、1,10-癸二胺、1,12-十二烷二胺、1,18-十八烷二胺、3-甲基庚二胺、4,4-二甲基庚二胺、4-甲基壬二胺、5-甲基壬二胺、2,5-二甲基己二胺、2,5-二甲基庚二胺、2,2-二甲基丙二胺、N-甲基-双(3-氨基丙基)胺、3-甲氧基己二胺、1,2-双(3-氨基丙氧基)乙烷、双(3-氨基丙基)硫醚、1,4-环己二胺、双-(4-氨基环己基)甲烷、间苯二胺、对苯二胺、2,4-二氨基甲苯、2,6-二氨基甲苯、间二甲苯二胺、对二甲苯二胺、2-甲基-4,6-二乙基-1,3-亚苯基-二胺、5-甲基-4,6-二乙基-1,3-亚苯基-二胺、联苯胺、3,3’-二甲基联苯胺、3,3’-二甲氧基联苯胺、1,5-二氨基萘、双(4-氨基苯基)甲烷、双(2-氯-4-氨基-3,5-乙基苯基)甲烷、双(4-氨基苯基)丙烷、2,4-双(对氨基-叔丁基)甲苯、双(对氨基-叔丁基苯基)醚、双(对甲基-邻氨基苯基)苯、双(对甲基-邻氨基戊基)苯、1,3-二氨基-4-异丙基苯、双(4-氨基苯基)硫醚、双-(4-氨基苯基)砜(也称为4,4’-二氨基二苯基砜(DDS))和双(4-氨基苯基)醚。可以使用上述化合物的任何结构异构体(regioisomer)。可以使用上述中的任一种的C1-4烷基化或聚(C1-4)烷基化的衍生物，例如聚甲基化的1,6-已二胺。也可以使用这些化合物的组合。在一些实施方式中，有机二胺是间苯二胺、对苯二胺、4,4′-二氨基二苯砜、3,4′-二氨基二苯砜、3,3′-二氨基二苯砜或包含上述中的至少一种的组合。
聚醚酰亚胺可以具有如通过美国材料与试验学会(ASTM)D1238在340至370℃下使用6.7千克(kg)重量测量的0.1至10克/分钟(g/min)的熔融指数。在一些实施方式中，聚醚酰亚胺具有如通过凝胶渗透色谱法、使用聚苯乙烯标准测量的1,000至150,000克/摩尔(道尔顿)的重均分子量(Mw)。在一些实施方式中，聚醚酰亚胺具有10,000至80,000道尔顿的Mw。这种聚醚酰亚胺通常具有在间甲酚中在25℃下测量的大于0.2分升/克(dl/g)、或更具体地0.35至0.7dl/g的特性粘度。
聚醚酰亚胺组合物中使用的聚醚酰亚胺的量可以大幅变化，并且是有效地提供期望的机械性能和耐漏电起痕性的量。在一些情况下，聚醚酰亚胺以50wt％至90wt％、具体地50wt％至80wt％、以及更具体地50wt％至70wt％的量存在，各自基于聚醚酰亚胺组合物的总重量。
出乎意料地发现滑石作为用于改善聚醚酰亚胺的耐漏电起痕性能的有用的添加剂，尤其是在氟化聚合物的存在下。基于聚醚酰亚胺组合物的总重量，滑石的量为20至45wt.％，或25至45wt％，或35至45wt％。
滑石的粒径可以影响聚醚酰亚胺组合物的CTI性能。在一些实施方式中，二氧化钛具有2微米至6微米的D95。如在本文中使用的，D95是指颗粒的分隔粒径，其中参考样品的总分布中的95wt％的颗粒具有指出的或更小的粒径。例如，3.5微米的D95粒径是指样品中的95wt％的颗粒具有3.5微米或更小的直径。在一些实施方式中，通过sedigraph分析，使用例如Micromeritics Sedigraph 5120粒径分析系统确定粒径。
聚醚酰亚胺组合物进一步包括含氟聚合物。如在本文中所使用的，“含氟聚合物”包括含有源自氟化的α-烯烃单体，即包含至少一个氟原子取代基的α-烯烃单体，以及可选地，与氟化的α-烯烃单体反应性的非氟化的、烯属不饱和单体的重复单元的均聚物和共聚物。示例性的氟化α-烯烃单体包括但不限于CF2＝CF2、CHF＝CF2、CH2＝CF2、CH2＝CHF、CClF＝CF2、CCl2＝CF2、CC1F＝CC1F、CHF＝CC12、CH2＝CC1F、和CC12＝CClF、CF3CF＝CF2、CF3CF＝CHF、CF3CH＝CF2、CF3CH＝CH2、CF3CF＝CHF、CHF2CH＝CHF、以及CF3CH＝CH2。具体地，氟化α-烯烃单体是以下的一种或多种：四氟乙烯(CF2＝CF2)、三氟氯乙烯(CC1F＝CF2)、偏二氟乙烯(CH2＝CF2)、和六氟丙烯(CF2＝CFCF3)。示例性的非氟化的单烯属不饱和单体包括但不限于乙烯、丙烯、丁烯、(甲基)丙烯酸酯单体如甲基丙烯酸甲酯和丙烯酸丁酯、烯属不饱和芳族单体如苯乙烯、乙烯基醚如环己基乙烯基醚、乙基乙烯基醚、和正丁基乙烯基醚、以及乙烯基酯如乙酸乙烯酯和叔羰酸乙烯酯。示例性的含氟聚合物包括但不限于聚(四氟乙烯)均聚物(PTFE)、聚(六氟乙烯)、聚(四氟乙烯-六氟乙烯)、和聚(四氟乙烯-乙烯-丙烯)。具体的示例性含氟聚合物是PTFE，其可以是纤维形成的或非纤维形成的。
