CN107852059A - 固体绝缘材料、其用途和由其制造的绝缘体系 - Google Patents

固体绝缘材料、其用途和由其制造的绝缘体系 Download PDF

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Publication number
CN107852059A
CN107852059A CN201680041819.XA CN201680041819A CN107852059A CN 107852059 A CN107852059 A CN 107852059A CN 201680041819 A CN201680041819 A CN 201680041819A CN 107852059 A CN107852059 A CN 107852059A
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China
Prior art keywords
insulating material
solid insulating
material according
binder tape
weight
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Granted
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CN201680041819.XA
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CN107852059B (zh
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J.休伯
D.希尔姆
M.于布勒
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Yinmengda Co ltd
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Siemens AG
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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Abstract

本发明涉及一种固体绝缘材料，特别地带状的固体绝缘材料，其在真空浸渍工艺中的用途和由其制造的绝缘体系以及具有该绝缘体系的电机，特别地用于中压和高压范围，即用于中压和高压机器、尤其是在中压和高压范围内的旋转电机以及用于电气开关装置的半成品。所述固体绝缘材料和由其制造的绝缘体系的特征在于，其可以无酸酐的方式制造。

Description

固体绝缘材料、其用途和由其制造的绝缘体系
本发明涉及一种固体绝缘材料，特别地带状的固体绝缘材料，其在真空浸渍工艺中的用途和由其制造的绝缘体系以及具有该绝缘体系的电机，特别地用于中压和高压范围，即用于中压和高压机器、尤其是在中压和高压范围内的旋转电机以及用于电气开关装置的半成品。
电机(电动机、发电机)在其定子叠片铁芯的大部分纵向槽中具有通常由铜或其它高导电率的材料制成的特定类型的线圈绕组或导体棒
在电动机的情况下，通过以时间选择性的方式提供电流(通电)产生沿所有方向传播的磁场，其驱动悬挂在定子的孔中的并且自由旋转的转子，所述转子例如由于很多个施加的永磁体而以强制旋转的形式对感应磁场作出反应，并因此将电能转换为动能。在此，叠片铁芯电接地，而线圈却处于高的千伏电位。装配在定子槽中的线圈因此必须相对于地电位电绝缘。为此，每一个线圈例如用特定的带如云母带多次(重复)地且以限定重叠的方式(definiert-überlappt)绝缘。
优选使用云母，因为其作为颗粒形式的、特别地作为片状的无机阻挡材料能够在局部放电下有效且长时间地，例如在机器的整个寿命期间延缓电蚀，并且具有良好的化学耐受性和耐热性。云母带由云母纸和一种或多种载体如织物、膜(箔)组成，其通过胶带粘合剂(Bandkleber)相互连接。云母带是必要的，因为云母纸单独地不具有绝缘过程所需的机械强度。根据应用，可将添加剂添加到胶带粘合剂中，例如固化催化剂，其对外部施加的浸渍剂的热固化具有引发作用：在用云母带绝缘的线圈被装配到定子叠片铁芯中并电连接之后，为了避免在以后的操作中的局部放电而消除绕组空腔中和特别地定子叠片铁芯的槽间隙中的空气。由于从通电的经绝缘的线圈到叠片铁芯的距离通常保持尽可能小，因而在那里几kV/mm的场强并不罕见。相应地，绝缘材料经受应力。
