CN107429139B - 用于绝缘体系中的绝缘胶带的胶带粘合剂和绝缘体系 - Google Patents
用于绝缘体系中的绝缘胶带的胶带粘合剂和绝缘体系 Download PDFInfo
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Abstract
本发明涉及用于绝缘体系中的绝缘胶带的胶带粘合剂和绝缘体系，特别是用于在1kV以上的高电压范围内的电机的绝缘体系，其具有无酸酐的浸渍树脂，例如具有环氧乙烷官能度的浸渍树脂。通过本发明首次提供了一种适合于常规浸渍方法的用于绝缘体系的胶带粘合剂，所述绝缘体系包括诸如云母的固体绝缘材料、无酸酐的浸渍树脂和用于无酸酐的浸渍树脂的促进剂，其中关于整个体系的储存稳定性，相对于无酸酐的浸渍树脂的促进剂或固化催化剂的反应性来调整所述胶带粘合剂。
Description
本发明涉及用于绝缘体系中的绝缘胶带的胶带粘合剂和绝缘体系，特别是用于在1kV以上的高压范围内的电机的绝缘体系，所述绝缘体系包括无酸酐(不含酸酐)的浸渍树脂，例如具有环氧乙烷官能度的浸渍树脂。
电机在定子叠片铁心的多个纵向槽中包含通常由铜制成的特殊类型的线圈绕组，其通过随时间变化选择性地通电而产生向四周传播的磁场，该磁场又驱动被悬挂在定子的孔中且自由旋转的转子，所述转子例如可基于多个所应用的永磁体而以强制旋转的形式对感应磁场作出反应，并因此可以将电能转换成动能。这里，叠片铁心处于接地电位，线圈反而处于高的千伏电位。因此，安装在定子槽中的线圈必须是对地(gegen Masse)电绝缘的。
为此，每个线圈均用特殊的基于云母纸的带(云母带)多次地且以重叠经限定的方式来绝缘。之所以使用云母，是因为云母作为片状的无机固体绝缘材料能够在电气局部放电情况下有效地且长时间地阻滞电气腐蚀，并且具有良好的化学和热稳定性。云母带例如由云母纸和一个或多个通过胶带粘合剂彼此连接的载体(例如膜)组成。相对于云母纸而言，优选使用云母带，因为云母纸单独地不具有绝缘过程所需的机械强度。
按照应用，可以向胶带粘合剂中添加另外的添加剂，例如对随后外部施加的浸渍剂的热固化具有催化作用的促进剂：在用云母带绝缘的线圈被装配到定子叠片铁心中并且电连接之后，为了在稍后的操作期间避免局部放电，绕组的空腔中的空气、特别地定子叠片铁心的槽间隙中的空气被浸渍剂置换(排挤出)。由于通电的绝缘线圈相对于叠片铁心的距离通常保持尽可能小，因此在那里几kV/mm的场强并不少见。与之相应地，必须选择绝缘材料。
可热固化的环氧树脂/酸酐混合物已被证明对于这些目的是可靠的。在本领域技术人员已知的作为真空压力浸渍的“VPI方法”中，根据现有技术，在真空室中电机的由其各个部件组成的定子与所安装的经云母带绝缘的线圈一起完全地被低粘度的环氧树脂/邻苯二甲酸酐制剂所淹没，然后在施加压力下浸渍。取决于云母带中的促进剂与浸渍剂之间的相互作用，在浸渍阶段期间就已发生渗透到云母带绝缘中的浸渍剂的凝胶化。
然而，由于邻苯二甲酸酐是呼吸系统敏化物质，因此对生产例如由DE102014219844.5已知的完全无酸酐的绝缘体系，例如具有环氧乙烷官能度的浸渍树脂，是非常令人感兴趣的。
最终固化通常在标准压力下在工业炉中进行。在此，云母带中的促进剂(胶带促进剂)的任务是在规定的温度下在期望的时间内凝胶化和固化所施加的浸渍树脂，该浸渍树脂至此始终为具有邻苯二甲酸酐的环氧树脂。已经成为工业标准的浸渍剂是蒸馏的双酚A二缩水甘油醚和甲基六氢邻苯二甲酸酐的混合物，这种粘度非常低的制剂在没有促进剂物质的情况下在浸渍温度下具有所需的长的储存稳定性(例如初始粘度在几周后才加倍)，但是在催化活性物质的存在下迅速反应成高分子聚合物。然而，由于云母带同样必须具有足够长的储存稳定性，所以胶带粘合剂和胶带促进剂应当互为惰性的。理想情况下，所有的三种组分(胶带粘合剂、胶带促进剂和浸渍剂)只在VPI过程中相遇的时刻才相互反应。由此能实现最佳的交联和结合，相容性和最终免于缺陷和缩孔，并由此实现了在固化时最终形成的电机“主绝缘”的长的电气寿命。
由于浸渍剂(“浸渍树脂”)至今仍然是环氧树脂-邻苯二甲酸酐混合物，因而为引发固化通常选择胺衍生物。例如，胶带促进剂通常是取代的胺，例如基于哌嗪等，因为通过这种物质可以在热固化期间调节环氧树脂/酸酐混合物中的较高的玻璃化转变温度。另外，环烷酸锌是已建立的胶带促进剂。
由于在理想的情况下，为了达到与浸渍树脂的最佳相容性或反应性，胶带粘合剂同样是环氧乙烷官能化的，因而云母带中的储存稳定性会出现问题。特别地，在使用无酸酐的浸渍树脂的情况下使用如下的促进剂，该促进剂引发阴离子和/或阳离子聚合机理并因此对于常规胶带粘合剂显示出比现有技术中通常使用的用于酸酐-反应性树脂混合物的促进剂更少的惰性。
相应地，本发明要解决的技术问题是找到一种用于无酸酐的浸渍树脂的胶带粘合剂，其具有相应的反应性促进剂，在其它方面该胶带粘合剂满足迄今为止对在具有含酸酐的浸渍剂的绝缘体系中使用的胶带粘合剂所作的类似要求。
该技术问题通过如在权利要求书、说明书和附图中公开的本发明的技术方案来解决。