含氟聚合物可以相关于，例如由另一种共聚物，例如包括源自上述非氟化烯属不饱和单体等的单元的共聚物包封。在一些实施方式中，共聚物是刚性共聚物如苯乙烯-丙烯腈共聚物(SAN)。包封在SAN中的PTFE被称为TSAN。基于包封的含氟聚合物的总重量，示例性的TSAN包含25至75wt％，具体地50wt％的PTFE和25至75wt％，具体地50wt％的SAN。基于共聚物的总重量，SAN可以包含，例如，75wt％的苯乙烯和25wt％的丙烯腈。
可以用于即成组合物的一种含氟聚合物组合物在商品名3M MM5935EF下可商购自3M，并且特别有效地用于配制组合物，当连同本文所公开的芳族聚碳酸酯、聚醚酰亚胺、和可选的三氯苯磺酸钠一起使用时，其可以获得良好的阻燃性、低烟密度、和低热量释放的组合。
聚醚酰亚胺组合物可以包括通常并入该类型的聚合物组合物的各自添加剂，条件是选择这些添加剂使得不能显著不利地影响组合物的期望的性质。示例性的添加剂包括催化剂、抗冲改性剂、填料、抗氧化剂、热稳定剂、光稳定剂、紫外光(UV)吸收添加剂、淬灭剂、增塑剂、润滑剂、脱模剂、抗静电剂、视觉效果添加剂如染料、颜料、和光效应添加剂、阻燃剂、抗滴落剂和辐射稳定剂。可以使用添加剂的组合，例如，热稳定剂、脱模剂以及可选地紫外光稳定剂的组合。在一些实施方式中，聚醚酰亚胺组合物进一步包含选自加工助剂、热稳定剂、紫外光吸收剂、着色剂、阻燃剂或包含上述中的至少一种的组合的添加剂。通常，以通常已知有效的量使用添加剂。基于组合物的总重量，上述添加剂(除任何填料之外)通常以0.0001wt％至20wt％或0.005至20wt％、具体地0.01至10wt％的量存在。可替换地，在一些实施方式中，组合物不包含可估计的量的添加剂，并且在一些实施方式中，不存在可检测的量的添加剂，即，组合物中基本不存在或不存在添加剂。因此，基于组合物的总重量，上述添加剂(除了任何填料之外)可以以0至0.1wt％、0至0.01wt％、0至0.001wt％、或0至0.0001wt％的量存在。在另一个实施方式中，除了热稳定剂、脱模剂和可选地紫外光稳定剂之外，组合物中不存在可估计量的任何添加剂。在又一个实施方式中，没有除了热稳定剂、脱模剂以及可选地紫外光稳定剂之外的可检检测量的任何添加剂存在于组合物中。
合适的抗氧化剂可以是化合物如亚磷酸酯、亚膦酸酯和受阻酚或包含上述中的至少一种抗氧化剂的组合。含磷稳定剂，包括亚磷酸三芳酯和膦酸芳酯是有用的添加剂。双官能的含磷化合物也可以是非种子的(unseeded)。优选的稳定剂可以具有大于300的分子量。一些示例性的化合物是作为IRGAFOS 168可获得自Ciba Chemical Co.的三-二叔丁基苯基亚磷酸酯和作为DOVERPHOS S-9228可商购自Dover Chemical Co.的双(2,4-二枯基苯基)季戊四醇二亚磷酸酯。
亚磷酸酯和亚膦酸酯的实例包括：亚磷酸三苯酯、二苯基烷基亚磷酸酯、苯基二烷基亚磷酸酯、三(壬基苯基)亚磷酸酯、三月桂基亚磷酸酯、三(十八烷基)亚磷酸酯、二硬脂基二亚磷酸季戊四醇酯、三(2,4-二叔丁基苯基)亚磷酸酯、二异癸基二亚磷酸季戊四醇酯、双(2,4-二叔丁基苯基)季戊四醇二磷酸酯、双(2,6-二叔丁基-4-甲基苯基)-季戊四醇二亚磷酸酯、二异癸氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨醇三亚磷酸酯、四(2,4-二叔丁基-苯基)4,4'-亚联苯基二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、2,2',2”-次氮基[三乙基三(3,3',5,5'-四叔丁基-1,1'-联苯基-2,2'-二基)亚磷酸酯]、2-乙基己基(3,3',5,5'-四叔丁基-1,1'-联苯基-2,2'-二基)亚磷酸酯和5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-二氧杂磷杂环丙烷。
设想了包含多于一种的有机磷化合物的组合。当组合使用时，有机磷化合物可以是相同类型或不同类型的。例如，组合可以包含两种亚磷酸酯或组合可以包含亚磷酸酯和亚膦酸酯。在一些实施方式中，具有大于300的分子量的含磷稳定剂是有用的。基于组合物的总重量，含磷稳定剂，例如亚磷酸芳酯通常以0.005至3wt％的量、具体地0.01至1.0wt％的量存在于组合物中。