作为根据现有技术的浸渍剂，已经发现可热固化的环氧树脂/酸酐混合物适用于真空浸渍工艺。
它们用于浸渍由各个部件组成的具有装配好的云母带绝缘线圈的电机定子或用于单独地浸渍线圈或导体棒。
在特定的真空浸渍工艺VPI(真空压力浸渍)工艺的过程中，这些定子或线圈迄今在真空室中整个用低粘度的环氧树脂/邻苯二甲酸酐配制剂充满，并且随后在压力下热凝胶化。通常在工业炉中在标准压力下进行最终固化。在此，固化催化剂具有如下的功能：使通常由环氧树脂和邻苯二甲酸酐组成的浸渍剂在给定的温度下在特定时间内凝胶化。迄今为止，工业标准浸渍剂是经蒸馏的双酚A-二缩水甘油醚和甲基六氢邻苯二甲酸酐的混合物。这种混合物具有足够低的粘度，从而一方面确保胶带绝缘的完全浸渍以及另一方面在不存在固化催化剂的情况下确保足够的储存稳定性。固化催化剂通常至少也被包含在固体绝缘材料如云母带中。这种云母带通过胶带粘合剂被保持在一起，因此必要的是，胶带粘合剂和固化催化剂相对于彼此是惰性的。
尤其有利的情形是，所有三种组分，即胶带粘合剂、固化催化剂和所施加的浸渍剂(beaufschlagtes)在VPI工艺期间当相遇时才彼此反应。如此实现了所述绝缘的最佳的交联和连接、相容性以及缩孔自由度(Lunkerfreiheit)，这又导致在固化过程中随后形成的电机的“主绝缘”的优化的寿命。
由于对邻苯二甲酸酐的无限制使用的毒理学担忧，将来会使用不含邻苯二甲酸酐或完全无酸酐(或不含酸酐)的基于环氧化物的浸渍剂，其使用固化催化剂聚合。
新型的固化催化剂与无酸酐的浸渍剂相匹配。越来越多地使用无酸酐的浸渍剂，如从较早的申请DE 102014219844.5、DE 102014221715.6、DE 102015205328.8、DE102015202053.3、DE 102015208527.9、DE 102015204885.3中所知的，其公开内容在此并入本说明书中。这需要使用固化催化剂，例如咪唑、哌嗪及其衍生物，而这些固化催化剂又要求固体绝缘材料中的不同的胶带粘合剂，它们在所述胶带粘合剂的情况下具有足够的储存稳定性。
因此，本发明目的在于提供固体绝缘材料、特别地用于固体绝缘材料的胶带粘合剂，以及固体绝缘材料在真空浸渍工艺中的用途并且最终提供具有这样制造的绝缘体系的电机，其中避免使用呼吸道致敏化的邻苯二甲酸酐。
因此，本发明的主题是一种固体绝缘材料，该固体绝缘材料能够与不含酸酐的浸渍剂一起在真空浸渍工艺中用于制造绝缘体系，其中所述固体绝缘材料包括载体、阻挡材料、固化催化剂和胶带粘合剂，所述固化催化剂和所述胶带粘合剂是相对于彼此惰性的，但在真空浸渍条件下与具有在浸渍温度下1小时至15小时的凝胶化时间的不含酸酐的浸渍剂反应，其中所述胶带粘合剂不含环氧乙烷基团。
此外，本发明的主题亦为如此制造的绝缘体系在电机、优选地旋转电机、特别优选地在中压和高压范围内的旋转电机以及电气开关装置、中压和高压应用、套管(Durchführungen)、变压器套管、发电机套管和/或HGü套管以及相应的半成品中的用途。
最后，本发明的主题还为包括这种绝缘体系的电机、优选地旋转电机、特别优选地在中压和高压范围内的电机以及电气开关装置、中压和高压应用、套管、变压器套管，发电机套管中和/或HGü套管和相应的半成品。
根据本发明的一个实施方案，已经发现具有至少两个游离的羟基基团的的分子，即例如二元醇、三元醇和/或多元醇是适合的胶带粘合剂。
根据一个实施方案，使用树脂状的二元醇或多元醇，其在从室温至约100℃的温度范围内作为粘稠至高粘度的材料存在。更具体地，已经发现在60至70℃的温度范围内具有0.5至100Pas、优选地1至50Pas、特别优选地2至20Pas的粘度的材料是适合的。例如，三环癸烷二甲醇(CAS 26896-48-0)符合该规格。
另一方面，在自100℃起的温度下才熔融(融化)和/或软化的固体(固态)热塑性二元醇和/或多元醇也可用作胶带粘合剂。例如，聚乙烯醇缩丁醛符合该规格。
