CN106812020B - 一种变压器绝缘纸用耐热助剂、制备方法及其应用 - Google Patents
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Abstract
本发明公开了属于变压器绝缘纸领域的一种提高变压器绝缘纸耐高温老化性能助剂的制备和应用方法。该方法是将具有高温自交联性的聚乙烯吡咯烷酮高分子化合物、引发剂与含氮化合物复配制得耐热助剂，通过涂布、喷涂或浸渍的方法施涂到绝缘纸表面。聚乙烯吡咯烷酮在高温下通过引发剂作用发生自交联反应形成三维网络结构，以形成化学键的方式将纸张纤维交织起来，增强了纤维间结合作用，有利于提高纸张的耐老化性能。添加本发明耐热助剂制备的绝缘纸耐高温老化性能优良，在同等条件下，耐高温老化性提高15‑30％，并且不影响变压器系统的绝缘性能。
Description
技术领域
本发明涉及变压器绝缘纸技术领域，尤其是涉及一种变压器绝缘纸用耐热助剂、制备方法和应用。
背景技术
变压器用绝缘纸的相关性能，在较大程度上决定着变压器的运行性能及正常使用寿命。随着变压器电压等级的提升，变压器用绝缘纸的性能也面临更高的要求。特别是应用于超、特高压输电变压器设备中的绝缘纸，长时间处在高温的环境中，纸张纤维会发生热降解、水解和氧化降解，造成聚合度的下降而使机械强度降低，对变压器安全性产生巨大影响。有专利采用丙烯腈改性纤维素生成氰乙基化纤维素的方法制备耐温绝缘纸，绝缘纸的耐老化性能虽显著提高，但其强度较原纸有所降低，并且工艺复杂不利于实现工业化生产。有专利采用添加含氮化合物热稳定剂如三聚氰胺、双氰胺方法提高纤维素的热稳定性，但该方法效果十分有限。有专利采用在植物纤维中添加某些高分子化合物如聚丙烯酰胺、葡甘聚糖、纳米纤维素改性物方法，利用氢键、离子键的作用来增加纤维分子链间的物理交联点，从而提高纸张的结合强度。添加上述耐热改性剂具有一定的耐热改性效果，但由于改性剂与纤维间作用力为范德华力非化学键力，作用力不强，在高温下易破坏断裂。
发明内容
为了克服上述现有技术的缺陷，本发明的目的在于提供一种变压器绝缘纸用耐热助剂的制备和应用方法。
本发明采用如下技术方案：变压器绝缘纸用耐热助剂主要由20％-80％的具有高温自交联性的聚乙烯吡咯烷酮高分子化合物、0.5-10％引发剂和10-70％含氮化合物复配而成。
上述变压器绝缘纸用耐热助剂，所述具有高温自交联性的聚乙烯吡咯烷酮高分子化合物的重均分子量为5000-20000000。
上述变压器绝缘纸用耐热助剂，引发剂为过硫酸钾和过硫酸铵中的至少一种。
上述变压器绝缘纸用耐热助剂，含氮化合物包括三聚氰胺、双氰胺、干酪素、大豆蛋白、三聚氰胺甲醛树脂、聚丙烯酰胺和三乙醇胺中的至少一种。
上述的变压器绝缘纸用耐热助剂的制备方法为将聚乙烯吡咯烷酮和含氮化合物溶解于水或水与乙醇的混合溶液中，室温或加热至40-90℃搅拌至其完全溶解，然后加入引发剂，室温下搅拌均匀，即得到耐热助剂。耐热助剂以水溶液或水与乙醇混合溶液的形式加入，浓度为2％-20％。
上述变压器绝缘纸用耐热助剂在制备耐热性特种纸中的应用，以浸渍、单面涂布、双面涂布或喷涂的施涂方式施涂在原纸上，且施涂量为1.0-8.0g/m2。
上述变压器绝缘纸用耐热助剂可应用于变压器绝缘纸、电机用纸、不锈钢衬纸、耐高温美纹纸或人造革离型纸。
本发明的技术方案能产生以下技术效果：施涂本发明耐热助剂制备的绝缘纸，其耐高温老化性能优良，在同等条件下，绝缘纸的耐高温老化性能提高15-30％。
本发明的优点为：绝缘纸在低于100℃的条件下使用时，耐温助剂聚乙烯吡咯烷酮含有大量极性基团，可与纤维间通过氢键相互作用提高原纸的机械强度。当绝缘纸在高于100℃的环境中使用时，聚乙烯吡咯烷酮在引发剂作用下会发生自交联反应，通过化学键的键合方式形成三维网络结构，这种三维网络结构耐高温性能好，并与原纸纤维交织在一起，极大地增加了纤维间的结合点和结合强度，其耐高温老化性能显著提高。此外，聚乙烯吡咯烷酮水溶性好，对三聚氰胺和双氰胺有助溶作用，复配耐温助剂无污染，使用方便。并且聚乙烯吡咯烷酮绝缘性能优良，对变压器油的性质无不良影响。本发明耐温助剂不仅用于变压器绝缘纸领域，亦可用于电机用纸、不锈钢衬纸、耐高温美纹纸、人造革离型纸等这类要求具有耐热性的特种纸领域。
具体实施方式