也可以将受阻苯酚用作抗氧化剂，例如烷基化的一元酚，以及烷基化的双酚或多酚。示例性的烷基化的一元酚包括2,6-二-叔丁基-4-甲基苯酚；2-叔丁基-4,6-二甲基苯酚；2,6-二-叔丁基-4-乙基苯酚；2,6-二-叔丁基-4-正-丁基苯酚；2,6-二-叔丁基-4-异丁基苯酚；2,6-二环戊基-4-甲基苯酚；2-(α-甲基环己基)-4,6-二甲基苯酚；2,6-双十八烷基-4-甲基苯酚；2,4,6-三环己基苯酚；2,6-二-叔丁基-4-甲氧基甲基苯酚；在侧链上是直链或支链的壬基苯酚，例如，2,6-二-壬基-4-甲基苯酚；2,4-二甲基-6-(1'-甲基十一-1'-基)苯酚；2,4-二甲基-6-(1'-甲基十七-1'-基)苯酚；2,4-二甲基-6-(1'-甲基十三-1'-基)苯酚或包含上述中的至少一种的组合。示例性的烷叉基双酚包括2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2'-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2'-亚甲基双(4-甲基-6-(α-甲基环己基)-苯酚]、2,2'-亚甲基双(4-甲基-6-环己基苯酚)、2,2'-亚甲基双(6-壬基-4-甲基苯酚)、2,2'-亚甲基双(4,6-二-叔丁基苯基)、2,2'-乙叉基(4,6-二-叔丁基苯酚)、2,2'-乙叉基(6-叔-丁基-4-异丁基苯酚)、2,2'-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚]、2,2'-亚甲基双[6-(α,α-二甲基苄基-4-壬基苯酚]、4,4'-亚甲基双-(2,6-二-叔-丁基苯酚)、4,4'-亚甲基双(6-叔丁基-2-甲基苯酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚、1,1,3-三(5-叔-丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基-苯基)-3-正癸基巯基丁烷、乙二醇双[3,3-双(3'-叔丁基-4'-羟苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯、双[2-(3'-叔丁基-2'-羟基-5'-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1,1-双-(3,5-二甲基-2-羟基苯基)丁烷、2,2-双-(3,5-二-叔丁基-4-羟基苯基)丙烷、2,2-双-(5-叔丁基-4-羟基2-甲基苯基)-4-正癸基巯基丁烷、1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷或包含上述中的至少一种的组合。
受阻酚化合物可以具有大于300g/mol的分子量。高分子量可以在高加工温度，例如大于300℃下，帮助保留聚合物中的受阻酚部分。基于组合物的总重量，受阻酚稳定剂通常以0.005wt％至2wt％、具体地0.01至1.0wt％的量存在于组合物中。
脱模剂的实例包括脂肪族和芳香族羧酸和它们的烷基酯，例如，硬脂酸、山嵛酸、季戊四醇四硬脂酸酯、丙三醇三硬脂酸酯和乙二醇二硬脂酸酯。也可以将聚烯烃，如高密度聚乙烯、线性低密度聚乙烯、低密度聚乙烯和类似的聚烯烃均聚物和共聚物用作脱模剂。基于组合物的总重量，脱模剂通常以0.05至10wt％、具体地0.1至5wt％存在于组合物中。优选地脱模剂将具有一般大于300的高分子量，以防止在熔融加工过程中脱模剂从熔融聚合物混合物中损失。
特别地，可以添加可选的聚烯烃来改变组合物的耐化学性和脱模特性。可以单独或组合地使用均聚物如聚乙烯、聚丙烯、聚丁烯。可以作为高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)或支链聚乙烯添加聚乙烯。也可以以与包含碳酸基团的化合物如马来酸或柠檬酸或它们的酸酐、包含丙烯酸基团的酸化合物如丙烯酸酯等以及包含上述中的至少一种的组合的共聚物形式使用聚烯烃。当存在时，以大于0至10wt％、具体地0.1至8wt％、更具体地0.5至5wt％的量使用聚烯烃，特别是HDPET，全部基于组合物的总重量。
在一些实施方式中，聚醚酰亚胺组合物可以进一步包含至少一种另外的聚合物。这种另外的聚合物的实例包括但不限于PPSU(聚苯砜)、聚醚酰亚胺、PSU(聚砜)、PPET(聚苯醚)、PFA(全氟烷氧基烷烃)、MFA(TFE四氟乙烯和PFVE全氟乙烯基醚的共聚物)、FEP氟化乙烯丙烯聚合物)、PPS(聚(苯硫醚))、PTFE(聚四氟乙烯)、PA(聚酰胺)、PBI(聚苯并咪唑)和PAI(聚(酰胺-酰亚胺))、聚(醚砜)、聚(芳砜)、聚苯、聚苯并噁唑、聚苯并噻唑以及它们的共混物和共聚物。当存在时，以大于0至20wt％、具体地0.1至15wt％、更具体地0.5至10wt％的量使用聚合物，全部基于组合物的总重量。在一些实施方式中，除本文描述的聚醚酰亚胺外，没有聚合物存在于聚醚酰亚胺组合物中。