当然，合适的材料相对于载体和/或阻挡材料具有足够的粘附性或粘性，因此它们可用作胶带粘合剂。
根据有利的实施方案，这样选择胶带粘合剂，使得它们充分地溶于浸渍剂中。为此，优选使用的胶带粘合剂具有与浸渍剂相匹配的极性。
例如，以下化合物(优选地具有羟基官能度)用作胶带粘合剂：内酯、己内酯、聚己内酯、特别地羟基官能的聚己内酯；
酯多元醇、聚酯多元醇、线性的聚酯多元醇、支化的聚酯多元醇、羟基官能的聚酯多元醇、羟基官能的树枝状聚酯多元醇，基于丙酸、特别地基于烷基取代的丙酸的聚酯多元醇，例如基于双-羟烷基丙酸的聚酯多元醇，例如基于2,2-双-羟甲基丙酸的多元醇；
缩醛(乙缩醛)、乙烯醇缩醛、聚乙烯醇缩醛、特别地羟基官能的聚乙烯醇缩醛，例如缩丁醛，乙烯醇缩丁醛，聚乙烯醇缩丁醛，特别地羟基官能的聚乙烯醇缩丁醛；
乙醛、乙烯醇缩乙醛、聚乙烯醇缩乙醛、特别地羟基官能的聚乙烯醇缩乙醛；
甲醛、乙烯醇缩甲醛、聚乙烯醇缩甲醛、特别地羟基官能的聚乙烯醇缩甲醛；
丙烯酸的共聚物、特别地丙烯酸与三环烷烃的共聚物，例如丙烯酸和4,8-双(羟甲基)三环[5.2.1.02,6]癸烷(CAS号：26896-48-0)的共聚物。
更特别地，上述化合物的任意混合物和/或共聚物和/或共混物也适合作为胶带粘合剂。
根据另一个实施方案，胶带粘合剂选自聚乙烯醇缩醛的组，其中作为聚乙烯醇计算的游离的羟基的含量小于35摩尔％、优选地小于30摩尔％、特别优选地小于25摩尔％。
由于它们的羟基，二元醇或多元醇适于聚合成阳离子或阴离子固化的、特别地不含邻苯二甲酸酐的制剂。
这里作为胶带粘合剂首次公开的化合物也优选地适合作为用于阳离子型(阳离子活性的)固化催化剂的载体。为此所必需的是，它们连同固化催化剂即使在约70℃的高温下也表现出对双分子羟基醚化反应没有催化作用仅略有催化作用。
作为不含酸酐的体系中的固化催化剂，适合的是例如阳离子型超酸和/或超酸盐，例如基于六氟锑酸盐、四氟硼酸盐或六氟磷酸盐的锍衍生物，还有阴离子型咪唑、咪唑衍生物、真空稳定的咪唑，特别地烷基咪唑如烷基甲基咪唑、特别地1-癸基-2-甲基咪唑，二烷基吡唑、特别地3,5-二甲基吡唑。
另外，也可使用哌嗪和/或哌嗪衍生物。
在固体绝缘材料中，载体呈织造织物如玻璃纤维织物，非织造织物(“无纺布”)如羊毛织物、特别地聚酯羊毛织物，纸和/或膜(箔)的形式。在这种情况下，膜形式的载体也可被穿孔。
在固体绝缘材料中，优选地颗粒状的阻挡材料位于该载体处、之中和/或之上。
阻挡材料优选地至少部分地呈片状。更具体地，例如可使用云母作为阻挡材料。
在一个优选的实施方案中，使用经涂覆的颗粒状的阻挡材料。更具体地，其可为经金属氧化物涂覆的颗粒状的阻挡材料，例如经氧化锡、氧化锌或氧化钛涂覆的颗粒。
在此，根据另一实施方案，提供颗粒状、特别地片状的阻挡材料的经掺杂的涂层(涂料)。
胶带粘合剂使固体绝缘材料中的至少一个载体和阻挡材料粘合。它以1-30重量％、优选地2-15重量％、特别优选地5-10重量％的量被包含在固体绝缘材料中。
根据本发明的有利的实施方式，固化催化剂(也称为“胶带固化催化剂”或“胶带促进剂”)以小于10重量％，例如0.001重量％至7.5重量％、优选地在0.01重量％至5重量％的范围内、特别优选地在0.1重量％至3.5重量％的范围内的浓度存在于固体绝缘材料中，使得可实现几小时的凝胶化时间。
根据本发明的有利的实施方式，第一固化催化剂在20℃至100℃、优选地50℃至80℃且特别优选地55℃至75℃的范围内的温度下引发浸渍树脂的聚合。
为了在固体绝缘材料中实现所需的储存稳定性，例如在室温下和特别地在持续数小时的真空保持温度和浸渍温度下，固化催化剂对于胶带粘合剂材料是相对惰性的。这特别地还在如下的真空保持温度和/或浸渍温度的条件下：处于例如在20℃至100℃、特别是在50℃至80℃、最优选地在55℃至75℃的范围内。例如，作为胶带粘合剂，合适的是二元醇、三元醇和/或多元醇。
本发明涉及固体绝缘材料，特别地带状的绝缘材料，其在真空浸渍工艺中的用途和由其制造的绝缘体系以及具有该绝缘体系的电机，特别地用于中压和高压范围，即用于中压和高压机器、尤其是在中压和高压范围内的旋转电机以及用于电气开关装置的半成品。所述固体绝缘材料和由其制造的绝缘体系的特征在于，其可以无酸酐的方式制造。