实施例一：将聚乙烯吡咯烷酮80g、三聚氰胺10g、双氰胺9.5g混合后溶于水中，加热至40℃，搅拌溶解后，降至室温再加入0.5g过硫酸铵，搅拌均匀后配成固含量为5％的耐热助剂。绝缘纸原纸预烘干至含80％水分，采用浸渍的方法用两辊表胶机进行表胶，浸胶量5-7g/m2。成纸经老化实验后的强度指标检测结果见表1。
实施例二：将聚乙烯吡咯烷酮50g溶于水中室温搅拌溶解，将双氰胺20g、干酪素25g溶于乙醇溶液中(乙醇用量为水的30％)室温搅拌溶解，再将两种溶液混合，搅拌均匀后，室温下再加入过硫酸铵5g，配成固含量为8％的耐热助剂。绝缘纸原纸预烘干至含70％水分，采用刮棒双面涂布，双面总涂布量4-6g/m2。成纸经老化实验后的强度指标检测结果见表1。
实施例三：将聚乙烯吡咯烷酮20g、双氰胺50g、聚丙烯酰胺20g加入水中，于90℃的条件下搅拌溶解，降至室温加入过硫酸钾10g，搅拌均匀配成固含量为20％的耐热助剂。绝缘纸原纸预烘干至含80％水分，采用喷涂方法在绝缘纸上喷涂耐热助剂，涂布量为5-6g/m2。成纸经老化实验后的强度指标检测结果见表1。
实施例四：将聚乙烯吡咯烷酮70g、双氰胺28g加入水中，于70℃的条件下搅拌溶解，降至室温加入过硫酸钾2g，搅拌均匀配成固含量为10％的耐热助剂。采用浸渍的方法在人造革离型纸原纸上施涂耐热助剂，涂布量为4-5g/m2。成纸经老化实验后的强度指标检测结果见表2。
实施例五：将聚乙烯吡咯烷酮60g加入水中搅拌溶解，三聚氰胺20g、大豆蛋白15g加入乙醇溶液中(乙醇用量为水的20％)搅拌溶解，再将两种溶液混合，搅拌均匀后加入过硫酸铵5g，配成固含量为15％的耐热助剂。采用单面涂布的方法在人造革离型纸原纸表面施涂耐热助剂，涂布量为1-3g/m2。成纸经老化实验后的强度指标检测结果见表2。
本发明实施例1-3的绝缘纸原纸采用100％未漂白硫酸盐针叶木浆，打浆度约48°SR，浆内添加0.5％聚酰胺多胺环氧氯丙烷湿强剂及0.5％两性聚丙烯酰胺干强剂。与实施例1-3对比的空白样为未施涂耐热助剂的绝缘纸原纸。
本发明实施例4-5的人造革离型纸原纸采用100％漂白硫酸盐针叶木浆与阔叶木硫酸盐浆4∶1比例抄配，针叶木打浆度45°SR，阔叶木打浆度40°SR，浆内添加1.5％阳离子淀粉、0.6％聚酰胺多胺环氧氯丙烷和0.06％阳离子聚丙烯酰胺。与实施例4-5对比的空白样为未施涂耐热助剂的人造革离型纸原纸。
耐热助剂施涂方法采用浸渍、单面涂布、双面涂布、喷涂中的一种。
绝缘纸耐高温老化实验方法：把绝缘纸放入插有铜丝的真空管中，加入#25变压器用油，将真空管抽真空并通入氮气密封，在150℃老化箱中老化7天，测绝缘纸的强度指标。
人造革离型纸老化实验方法：将人造革离型纸放入电热鼓风干燥箱中，在140℃的条件下老化2小时，测其强度指标。
表1绝缘纸耐温抗老化实验数据
表2人造革离型纸原纸抗老化实验数据
由表1和表2的数据可以得出，施涂本发明耐热助剂的绝缘纸原纸和人造革离型纸原纸的耐高温老化性能均有所提高。与空白样相比，施涂本发明耐热助剂绝缘纸原纸的耐高温老化性能提高17％-32％，人造革离型纸原纸耐高温老化性能提高11％。
Claims (4)
1.一种变压器绝缘纸用耐热助剂，其特征是：耐热助剂由20％-80％的具有高温自交联性的聚乙烯吡咯烷酮高分子化合物、0.5-10％引发剂和10-70％含氮化合物复配而成；所述具有高温自交联性的聚乙烯吡咯烷酮高分子化合物的重均分子量为5000-20000000；所述引发剂为过硫酸钾和过硫酸铵中的至少一种；所述的含氮化合物包括三聚氰胺、双氰胺、干酪素、大豆蛋白、三聚氰胺甲醛树脂、聚丙烯酰胺和三乙醇胺中的至少一种。
2.一种制备权利要求1所述的变压器绝缘纸用耐热助剂的方法，其特征是：将聚乙烯吡咯烷酮和含氮化合物溶解于水或水与乙醇的混合溶液中，室温或加热至40-90℃搅拌至其完全溶解，然后加入引发剂，室温下搅拌均匀，即得到耐热助剂。
3.根据权利要求2所述的制备变压器绝缘纸用耐热助剂的方法，其特征是：所述耐热助剂以水溶液或水与乙醇混合溶液的形式加入，浓度为2％-20％。
4.一种权利要求1所述的变压器绝缘纸用耐热助剂在制备变压器绝缘纸中的应用，其特征是：所述耐热助剂以浸渍、单面涂布、双面涂布或喷涂的施涂方式施涂在原纸上，且施涂量为1.0-8.0g/m2。
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