还可以可选地存在着色剂，如颜料和/或染料添加剂。有用的颜料可以包括例如无机颜料如金属氧化物和混合的金属氧化物如氧化锌、二氧化钛、氧化铁等；硫化物如硫化锌等；铝酸盐；磺酰硅酸钠(sodium sulfo-silicates)、硫酸盐、铬酸盐等；炭黑；铁酸锌；群青蓝；有机颜料如偶氮，二偶氮，喹吖啶酮，苝，萘四羧酸，黄烷士酮，异吲哚啉酮，四氯异吲哚啉酮，蒽醌，蒽酮，二噁嗪，酞菁和偶氮色淀；颜料红101、颜料红122、颜料红149、颜料红177、颜料红179、颜料红202、颜料紫29、颜料蓝15、颜料蓝60、颜料绿7、颜料黄119、颜料黄147、颜料黄150和颜料棕24；或包含上述颜料中的至少一种的组合。基于组合物的总重量，通常以0至10wt％、具体地0至5wt％的量使用颜料。在某些情况下，在期望改进冲击的情况下，颜料如二氧化钛将具有小于5微米的平均粒径。
在一些情况下，期望具有基本不含溴和氯的聚醚酰亚胺组合物。“基本上不含”溴和氯是指按组合物的重量计，组合物具有小于3wt％的溴和氯，以及在其他实施方式中，具有小于1wt％的溴和氯。在其他实施方式中，组合物不含卤素。将“不含卤素”定义为具有每百万重量份总的组合物小于1000重量份卤素(ppm)的卤素含量(氟、溴、氯和碘的总量)。通过普通的化学分析如原子吸收可以确定卤素的量。
可以通过在用于形成紧密共混物的条件下，共混成分来制备聚醚酰亚胺组合物。这样的条件经常包括在单或双螺杆挤出机、搅拌钵或类似的混合设备中的熔融混合，该设备可以向组分施加剪切。由于它们的更强的混合能力和自卸脱(self wiping)能力，所以双螺杆挤出机相比单螺杆挤出机经常是优选的。通过挤出机中的至少一个排气口向共混物施加真空来去除组合物中的挥发性杂质通常是有利的。经常有利的是，在熔融之前干燥PET和聚酰亚胺聚合物。经常在290至340℃下完成熔融加工，以避免过多的聚合物降解，同时仍然允许足够的熔融以获得不含任何脱离的成分的紧密的聚合物混合物。也可以使用40微米至100微米的烛式过滤器或网式过滤器熔融过滤聚合物，以除去不期望的黑斑或其他非均匀的污染物。
在示例性的过程中，将各种组分放置到挤出混合机中，以产生连续的丝束，将其冷却然后切成粒料。在另一个步骤中，通过干燥共混将组分混合，然后在研磨机中流体化并分割，或挤出并切割。例如，还可以通过注射模制或传递模制技术混合和直接模制组合物和任何可选的组分。优选地，所有组分尽可能地不含水。此外，进行混合以确保在机器中较短的停留时间；仔细控制温度；利用摩擦热；以及获得组分之间的紧密共混物。然后，在便于用于热塑性组合物的任何设备，如Newbury或van Dorn型注射模制机中，使用250℃至320℃的常规缸体温度和55℃至120℃的常规模具温度模制聚醚酰亚胺组合物。
如以上的讨论，将聚醚酰亚胺组合物配制为具有优异的耐漏电起痕性。在一些实施方式中，组合物具有根据ASTM D-3638-85确定的大于或等于50滴、大于或等于60滴、大于或等于70滴、大于或等于80滴、大于或等于90滴或大于或等于100滴的250伏特下的至漏电起痕的滴数。
聚醚酰亚胺组合物可以进一步具有根据ASTM D638确定的大于或等于50MPa(兆帕斯卡)、大于或等于60MPa、大于或等于70MPa、或大于或等于80MPa的拉伸强度。
聚醚酰亚胺组合物可以进一步具有根据ASTM D638确定的大于或等于6000GPa(千兆帕斯卡)、大于或等于7000GPa、大于或等于8000GPa、或大于或等于10,000GPa的拉伸模量。
聚醚酰亚胺组合物可以进一步具有在3.2毫米注射模制棒上在1.82MPa应力下根据ASTM D648测量的190至230℃、更具体地195至220℃的热变形温度(HDT)。
还提供了包含聚醚酰亚胺组合物的成形、成型或模制的制品。通过各种方式如注射模制、挤出、旋转模制、吹塑和热成型可以将聚醚酰亚胺组合物模制成有用的成型制品。因此，聚醚酰亚胺组合物可以用于形成泡沫制品、模制品、热成型制品、挤出膜、挤出片材、多层制品的一个或更多个层(例如，盖层)、用于涂覆的制品的基底或用于金属化的制品的基底。
在另一个实施方式中，以下制品中至少一种包含在本公开所涵盖的组合物中或源自本公开所涵盖的组合物：太阳能装置、电气接线盒、电气连接件、电动汽车充电器、室外电器外壳、智能电表外壳、智能电网电力节点、PV(光伏)框架和微型断路器(MCB)应用。
通过以下非限制性实施例进一步示出具有改善的CTI性能和平衡的机械性质的聚醚酰亚胺组合物。除非另外明确指出，否则所有份数和百分比是按重量计。除非另外明确指出，否则所有温度是摄氏度。
实施例
在表1中描述了用于实施例的材料。
表1.
