CN102958690A - 适用于电绝缘的多层结构 - Google Patents
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Abstract
本发明公开了一种多层结构,其包括(a)包含芳族聚酰胺和纤维素的第一层,其中(i)所述芳族聚酰胺以0至50重量%的絮状物和50至100重量%的纤条体的量作为间位芳族聚酰胺存在,(ii)所述纤维素以纤维素纸浆纤维形式存在,并且(iii)所述芳族聚酰胺以16至75重量%的量存在,并且所述纤维素以25至84重量%的量存在,所述百分比是基于所述芳族聚酰胺和纤维素计的;和(b)包含纤维素纸浆纤维的第二层,前提条件是所述第二层不包含芳族聚酰胺。所述多层结构尤其适合用于变压器。
Description
发明领域
本发明涉及一种适用于电绝缘的多层结构。
相关领域说明
由纤维素纸浆制成的牛皮纸由于其良好的绝缘特性且较为经济而被广泛用作油浸式变压器中的固体电绝缘物。然而,该纤维素聚合物易于因长期暴露于高温而水解。通过共混高温合成纤维与纤维素纸浆能够改善热稳定性以及机械强度。加入聚合物粘合剂以有利于合成纤维与纤维素纸浆之间的粘结。然而,在纸材加工期间以及在高温运行时其与变压器线圈接触的使用期间,聚合物粘合剂可导致纸材中的不均匀性和粘着问题。
因此期望制备出一种具有改善的热稳定性和机械强度的用于电绝缘的纸材,同时降低其在加工和最终使用期间的粘着性。
发明概述
本发明涉及多层结构,其包括:
(a)包含芳族聚酰胺和纤维素的第一层,其中
(i)所述芳族聚酰胺以0至50重量%的絮状物和50至100重量%的纤条体的量作为间位芳族聚酰胺存在,
(ii)所述纤维素以纤维素纸浆纤维形式存在,并且
(iii)所述芳族聚酰胺以16至75重量%的量存在,并且
所述纤维素以25至84重量%的量存在,
所述百分比是基于所述芳族聚酰胺和纤维素计的;和
(b)包含纤维素纸浆纤维的第二层,前提条件是所述第二层不包含芳族聚酰胺。
本发明的其他实施方案在第二层的不面向第一层的一侧上包括一个或多个附加层,即附加层不位于第一层和第二层之间。如果存在至少三个或四个层,则认为第一层表示某个构造中的外层。
任何附加层均可具有第一层和第二层的构造。四层构造的实例包括第一层和第二层的组合物(按任何顺序)。
上述多层构造为一种适用于具有电导体的装置的电绝缘物。优选的是用于变压器中。
发明详述
在本公开中,使用了术语“层”。然而,在某些情况下,所述层可被描述为“纸材”。纸材一般将具有不大于1.0毫米的厚度。因此,在优选的用途中,所公开的层将各自具有不大于1.0毫米的厚度。
多层构造中所需的第一层为包括芳族聚酰胺和纤维素的层,其中
(i)所述芳族聚酰胺以0至50重量%的絮状物和50至100重量%的纤条体的量作为间位芳族聚酰胺存在,
(ii)所述纤维素以纤维素纸浆纤维形式存在。
如本文所用,术语“芳族聚酰胺(aramid)”是指芳族聚酰胺(aromatic polyamide),其中至少85%的酰胺(-CONH-)连接基直接连接到两个芳族环。任选地,可将添加剂用于芳族聚酰胺并且可分散在整个聚合物结构中。已发现,按重量计至多达约10%的其他聚合材料能够与芳族聚酰胺共混。还发现能够使用共聚物,所述共聚物具有多达10%的取代芳族聚酰胺的二胺的其他二胺或多达10%的取代芳族聚酰胺的二甲酰氯的其他二甲酰氯。间位芳族聚酰胺为其中酰胺连接基相对于彼此处在间位的那些芳族聚酰胺。一种优选的间位芳族聚酰胺为聚(间苯二甲酰间苯二胺)。
如本文所用,术语“絮状物”是指被切割成短的长度且通常用于制备湿铺纸片的纤维。通常,絮状物具有3毫米至20毫米的长度。优选3毫米至7毫米的长度。絮状物通常通过使用本领域熟知的方法将连续纤维切割成所需长度来产生。