本发明提供了一种用于绝缘体系的胶带粘合剂，其在浸渍温度下的动态粘度为1-100Pa*s，其包括由以下称为“A(OH)n”链段的双酚、二醇、三醇和/或更高级的醇与以下称为“Cy”链段的环氧环己烷或环氧环己烷衍生物形成的加成产物。本发明还提供一种绝缘体系，其包括固体绝缘材料、无酸酐的浸渍树脂、促进剂和胶带粘合剂。
根据有利的实施方案，适合作为胶带粘合剂的是这样的化合物，该化合物根据化学环氧乙烷-羟基反应由环氧环己烷和/或单环氧的环氧环己烷衍生物和二醇、三醇和/或高级醇、醇衍生物、脂族酯、脂环族酯和/或芳族性质的酯、以及芳族和脂环族双酚A(OH)n(A在此根据路易斯经验式命名法对应于在形式上消掉n个OH基团的分子式剩余部分，其中n＝2至20)反应生成新的邻位羟基，并且在真空和温度介导(控制)的蒸馏除去未反应的环氧环己烷或环氧环己烷衍生物之后在浸渍温度下具有1-100Pa*s的粘度。
A(OH)n的合适实例是：
-单乙二醇(C2H4)(OH)2、丁二醇(C4H8)(OH)2、丁烯二醇(C4H6)(OH)2、丁炔二醇(C4H4)(OH)2、聚乙二醇H(OC2H4)x(OH)2(其中x＝1至5000)、丙二醇(C3H6)(OH)2、聚丙二醇H(OC3H6)x(OH)2(其中x＝1至5000)、二甘醇(C2H8O)(OH)2、丙二醇(C3H6)(OH)2、新戊二醇(C5H10)(OH)2、环戊二醇(C5H8)(OH)2、环戊烯二醇(C5H6)(OH)2、甘油(C3H5)(OH)3、戊二醇(C5H10)(OH)2、季戊四醇(C5H8)(OH)4、己二醇(Hexandiol)(C6H12)(OH)2、异己二醇(Hexylenglykol)(C6H12)(OH)2、庚二醇(C7H14)(OH)2、辛二醇(C8H16)(OH)2、聚己内酯二醇、聚己内酯三醇、氢醌(对苯二酚)(C6H4)(OH)2、间苯二酚(C6H4)(OH)2、(焦)儿茶酚(C6H4)(OH)2、噜忻喏(rucinol)(C10H12)(OH)2、三甘醇(C6H12)(OH)2,
-全芳族(vollaromatisches)、部分氢化和/或完全氢化的双酚A(C15H14)(OH)2、(C15H28)(OH)2,双酚F(C13H10)(OH)2,双酚S(C12H8O2S)(OH)2,
-三环癸烷二甲醇(C12H18)(OH)2,甘油碳酸酯(C4H5)(OH)1。
根据优选的实施方案，胶带粘合剂在70℃下的粘度为5-20Pa*s。
适合作为胶带粘合剂的化合物的选择在关于针对常规的1,2-二环氧化物、特别地具有重复单元n≥0的双酚A二缩水甘油醚和/或双酚F二缩水甘油醚的1,2-二环氧化物的阴离子和/或阳离子固化促进剂物质的反应性方面做出。在此，普遍认识是使用的胶带粘合剂优选不含环氧乙烷基团。具有较高真空稳定性的、引发阴离子聚合的促进剂，例如TMPT的三-N-甲基哌嗪衍生物，在不含环氧乙烷基团的胶带粘合剂的情况下赋予云母绝缘胶带所需的储存稳定性。
由于环氧环己烷和/或在脂族环上衍生化的环氧环己烷各自仅具有一个环氧乙烷基团，因而这些环氧基团与A(OH)n链段的羟基的反应不会产生之后能够反应的脂环族环氧乙烷基团，所述脂环族环氧乙烷基团可与绝缘胶带中的阴离子和/或阳离子控制的促进剂物质反应。
本发明的胶带粘合剂物质的合成例如通过相应的A(OH)n反应物与环氧环己烷和/或环氧环己烷衍生物的反应来实现。
由于在环氧乙烷/羟基反应期间环氧乙烷和羟基的反应按化学机理在目标分子中产生新的羟基基团，因而这些新型的胶带粘合剂衍生物还能够聚合成离子固化的，特别地不含邻苯二甲酸酐的制剂。
因此，这种新型胶带粘合剂同样适合作为离子活性促进剂类型(例如六氟锑酸盐、四氟硼酸盐和六氟磷酸盐和/或锍衍生物作为所谓的超酸或超酸盐的代表物)的载体或包封物，还可用于更为真空稳定的烷基甲基咪唑，特别地1-癸基-2-甲基咪唑。
在含有羟基的化合物的情况下，这些甚至在70℃左右的高温下也未示出或者仅示出很少的对双分子羟基醚化反应的催化。
为了说明目标结构，在下文中以结构式介绍可以单独使用或作为混合物使用的胶带粘合剂化合物的几个实施例：
所述胶带粘合剂是在室温下粘稠的至高度粘稠的或无定形固化的物质，其例如以50％-99.5重量％，优选60％-95重量％，特别优选70％-90重量％的含量与一种或多种在室温下为固体或液体的促进剂的混合物的形式存在。
作为促进剂例如可以使用离子活性固化催化剂，例如有机和/或无机超酸或超酸盐，烷基咪唑和/或烷基咪唑衍生物，烷基吡唑和/或烷基吡唑衍生物等。
作为浸渍剂优选使用无酸酐的浸渍树脂，例如浸渍树脂包括一种或多种选自由以下化合物组成的组的化合物：未蒸馏和/或蒸馏的、任选反应性稀释的双酚A二缩水甘油醚；未蒸馏和/或蒸馏的、任选反应性稀释的双酚F二缩水甘油醚；氢化的双酚A二缩水甘油醚和/或氢化的双酚F二缩水甘油醚，纯和/或用溶剂稀释的环氧酚醛清漆和/或环氧苯酚酚醛清漆；脂环族环氧树脂如3,4-环氧环己基甲基3,4-环氧环己基羧酸酯例如CY179、ERL-4221；Celloxide 2021P，己二酸双(3,4-环氧环己基甲基)酯例如ERL-4299；Celloxide2081，乙烯基环己烯二环氧化物，例如ERL-4206；Celloxide 2000，2-(3,4-环氧环己基-5,5-螺-3,4-环氧)-环己烷-间二