共混、挤出和模制条件
通过熔融混合聚醚酰亚胺和填料形成组合物。在2.5英寸的双螺杆真空排气挤出机中进行挤出。将挤出机设定在约300-350℃。在真空下以约250转/分钟(rpm)运行共混。以一次方法制造组合物。将挤出物在150℃下冷却、造粒和干燥。使用30秒的循环时间在340-350℃的设定温度和150-160℃的模具温度下注射模制测试样品。
测试步骤
在测试之前使所有模制样品处于50％相对湿度条件下至少48小时。使用ASTM测试方法测定性质。除非本文指定相反，否则所有测试标准是在提交本申请时有效的最新标准。
根据ASTM D256在3.2毫米厚的棒上测量缺口悬臂梁冲击值。在烘箱老化前将棒刻痕；在室温下测试样品。结果以焦耳/米(J/m)表示。
根据ASTM方法D638在23℃下用5毫米/分钟的十字头(crosshead)速度在3.2毫米的I型棒上测量拉伸性能。报告断裂(B)时的伸长率(伸长率％)。以MPa(兆帕斯卡)或GPa(千兆帕斯卡)报告拉伸模量、屈服拉伸强度、断裂拉伸强度。
根据ASTM D1238在337℃下使用6.7千克(Kg)重量测量熔体流动速率(MFR)。MFR以克/10分钟(g/10min)报告。
在3.2毫米的注射模制棒上在1.82MPa下根据ASTM D648测量热变形温度(HDT)。HDT以摄氏度(℃)报告。
根据ASTM D-3638用3mm正方形板(6x 6cm)进行耐漏电起痕测试。可以在任何给定电压下开始测试。在每个电压下，测试5个试样并记录平均滴数。在(至少)4个不同电压下进行测试，其中应有至少两个平均滴数高于50的数据点和两个平均滴数低于50的数据点。进行至50滴的电压外推，并基于该电压(VASTM)指定PLC类别。根据下表提供该指定。聚合物的CTI等级指示了在特定电压下聚合材料对于漏电起痕的耐性如何。CTI等级在CTI-0至CTI-5范围内，其中CTI-1等级指示聚合物比具有较低CTI等级(例如CTI-3)的聚合物更耐漏电起痕。
| VASTM | PLC |
| <100 | 5 |
| 100-174 | 4 |
| 175-249 | 3 |
| 250-399 | 2 |
| 400-599 | 1 |
| ≥600 | 0 |
采用筛选法来预测聚醚酰亚胺组合物的CTI-2性能。该方法采用ASTM D-3638方法，但仅在一个电压(250V)下进行测试。记录滴数直到失效并且施加不超过100滴。样品的CTI-2等级的预测是基于在250V下在失效以前达到至少50滴的电解质溶液。未获得CTI评级的预测是基于在250V下在达到50滴电解质溶液以前失效。用于预测CTI-2等级的筛选方法在本公开中被确定为CTI测试。
实施例1-9
实施例1-9显示了添加具有不同尺寸分布的滑石至含有聚醚酰亚胺和聚四氟乙烯的组合物对机械和CTI性能的影响。配方和结果示于表2。
表2
*比较例
比较例1显示，含有90wt％的PEI和10wt％的PTFE的组合物在250伏下至漏电起痕的滴数仅为5。当添加10wt％或15wt％滑石(比较例2和3)时，在250伏下至漏电起痕的滴数仅显示分别到7和19.6的轻微改善。然而，在添加25wt％至40wt％的具有不同尺寸分布的滑石时，在250伏下至漏电起痕的滴数增加到大于50。
结果是出乎意料的，这是因为对PEI单独添加40wt％的HTP超细滑石没有改善PEI的CTI性能，因为在250伏下至漏电起痕的滴数仅为25，没有通过50滴测试(比较例7)。然而，当将25wt％或35wt％的HTP超细滑石加入PEI和PTFE的组合时，显著改善组合物的CTI性能并通过50滴CTI测试(实施例8和9)。
这些实施例表明，含有25wt％至45wt％的滑石、5wt％至8wt％的PTFE、和50wt％至70wt％聚醚酰亚胺的组合物会实现大于或等于70MPa的拉伸强度、大于或等于7500GPa的拉伸模量、大于或等于175J/m的冲击强度、大于或等于200℃的热性能(HDT)、大于或等于50滴的250伏下至漏电起痕的滴数、以及大于或等于250伏的漏电起痕电压的组合。
实施例10-13
实施例10-13显示了向含有聚醚酰亚胺和滑石的组合物添加聚四氟乙烯对机械和CTI性能的影响。配方和结果示于表3。
表3
*比较例
这些实施例表明，含有75wt％聚醚酰亚胺和25wt％滑石(具有3.5微米或4.5微米的D95)的配方分别具有6和25的250伏下至漏电起痕的滴数。当添加7.5wt％的PTFE时，250伏下至漏电起痕的滴数分别增加至93.4和100。此外，含有PTFE的组合物还实现了大于或等于80MPa的拉伸强度、大于或等于6500GPa的拉伸模量、大于或等于200℃的热变形温度、以及大于或等于250伏的漏电起痕电压的组合。
实施例14-17
实施例14-17显示了向含有聚醚酰亚胺和滑石的组合物添加不同量的聚四氟乙烯对机械和CTI性能的影响。配方和结果示于表4。
表4
*比较例