如本文所用,术语“纤条体”是指非粒状、纤维质或膜状颗粒,其中它们的三维尺寸中的至少一维尺寸相对于最大尺寸具有微小的量值。这些颗粒能够通过使用非溶剂在高剪切下沉淀聚合材料的溶剂来制备。纤条体具有在0.2mm至1mm范围内的最大尺寸长度,其中长度与宽度的长宽比为5∶1至10∶1。厚度尺寸为大约几分之一微米,例如0.1微米至约1.0微米。纤条体在被干燥之前可按润湿状态使用,并且能够被沉积为形成组件的纸材。
如果对于间位芳族聚酰胺使用的是絮状物和纤条体的组合,则絮状物与纤条体的优选的重量比在0.5至4.0,更优选0.8至2.0的范围内。
术语“纤维素纸浆”是指通过如下方式制备的纤维质纤维素材料:以化学方式或机械方式从木材、纤维作物或废纸中分离出纤维。纤维素纸浆纤维为本发明的多层结构的一种所需的组分。优选的纤维素纸浆为未漂白的软木纸浆。
另一个要求存在于多层结构的第一层中,即芳族聚酰胺以16至75重量%的量存在,并且纤维素以25至84重量%的量存在,所述百分比是基于芳族聚酰胺和纤维素计的。更优选范围的一个实例为25至50重量%的芳族聚酰胺和50至75重量%的纤维素。
所需的第二层包括纤维素纸浆纤维,前提条件是第二层不包含芳族聚酰胺。本发明的多层结构通常在常规的造纸机上形成。常规的添加剂可用于第二层的形成,虽然附加的添加剂不是必要的。合适添加剂的实例包括聚合物粘合剂诸如聚乙烯基醇、聚乙酸乙烯酯、聚酰胺树脂、环氧树脂、酚醛树脂、聚脲、聚氨酯、三聚氰胺甲醛和聚酯。
如果与所需第一层和第二层结合地使用一个或多个附加层,则能够获得改善的性能。希望在附加构造中第一层为外层。另一个附加层可具有第一层的组成(具有相同或不同的芳族聚酰胺/纤维素比率)或不具有芳族聚酰胺的第二纤维素层可与第二层相同或不同。
本发明的多层结构能够用作电绝缘纸材,并且该结构尤其适用于制造变压器,即通过感应耦合的导体(变压器线圈)将电能从一个电路传递至另一个电路的装置。合适的变压器包括大型变压器,包括具有处理至少200kVA且更一般地至少400kVA容量的变压器。此类大型变压器通常将包含油,这是人们熟知的。优选地,当电绝缘纸材包裹在变压器的导电线圈周围时,绝缘纸材的第一含芳族聚酰胺层邻近线圈定位。期望第一含芳族聚酰胺层中不含聚合物粘合剂以防止粘附并在使用期间减少多层结构的热降解。
测试方法
在下文所提供的实施例中使用了以下测试方法。
根据ASTM D 645和ASTM D 645-M-96测量并按g/m2报告基重。
根据ASTM D 646-96测量并按mm报告厚度。
根据ASTM D 828-93用2.54cm宽的测试样品和18cm的隔距来测量并按MPa报告拉伸强度。
根据ASTM D 2413进行老化研究。将单一温度单元老化系统放置在160℃下的具有氮填充的顶部空间的常规实验室烘箱中并持续340至2,720小时。油浸渍是通过如下方式进行的:将测试样本在115±5℃的温度和75Pa(0.5托)或更小的绝对压力下彻底干燥至少16小时,随后在大气压下暴露于油中8小时或更长时间以便使纸材完全浸渍在油中。
根据ISO 5267/2和TAPPI T227测量并按ml报告加拿大标准游离度。
根据ISO 5267/1测量并按ml报告肖伯-黎格勒游离度。
使用常规的纸材制造技术制备了多层的纸材结构。
比较实施例A