烷例如ERL-4234；六氢邻苯二甲酸二缩水甘油酯例如CY184、EPalloy 5200；四氢邻苯二甲酸二缩水甘油醚例如CY192；缩水甘油化的氨基树脂(N,N-二缩水甘油基-对-缩水甘油氧基苯胺例如MY0500、MY0510，N,N-二缩水甘油基-间-缩水甘油氧基苯胺例如MY0600、MY0610，N,N,N',N'-四缩水甘油基-4,4'-亚甲基二苯胺例如MY720、MY721、MY725和上述化合物的任意混合物。
为了制造胶带粘合剂，环氧环己烷、4-乙烯基环氧环己烷和/或在脂环族环上具有R1R1基团的任何其它环己烯衍生物与一元醇和/或一个二元和/或多个更高级的脂族、脂环族，芳族和/或杂环醇，烷基/芳基醇衍生物和/或酯和/或双酚A(OH)n反应，其中A＝(CxHy)，优选x＝1-30和y＝1-100，必要时通过使用催化剂K，即n在1至5000的范围内，优选2-10。
通过本发明首次提供了一种适合于常规浸渍方法的用于绝缘体系的胶带粘合剂，其包括诸如云母的固体绝缘材料、无酸酐的浸渍树脂和用于无酸酐的浸渍树脂的促进剂，其中关于整个体系的储存稳定性，相对于无酸酐的浸渍树脂的促进剂或固化催化剂的反应性来调整所述胶带粘合剂。
Claims (9)
1.绝缘体系，其包括固体绝缘材料、无酸酐的浸渍树脂、促进剂和用于绝缘体系中的绝缘胶带的胶带粘合剂，所述胶带粘合剂在70℃下的粘度为5-20Pa*s并且包括由以下称为“A(OH)n”链段的双酚、二醇、三醇和/或更高级的醇与以下称为“Cy”链段的环氧环己烷或环氧环己烷衍生物形成的加成产物，其中该胶带粘合剂不含环氧乙烷基团。
2.根据权利要求1所述的绝缘体系，其中A(OH)n选自以下化合物的组的化合物：
- 单乙二醇(C2H4)(OH)2；丁二醇(C4H8)(OH)2；丁烯二醇(C4H6)(OH)2；丁炔二醇(C4H4)(OH)2；聚乙二醇H(OC2H4)x(OH)2，其中x = 1至5000；丙二醇(C3H6)(OH)2；聚丙二醇H(OC3H6)x(OH)2，其中x = 1至5000；二甘醇(C2H8O)(OH)2；丙二醇(C3H6)(OH)2；新戊二醇(C5H10)(OH)2；环戊二醇(C5H8)(OH)2；环戊烯二醇(C5H6)(OH)2；甘油(C3H5)(OH)3；戊二醇(C5H10)(OH)2；季戊四醇(C5H8)(OH)4；己二醇(C6H12)(OH)2；异己二醇(C6H12)(OH)2；庚二醇(C7H14)(OH)2；辛二醇(C8H16)(OH)2；聚己内酯二醇；聚己内酯三醇；氢醌(C6H4)(OH)2；间苯二酚(C6H4)(OH)2；儿茶酚(C6H4)(OH)2；噜忻喏(C10H12)(OH)2；三甘醇(C6H12)(OH)2,
- 全芳族、部分氢化和/或完全氢化的双酚A (C15H14)(OH)2、(C15H28)(OH)2, 双酚F(C13H10)(OH)2, 双酚S (C12H8O2S)(OH)2,
- 三环癸烷二甲醇 (C12H18)(OH)2。
3.根据权利要求1所述的绝缘体系，其中所述胶带粘合剂以50-99.5重量％的含量与促进剂以混合物的形式存在。
4.根据权利要求3所述的绝缘体系，其中所述胶带粘合剂以60 -95重量％的含量与促进剂以混合物的形式存在。
5.根据权利要求4所述的绝缘体系，其中所述胶带粘合剂以70-90重量％的含量与促进剂以混合物的形式存在。
6.根据权利要求1至5中任一项所述的绝缘体系，其中所述促进剂选自以下化合物的组：超酸或超酸盐，烷基甲基咪唑和/或二烷基吡唑。
7.根据权利要求6所述的绝缘体系，其中所述超酸或超酸盐为六氟锑酸盐、四氟硼酸盐、六氟磷酸盐和/或锍衍生物。
8.根据权利要求6所述的绝缘体系，其中所述烷基甲基咪唑为1-癸基-2-甲基-咪唑。
9.根据权利要求6所述的绝缘体系，其中所述二烷基吡唑为3,5-二甲基-吡唑。
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| DE (1) | DE102015205328A1 (zh) |
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| WO (1) | WO2016150764A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015205328A1 (de) | 2015-03-24 | 2016-09-29 | Siemens Aktiengesellschaft | Bandkleber für ein Isolierband in einem Isolationssystem und Isolationssystem |