这些结果表明，含有20wt％至30wt％滑石、大于5wt％但小于10wt％的PTFE、以及大于65wt％但小于72wt％的PEI的组合物可以实现期望的水平的拉伸强度、冲击强度、HDT、和CTI性能。
实施例18-21
实施例18-21显示了向含有不同类型的聚醚酰亚胺和PTFE的组合物添加滑石的影响。配方和结果示于表5。
表5
*比较例
比较例18显示，含有70wt％的PEI2和30wt％的滑石的组合物在250伏下至漏电起痕的滴数仅为23。当滑石的量增加到40wt％或50wt％(比较例19和20)时，在250伏下至漏电起痕的滴数增加到100。然而，添加增加量的滑石可能损害组合物的拉伸强度和弯曲强度。当聚醚酰亚胺组合物含有PTFE时，需要较少的滑石以通过50滴CTI测试。实施例21显示，将PTFE与滑石一起加入PEI2导致组合物具有大于或等于50MPa的拉伸强度、大于或等于10,00GPa的拉伸模量、大于或等于90J/m的冲击强度、大于或等于200℃的HDT、大于或等于50滴的250伏下至漏电起痕的滴数、以及大于或等于300伏的漏电起痕电压的组合。
实施例22-25
实施例22-25示出了向含有聚醚酰亚胺砜和滑石的组合物添加聚四氟乙烯的影响。配方和结果示于表6。
表6
*比较例
这些实施例显示，结合40wt％或50wt％的滑石与聚醚酰亚胺砜PEI3和PTFE可以实现平衡的机械和CTI性能。
实施例26-29
实施例26-29显示向聚醚酰亚胺砜PEI4添加滑石和PTFE对机械和CTI性能的影响。配方和结果示于表7。
表7
*比较例
比较例26显示，含有70wt％的PEI4和30wt％滑石的组合物在250伏下至漏电起痕的滴数仅为23。当滑石的量增加到40wt％或50wt％时，在250伏下至漏电起痕的滴数分别增加到91和100。当PTFE存在时，仅需要40wt％滑石以将在250伏下至漏电起痕的滴数增加至100。含有PTFE的组合物还具有平衡的机械性能。
以下所阐述的是聚醚酰亚胺组合物、制造方法以及包含其的制品的具体实施方式。
在一种实施方式中，基于组合物的总重量，组合物包含45wt％至75wt％的聚醚酰亚胺；20wt％至45wt％的滑石；以及5wt％至15wt％的氟化聚合物如聚四氟乙烯；其中根据ASTM D-3638-85，组合物具有大于或等于50滴的在250伏下至漏电起痕的滴数。
聚醚酰亚胺包含式(1)的单元，其中R相同或不同，并且是取代的或未取代的二价有机基团，T是-O-或式-O-Z-O-的基团，其中-O-或-O-Z-O-基团的二价键在3,3'、3,4'、4,3'或4,4'位；并且其中Z是可选地被1至6个C1-8烷基基团、1至8个卤素原子或它们的组合取代的芳香族C6-24单环或多环部分，条件是不超过Z的化合价，优选地，R是式(2)的二价基团，其中Q1是-O-、-S-、-C(O)-、-SO2-、-SO-、-CyH2y-，其中y是1至5的整数，或它们的卤代衍生物，或-(C6H10)z-，其中z是1至4的整数，并且Z是式(3a)的二价基团，其中Q是-O-、-S-、-C(O)-、-SO2-、-SO-或-CyH2y-，其中y是1至5的整数，或其卤代衍生物，更优选地，R是间亚苯基以及Q是异丙叉基，以及在一种实施方式中，R基团的至少50摩尔百分数(mol％)是双(3,4’-亚苯基)砜、双(3,3’-亚苯基)砜或包含上述中的至少一种的组合，并且其余的R基团是对亚苯基、间亚苯基或包含上述中的至少一种的组合；且Z是2,2-(4-亚苯基)异丙叉基。
基于组合物的总重量，一种示例性组合物包含50wt％至70wt％的聚醚酰亚胺；25wt％至45wt％的滑石；以及5wt％至8wt％的聚四氟乙烯；其中组合物具有：根据ASTM D-3638-85的大于或等于50滴的在250伏下至漏电起痕的滴数；以及根据ASTM D-3638-85的大于或等于250伏的漏电起痕电压。可选地，组合物具有：根据ASTM D638测定的大于或等于70MPa的拉伸强度；根据ASTM方法D638测定的大于或等于6500GPa的拉伸模量，以及根据ASTM D648，在1.82MPa应力下，对3.2毫米注射模制棒测量的大于或等于200℃的热变形温度。
基于组合物的总重量，另一示例性组合物包含45wt％至55wt％的聚醚酰亚胺砜；35wt％至45wt％的滑石；以及8wt％至15wt％的聚四氟乙烯；其中组合物具有：根据ASTM D-3638-85大于或等于50滴的在250伏下至漏电起痕的滴数；以及根据ASTM D-3638-85大于或等于300伏的漏电起痕电压，其中聚醚酰亚胺砜包含式(1)的单元，其中R是化学式的二价基团，其中Q1是-SO2-，并且T是-O-或化学式-O-Z-O-的基团，其中-O-或-O-Z-O-基团的二价键处于3,3'、3,4'、4,3'、或4,4'位置；并且其中Z是可选地由1至6个C1-8烷基基团、1至8个卤素原子、或它们的组合所取代的芳香族C6-24单环或多环部分，条件是不超过Z的化合价。可选地组合物具有：根据ASTM D638测定的大于或等于40MPa的拉伸强度；根据ASTM方法D638测定的大于或等于11,000GPa的拉伸模量，以及根据ASTMD648，在1.82MPa应力下，对3.2毫米注射模制棒测量的大于或等于210℃的热变形温度。