两层的纸材结构由两个100重量%的纤维素纸浆纤维层制成。每个层均由源自Celco Company(Chile)的3g纤维素木浆(软木)的含水分散体制备而成。纸浆被磨浆至250ml的加拿大标准游离度。将含水分散体与8升水一起倒入到21×21cm的手抄纸模具中,并且形成湿铺纸片。将两个纤维素纸浆纤维的湿铺纸片一起放置在两片吸墨纸之间,用擀棒以手横压并放入手抄纸干燥器中,在150℃下干燥10分钟。将干燥的两个层的片材以2800N/cm的线压力在金属辊和软辊之间压延,其中金属辊被加热至80℃。表中列出了所得两层的纸材结构的特性。
实旋例1至4
根据本发明的两层的纸材结构由一个含芳族聚酰胺层和一个无芳族聚酰胺层制成。含芳族聚酰胺层由从未干燥的聚(间苯二甲酰间苯二胺)纤条体的浆液的含水分散体制成。间位芳族聚酰胺纤条体是按美国专利3,756,908一般所述的方式制造的,并且这些纤条体具有330ml的肖伯-黎格勒游离度。
无芳族聚酰胺层是用如比较实施例A所述的纤维素木浆制备的。
调整芳族聚酰胺与纤维素纸浆纤维的比率以便这些层将具有20重量%、30重量%、40重量%和50重量%的芳族聚酰胺含量。将含水分散体在英式纸浆评测设备(British Pulp Evaluation Apparatus)中一起混合3分钟,然后与8升水一起倒入21×21cm的手抄纸模具中,并且形成湿铺纸片。使用相同的设备由相同纤维素木浆的含水分散体制备了无芳族聚酰胺层。将含芳族聚酰胺湿铺纸片和无芳族聚酰胺湿铺纸片一起放置在两片吸墨纸之间,用擀棒以手横压并放入手抄纸干燥器中,在150℃下干燥。将干燥的两个层状片材如比较实施例A所述的那样压延。表中列出了所得两层的纸材结构的特性。
比较实施例B
两层的纸材结构由两个100重量%的芳族聚酰胺含量的层制成。这些层是使用实施例1-4所述的含芳族聚酰胺层方法制成的,不同的是使用了100%的芳族聚酰胺含量而没有纤维素纸浆纤维。表中列出了所得两层的纸材结构的特性。
比较实施例C
制造了单层的纸材结构,从而示出了典型的现有技术的纸材结构。这些层是使用实施例1-4所述的含芳族聚酰胺层方法制成的,不同的是使用了70重量%的纤维素木浆、作为聚合物粘合剂的20重量%的70-62聚(乙烯醇)(购自DuPont Company)、和用作含水分散体的10重量%的芳族聚酰胺絮状物。间位芳族聚酰胺絮状物为线密度为0.22特且长度为0.64cm的聚(间苯二甲酰间苯二胺)絮状物(由DuPont Company以商品名出售)。表中列出了所得两层的纸材结构的特性。
下文的实施例4和5示出了使用造纸机以连续方法来制备本发明的多层结构。
实施例5
在使用4个成形滚筒的多滚筒式造纸机上形成了具有3层结构的纸材。
喂送给第一滚筒和第四滚筒的浆液由水与实施例1-4所述的芳族聚酰胺纤条体和纤维素纸浆组成,具有按它们的总含量计25重量%的芳族聚酰胺纤条体和75重量%的纤维素纸浆。
喂送给第二滚筒和第三滚筒的浆液仅由水和纤维素纸浆组成。
源自浆液的固体被沉积在成形滚筒的筛网上,并且从这些滚筒上转移到移动的毡上。
使湿的多层纸片经过湿压机和干燥器,并且最终经过具有加热至约80℃的金属辊的压延机。
所产生的纸材具有三层结构,其中第一层为芳族聚酰胺-纤维素,第二层为100%的纤维素,并且第三层为芳族聚酰胺-纤维素。每个层的基重相应地为39g/m2、78g/m2和39g/m2。该纸材具有156g/cm3的总基重、0.130mm的厚度和0.85g/cm3的表观密度。
实施例6
在配有初级流浆箱和次级流浆箱的长网造纸机上形成了2层结构。
喂送给初级流浆箱的浆液由水与实施例1-4所述的纤维素纸浆组成。
喂送给次级流浆箱的浆液由水与纤维素纸浆、间位芳族聚酰胺纤条体和间位芳族聚酰胺絮状物组成。该浆液的固体组成为:
-纤维素纸浆:50重量%;
-间位芳族聚酰胺纤条体:30重量%;
-间位芳族聚酰胺絮状物:20重量%。
纤维素纸浆、间位芳族聚酰胺纤条体和间位芳族聚酰胺絮状物与实施例1-4中的相同,不同的是絮状物长度为3mm。