| DE102015213537A1 (de) | 2015-07-17 | 2017-01-19 | Siemens Aktiengesellschaft | Fester, insbesondere bandförmiger, Isolationswerkstoff, Formulierung für ein Imprägniermittel zur Herstellung eines Isolationssystems in einem Vakuumimprägnierverfahren damit und Maschinen mit derartigem Isolationssystem |
| DE102015213535A1 (de) | 2015-07-17 | 2017-01-19 | Siemens Aktiengesellschaft | Fester Isolationswerkstoff, Verwendung dazu und damit hergestelltes Isolationssystem |
| DE102015213815A1 (de) | 2015-07-17 | 2017-01-19 | Siemens Aktiengesellschaft | Fester Isolationswerkstoff, Verwendung dazu und damit hergestelltes Isolationssystem |
| DE102016203867A1 (de) | 2016-03-09 | 2017-09-14 | Siemens Aktiengesellschaft | Fester Isolationswerkstoff, Verwendung dazu und damit hergestelltes Isolationssystem |
| US20200058416A1 (en) * | 2016-11-01 | 2020-02-20 | Huntsman Advanced Materials Licensing (Switzerland) Gmbh | Electrical Insulation System Based on Epoxy Resins for Generators and Motors |
| DE102017201498A1 (de) | 2017-01-31 | 2018-08-02 | Siemens Aktiengesellschaft | Wickelbandisoliersystem für elektrische Maschinen, Verwendung dazu sowie elektrische Maschine |
| EP3716290A1 (de) * | 2019-03-28 | 2020-09-30 | Siemens Aktiengesellschaft | Formulierung für ein isolationssystem, isolationssystem daraus und elektrische maschine mit isolationssystem |
| WO2021043541A1 (de) | 2019-09-04 | 2021-03-11 | Siemens Aktiengesellschaft | Bandbeschleuniger und verwendung davon, fester isolationswerkstoff und anhydrid-freies isolationssystem |
| EP3996113A1 (de) * | 2020-11-05 | 2022-05-11 | Siemens Aktiengesellschaft | Glimmschutzband für rotierende elektrische hochspannungsmaschine, verwendung dazu und elektrische maschine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039322A (zh) * | 1988-07-14 | 1990-01-31 | 西门子公司 | 制造用于导电体的热硬化环氧树脂-酸酐混合物浸渍绝缘层的绝缘带 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2656290A (en) * | 1948-10-28 | 1953-10-20 | Westinghouse Electric Corp | Processes for producing electrical coils insulated with mica and synthetic resins and the products thereof |