前述实施方式中任一项的组合物可以可选地进一步包含添加剂，其选自加工助剂、热稳定剂、染料、阻燃剂、或包含前述至少一种的组合。
在另一实施方式中，一种绝缘材料包含上述实施方式中任一项的组合物。
还公开了由上述实施方式中任一项的组合物制成的制品，选自模制品、热成型制品、挤出膜、挤出片材、多层制品的一个或多个层、用于涂覆制品的基底和用于金属化制品的基底。
一种制造制品的方法，包括模制、挤出或浇铸上述实施方式中的任一项的组合物以形成制品。
一种控制制品的电流的漏电起痕的方法，包括：提供上述实施方式中任一项的组合物，以及加工组合物以形成制品。
对于任意上述制品或方法，制品可以是太阳能装置、电接线盒、电气连接器、电动车辆充电器、室外电器外壳、智能电表外壳、智能电网电力节点、光伏框架和微型断路器。
除非上下文另有明确规定，否则单数形式“一个”、“一种”和“该”包括复数指示物。“或”是指“和/或”。涉及相同组分或性质的所有范围的端点包括在内并且可独立地组合。除非另有定义，否则在本文中使用的技术和科学术语具有与本发明所属领域的技术人员通常理解的相同的含义。
如在本文中使用的，“组合”包括共混物、混合物、合金、反应产物等。利用标准命名法描述化合物。例如，未由任何指定基团取代的任何位置应被理解为具有由指定键或氢原子填充的化合价。使用不在两个字母或符号之间的短线(“-”)来指示取代基的连接点。例如，-CHO通过羰基的碳附接。
术语“烷基”包含支链或直链、未取代的脂肪族C1-30烃基团，例如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、仲戊基、正己基和仲己基、正庚基和仲庚基、以及正辛基和仲辛基。“烯基”指的是直链或支链，具有至少一个碳-碳双键的一价烃基团(例如，乙烯基(-HC＝CH2))。“烷氧基”是指经由氧连接的烷基基团(即烷基-O-)，例如甲氧基、乙氧基和仲丁氧基基团。“亚烷基”是指直链或支链、饱和的、二价的脂肪族烃基团(例如亚甲基(-CH2-)或亚丙基(-(CH2)3-))。“环亚烷基”指的是二价环状的亚烷基基团，-CnH2n-x，其中x代表由环化替代的氢的数量。术语“芳基”是指含有特定数量的碳原子的芳香族烃基团，如苯基、环庚三烯酮、茚满基或萘基。前缀“杂”是指包含至少一个是杂原子(例如，1、2或3个杂原子)的环成员的化合物或基团，其中杂原子各自独立地是N、O、S或P。
“取代的”是指由至少一个(例如1、2、3或4个)取代基代替氢取代化合物或基团，其中各个取代基独立地是硝基(-NO2)、氰基(-CN)、羟基(-OH)、卤素、硫醇(-SH)、硫代氰基(-SCN)、C1-6烷基、C2-6烯基、C2-6炔基、C1-6卤烷基、C1-9烷氧基、C1-6卤代烷氧基、C3-12环烷基、C5-18环烯基、C6-12芳基、C7-13芳基亚烷基(例如苄基)、C7-12烷基亚芳基(例如甲苯酰基)、C4-12杂环烷基、C3-12杂芳基、C1-6烷基磺酰基(-S(＝O)2-烷基)、C6-12芳基磺酰基(-S(＝O)2-芳基)或甲苯磺酰基(CH3C6H4SO2-)，条件是不超过取代原子的正常化合价，且取代不会显著不利地影响制造、稳定性或期望的化合物的性质。当化合物被取代时，指定数目的碳原子是在基团中碳原子的总数，包括取代基的那些。
通过引证将所有引用的参考文献以它们的全部内容合并于此。
尽管出于举例说明的目的已经阐述了典型的实施方式，但是上述说明书不应当被认为是对本文中的范围的限制。因此，在不背离本文中的精神和范围的情况下，本领域的技术人员可以想到各种修改、适应和替换。
Claims (17)
1.一种组合物，基于所述组合物的总重量，包含
45wt％至75wt％的聚醚酰亚胺；和
20wt％至45wt％的滑石；以及
5wt％至15wt％的氟化聚合物；
其中，所述组合物具有根据ASTM D-3638-85的大于或等于50滴的在250伏特下至漏电起痕的滴数。
2.根据权利要求1所述的组合物，其中，所述聚醚酰亚胺包含下式的单元：
其中
R相同或不同，并且是取代的或未取代的二价有机基团，
T是-O-或式-O-Z-O-的基团，其中-O-或-O-Z-O-基团的二价键处于3,3'、3,4'、4,3'或4,4'位置；并且其中，Z是可选地被1至6个C1-8烷基基团、1至8个卤素原子或它们的组合取代的芳香族C6-24单环或多环部分，条件是不超过Z的化合价。
3.根据权利要求1或权利要求2所述的组合物，其中，
R是下式的二价基团：
其中，Q1是-O-、-S-、-C(O)-、-SO2-、-SO-、-CyH2y-，其中y是1至5的整数，或它们的卤代衍生物、或-(C6H10)z-，其中z是1至4的整数，并且