在从网上取下之后,使2层的片材经过湿压机和干燥器部分。
将干燥的片材附加地在加热至180℃的两个金属辊之间压延。
最终2层的纸材结构具有130g/m2的基重、0.125mm的厚度和0.85g/cm3的表观密度。其初始拉伸强度在纵向上为82MPa,并且在横向上为-43MPa。
表中的拉伸强度数据表明,与不含芳族聚酰胺的比较实施例A和表示在单层构造中包含芳族聚酰胺和聚合物粘合剂的现有技术的纸材结构的比较实施例C相比,包括本发明的实施例1-4的含芳族聚酰胺层的多层的纸材结构在加速热老化时具有较高的拉伸强度保留%。
据认为,当将本发明的多层的纸材结构的含芳族聚酰胺层放置成接触变压器线圈时,由于含芳族聚酰胺层中不含聚合物粘合剂材料,该纸材结构具有抗热降解和抗粘着特性。
Claims (14)
1.多层结构,包括:
(a)包含芳族聚酰胺和纤维素的第一层,其中
(i)所述芳族聚酰胺以0至50重量%的絮状物和50至100重量%的纤条体含量作为间位芳族聚酰胺存在,
(ii)所述纤维素以纤维素纸浆纤维形式存在,并且
(iii)所述芳族聚酰胺以16至75重量%的量存在,并且所述纤维素以25至84重量%的量存在,所述百分比是基于所述芳族聚酰胺和纤维素计的;和
(b)包含纤维素纸浆纤维的第二层,前提条件是所述第二层不包含芳族聚酰胺。
2.根据权利要求1所述的多层结构,其中所述芳族聚酰胺为聚(间苯二甲酰间苯二胺)。
3.根据权利要求1所述的多层结构,其中所述第一层不包含聚合物粘合剂。
4.根据权利要求1所述的多层结构,其中所述第一层包含25至50重量%的芳族聚酰胺和50至75重量%的纤维素。
5.根据权利要求1所述的多层结构,其中所述第一层包含以0.5至4.0的重量比存在的絮状物和纤条体。
6.根据权利要求5所述的多层结构,其中所述重量比为0.8至2.0。
7.根据权利要求1所述的多层结构,所述多层结构具有至少一个附加层,所述附加层包括:
(a)包含芳族聚酰胺和纤维素的层,其中
(i)所述芳族聚酰胺以0至50重量%的絮状物和50至100重量%的纤条体含量作为间位芳族聚酰胺存在,
(ii)所述纤维素以纤维素纸浆纤维形式存在,并且
(iii)所述芳族聚酰胺以16至75重量%的量存在,并且
所述纤维素以25至84重量%的量存在,
所述百分比是基于所述芳族聚酰胺和纤维素计的;或
(b)包含纤维素纸浆纤维的附加层,前提条件是所述第二层不包含芳族聚酰胺。
8.根据权利要求7所述的多层结构,所述多层结构中同时存在两个附加层。
9.根据权利要求7所述的多层结构,所述多层结构具有与所述第一层或所述第二层相同的附加层。
10.装置,包括电导体和电绝缘多层结构材料,所述多层结构材料包括:
(a)包含芳族聚酰胺和纤维素的第一层,其中
(i)所述芳族聚酰胺以0至50重量%的絮状物和50至100重量%的纤条体含量作为间位芳族聚酰胺存在,
(ii)所述纤维素以纤维素纸浆纤维形式存在,并且
(iii)所述芳族聚酰胺以16至75重量%的量存在,并且
所述纤维素以25至84重量%的量存在,
所述百分比是基于所述芳族聚酰胺和纤维素计的;和
(b)包含纤维素纸浆纤维的第二层,前提条件是所述第二层不包含芳族聚酰胺。
11.根据权利要求10所述的装置,所述装置为变压器。
12.根据权利要求11所述的变压器,所述变压器为油浸式的。
13.根据权利要求10所述的变压器,所述变压器具有至少200kVA的容量。
14.根据权利要求13所述的变压器,所述变压器具有至少400kVA的容量。
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