| DE1162898B (de) * | 1961-06-23 | 1964-02-13 | Siemens Ag | Glimmerband zur Herstellung einer mit einer heisshaertenden Epoxydtraenkharzmischung impraegnierten Isolierhuelse fuer elektrische Leiter, insbesondere fuer die Wicklungsstaebe bzw. Spulen elektrischer Maschinen |
| DE19720555A1 (de) | 1997-05-16 | 1998-11-19 | Abb Research Ltd | Statorwicklungsisolierung |
| GB9913627D0 (en) * | 1999-06-12 | 1999-08-11 | Ciba Geigy Ag | Process for the preparation of reaction products of cycloaliphatic epoxides with multifunctional hydroxy compounds |
| CA2571054A1 (en) | 2004-06-16 | 2006-01-26 | Isovolta Ag | Mica tape having maximized mica content |
| JP5611182B2 (ja) * | 2011-12-07 | 2014-10-22 | 株式会社日立製作所 | ドライマイカテープ、並びにそれを用いた電気絶縁線輪及び回転電機 |
| DE102014219844A1 (de) | 2014-09-30 | 2016-03-31 | Siemens Aktiengesellschaft | Isolationssystem für elektrische Maschinen |
| DE102015205328A1 (de) | 2015-03-24 | 2016-09-29 | Siemens Aktiengesellschaft | Bandkleber für ein Isolierband in einem Isolationssystem und Isolationssystem |
-
2015
- 2015-03-24 DE DE102015205328.8A patent/DE102015205328A1/de not_active Withdrawn
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2016
- 2016-03-15 CN CN201680017313.5A patent/CN107429139B/zh active Active
- 2016-03-15 BR BR112017019546-1A patent/BR112017019546B1/pt active IP Right Grant
- 2016-03-15 US US15/560,652 patent/US10544338B2/en active Active
- 2016-03-15 EP EP16712289.4A patent/EP3245063B1/de active Active
- 2016-03-15 WO PCT/EP2016/055557 patent/WO2016150764A1/de active Application Filing
- 2016-03-15 RU RU2017132974A patent/RU2692730C2/ru active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039322A (zh) * | 1988-07-14 | 1990-01-31 | 西门子公司 | 制造用于导电体的热硬化环氧树脂-酸酐混合物浸渍绝缘层的绝缘带 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107429139A (zh) | 2017-12-01 |
| WO2016150764A1 (de) | 2016-09-29 |
| RU2017132974A3 (zh) | 2019-04-24 |
| BR112017019546A2 (pt) | 2018-05-02 |
| DE102015205328A1 (de) | 2016-09-29 |
| US20180094177A1 (en) | 2018-04-05 |
| US10544338B2 (en) | 2020-01-28 |
| RU2692730C2 (ru) | 2019-06-26 |
| EP3245063A1 (de) | 2017-11-22 |
| BR112017019546B1 (pt) | 2022-04-12 |
| EP3245063B1 (de) | 2022-07-20 |
| RU2017132974A (ru) | 2019-04-24 |
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