Z是下式的二价基团：
其中，Q是-O-、-S-、-C(O)-、-SO2-、-SO-或-CyH2y-，其中y是1至5的整数或它们的卤代衍生物。
4.根据权利要求3所述的组合物，其中，R是间亚苯基并且Q是异丙叉基。
5.根据权利要求3所述的组合物，其中，
至少50摩尔百分数(mol％)的R基团是双(3,4’-亚苯基)砜、双(3,3’-亚苯基)砜或包含上述中的至少一种的组合，且剩余的R基团是对亚苯基、间亚苯基或包含上述中的至少一种的组合；并且Z是2,2-(4-亚苯基)异丙叉基。
6.根据权利要求1至5中任一项所述的组合物，其中，所述氟化聚合物包括聚四氟乙烯。
7.根据权利要求1至6中任一项所述的组合物，基于所述组合物的总重量，包含
50wt％至70wt％的聚醚酰亚胺；和
25wt％至45wt％的滑石；以及
5wt％至8wt％的聚四氟乙烯；
其中，所述组合物具有：
根据ASTM D-3638-85的大于或等于50滴的在250伏特下至漏电起痕的滴数；以及
根据ASTM D-3638-85的大于或等于250伏特的漏电起痕电压。
8.根据权利要求7所述的组合物，其中，所述组合物具有：
根据ASTM D638测定的大于或等于70MPa的拉伸强度；
根据ASTM方法D638测定的大于或等于6500GPa的拉伸模量，以及
根据ASTM D648，在1.82MPa应力下，对3.2毫米注射模制棒测量的大于或等于200℃的热变形温度。
9.根据权利要求1-3和5-6中任一项所述的组合物，基于所述组合物的总重量，包含
45wt％至55wt％的聚醚酰亚胺砜；和
35wt％至45wt％的滑石；以及
8wt％至15wt％的聚四氟乙烯；
其中，所述组合物具有：
根据ASTM D-3638-85的大于或等于50滴的在250伏特下至漏电起痕的滴数；以及
根据ASTM D-3638-85的大于或等于300伏特的漏电起痕电压，
其中，聚醚酰亚胺砜包含下式的单元：
其中，
R是下式的二价基团：
其中，Q1是-SO2-，并且
T是-O-或式-O-Z-O-的基团，其中-O-或-O-Z-O-基团的二价键处于3,3'、3,4'、4,3'或4,4'位置；并且其中，Z是可选地被1至6个C1-8烷基基团、1至8个卤素原子或它们的组合取代的芳香族C6-24单环或多环部分，条件是不超过Z的化合价。
10.根据权利要求9所述的组合物，其中，所述组合物具有：
根据ASTM D638测定的大于或等于40MPa的拉伸强度；
根据ASTM方法D638测定的大于或等于11,000GPa的拉伸模量，以及
根据ASTM D648，在1.82MPa应力下，对3.2毫米注射模制棒测量的大于或等于210℃的热变形温度。
11.根据权利要求1至10中任一项所述的组合物，进一步包含选自加工助剂、热稳定剂、颜料、阻燃剂或包含上述中的至少一种的组合的添加剂。
12.一种绝缘材料，包含权利要求1至11中任一项所述的组合物。
13.一种由权利要求1至11中任一项所述的组合物制成的制品，所述制品选自模制制品、热成型制品、挤出膜、挤出片材、多层制品的一个或多个层、用于涂覆制品的基底和用于金属化制品的基底。
14.一种由权利要求1至11中任一项所述的组合物制成的制品，其中，所述制品是太阳能装置、电气接线盒、电气连接器、电动车辆充电器、室外电器外壳、智能电表外壳、智能电网电力节点、光伏框架和微型断路器。
15.一种制造制品的方法，包括模制、挤出或浇铸权利要求1至11中任一项所述的组合物以形成制品。
16.一种控制制造的制品的电流漏电起痕的方法，所述方法包括：提供权利要求1至11中任一项所述的组合物，以及加工所述组合物以形成制造的制品。
17.根据权利要求16所述的方法，其中，所述制品是太阳能装置、电气接线盒、电气连接器、电动车辆充电器、室外电器外壳、智能电表外壳、智能电网电力节点、光伏框架和微型断路器。
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| PCT/US2016/018899 WO2016137876A1 (en) | 2015-02-23 | 2016-02-22 | Electrical tracking resistance compositions, articles formed therefrom, and methods of manufacture thereof |
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| CN107250268B (zh) * | 2015-02-23 | 2019-12-27 | 沙特基础工业全球技术有限公司 | 耐漏电起痕组合物、由其形成的制品及其制造方法 |
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