Claims (19)

1.一种固体绝缘材料，其能够与不含酸酐的浸渍剂一起用于在真空浸渍工艺中制造绝缘体系，其中所述固体绝缘材料包括载体、阻挡材料、固化催化剂和胶带粘合剂，所述固化催化剂和所述胶带粘合剂是相对于彼此惰性的，但在真空浸渍条件下与具有在浸渍温度下1小时至15小时的凝胶化时间的不含酸酐的浸渍剂反应，其中所述胶带粘合剂不含环氧乙烷基团，并且其中所述胶带粘合剂具有至少两个游离的羟基，即例如二元醇、三元醇和/或多元醇。
2.根据权利要求1所述的固体绝缘材料，其中所述胶带粘合剂在60℃至70℃的温度范围内表现出0.5至100Pas、优选地1至50Pas、特别优选地2至20Pas的粘度。
3.根据权利要求1或2所述的固体绝缘材料，其中所述胶带粘合剂为三环癸烷二甲醇。
4.根据权利要求1所述的固体绝缘材料，其中所述胶带粘合剂在100℃以上的温度才熔化和/或软化。
5.根据权利要求4所述的固体绝缘材料，其中所述胶带粘合剂是聚乙烯醇缩醛。
6.根据前述权利要求之一所述的固体绝缘材料，其中所述胶带粘合剂选自以下化合物：
内酯、己内酯、聚己内酯、特别地羟基官能的聚己内酯；
酯多元醇、聚酯多元醇、线性的聚酯多元醇、支化的聚酯多元醇、羟基官能的聚酯多元醇、羟基官能的树枝状聚酯多元醇，基于丙酸、特别地基于烷基取代的丙酸的聚酯多元醇，例如基于双-羟烷基丙酸的聚酯多元醇，如基于2,2-双-羟甲基丙酸的多元醇；
缩醛、乙烯醇缩醛、聚乙烯醇缩醛、特别地羟基官能的聚乙烯醇缩醛，例如缩丁醛，乙烯醇缩丁醛，聚乙烯醇缩丁醛，特别地羟基官能的聚乙烯醇缩丁醛；
乙醛、乙烯醇缩乙醛、聚乙烯醇缩乙醛、特别地羟基官能的聚乙烯醇缩乙醛；
甲醛、乙烯醇缩甲醛、聚乙烯醇缩甲醛、特别地羟基官能的聚乙烯醇缩甲醛；
丙烯酸的共聚物、特别地丙烯酸与三环烷烃的共聚物，例如丙烯酸和CAS号26896-48-0的4,8-双(羟甲基)三环[5.2.1.02,6]癸烷的共聚物，所有前述化合物优选为羟基官能的，以及前述化合物的任意混合物、掺混物、共聚物和/或共混物。
7.根据权利要求6所述的固体绝缘材料，其中所述胶带粘合剂选自聚乙烯醇缩醛的组，其特征在于，作为聚乙烯醇计算的游离的羟基的含量小于35摩尔％、优选地小于30摩尔％、特别优选地小于25摩尔％。
8.根据前述权利要求之一所述的固体绝缘材料，其中所述固化催化剂选自以下化合物：阳离子型超酸和/或超酸盐，例如基于六氟锑酸盐、四氟硼酸盐或六氟磷酸盐的锍衍生物，还有阴离子型咪唑、咪唑衍生物、真空稳定的咪唑，特别地烷基咪唑，例如烷基甲基咪唑、特别地1-癸基-2-甲基咪唑，二烷基吡唑、特别地3,5-二甲基吡唑，哌嗪和/或哌嗪衍生物，以及前述化合物的任意混合物。
9.根据前述权利要求之一所述的固体绝缘材料，其中该固体绝缘材料包括以织造织物、非织造织物和/或膜形式的载体。
10.根据权利要求9所述的固体绝缘材料，其中该固体绝缘材料包括穿孔膜。
11.根据前述权利要求之一所述的固体绝缘材料，其中该固体绝缘材料包括颗粒状的阻挡材料。
12.根据前述权利要求之一所述的固体绝缘材料，其中颗粒状的阻挡材料至少部分地包括片状的阻挡材料颗粒。
13.根据权利要求11或12所述的固体绝缘材料，其中阻挡材料的颗粒是经涂覆的。
14.根据权利要求11至13之一所述的固体绝缘材料，其中涂料包括金属氧化物。
15.根据权利要求11至14之一所述的固体绝缘材料，其中涂料是经掺杂的。
16.根据前述权利要求之一所述的固体绝缘材料，其以在1-30重量％、优选地2-15重量％、特别优选地5-10重量％的范围内的量包含胶带粘合剂。
17.根据前述权利要求之一所述的固体绝缘材料，其以小于10重量％，例如0.001重量％至7.5重量％、优选地在0.01重量％至5重量％的范围内、特别优选地在0.1重量％至3.5重量％的范围内的浓度包含固化催化剂。
18.通过用根据权利要求1至17之一所述的固体绝缘材料真空浸渍而制造的绝缘体系在中压和高压机器、特别地中压和高压范围内的旋转电机中，以及在电气开关设备、中压和高压应用、套管、变压器套管、发电机套管和/或HGü套管中，以及在相应的半成品中的用途。
19.电机、优选地旋转电机、特别优选地在中压和高压范围内的旋转电机以及电气开关设备、中压和高压应用、套管、变压器套管、发电机套管和/或HGü套管以及相应的半成品，其包括由根据权利要求1至17之一所述的固体绝缘材料制造的绝缘体系。
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