CN106758460A - 一种高击穿强度的变压器用芳纶纤维基绝缘纸及其制备方法 - Google Patents
一种高击穿强度的变压器用芳纶纤维基绝缘纸及其制备方法 Download PDFInfo
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Abstract
本发明公开一种高击穿强度的变压器用芳纶纤维基绝缘纸,由以下重量份的原料组成:芳纶纤维38‑50,玻璃纤维13‑25,氯磺酸50‑70,三氯氧磷18‑25,氯化铵3‑7,去离子水适量,氯仿适量,乙烯基三甲氧基硅烷0.2‑1,纳米二氧化硅10‑20,无水乙醇适量,环己酮适量,溴化亚铜1‑2,联吡啶2‑6,抗氧剂CA 1‑2,羟甲基纤维素钠2‑4,蒙脱土3‑6,高岭土2‑5,炭黑1‑4。本发明将芳纶纤维与玻璃纤维混合打浆处理,之后在纤维表面引入‑SO2Cl基团,与经双键修饰的纳米二氧化硅反应,达到改善纤维界面粘结性的效果,提高了绝缘纸的机械性能、耐腐蚀、耐高温和强度等性能,且产品的介电常数低。
Description
技术领域
本发明涉及变压器技术领域,尤其涉及一种高击穿强度的变压器用芳纶纤维基绝缘纸及其制备方法。
背景技术
绝缘纸广泛用作电机、电缆、电容器和变压器等设备的绝缘材料,也是层压制品、复合材料和预浸材料等绝缘材料的主要组成材料。由于绝缘纸的特殊用途,要求其必须具备一些不同于其它纸种的特性,主要包括机械性能、电气性能和热稳定性。
目前我国生产的绝缘纸板以B级、F级为主,在某些性能方面存在不足,如性能不稳定、机械强度差、耐高温性不够、耐老化性能差、对环境造成污染等问题,严重影响了变压器设备向小型化、大容量化、特高压发展的前景。
张红蕊、梁国正等人在其《超支化聚硅氧烷接枝改性芳纶纤维的研究》一文中,选用超支化聚硅氧烷对芳纶纤维进行表面改性,通过原位聚合法,得到改性芳纶纤维(HSi-g-KF),超支化聚硅氧烷(HSis)带有的大量活性官能团提高了HSi-g-KF纤维的表面浸润性,-Si-O-和-Si-C-链段则显著提高了HSi-g-KF纤维的抗紫外辐照性,使得芳纶纤维的表面粘结性、抗老化性和阻燃性能都有所提升。
微纳米级二氧化硅(SiO2)空心微球已经被掺杂在高分子材料聚酰亚胺中来降低介电常数,介电常数从2.3降到1.8,并且二氧化硅的价格相对低廉,可明显降低成本。所以本发明选择纳米二氧化硅对绝缘纸进行改性,达到变压器设备向小型化发展的需求。
发明内容
本发明目的就是为了弥补已有技术的缺陷,提供一种高击穿强度的变压器用芳纶纤维基绝缘纸及其制备方法。
一种高击穿强度的变压器用芳纶纤维基绝缘纸,由以下重量份的原料组成:芳纶纤维38-50份,玻璃纤维13-25份,氯磺酸50-70份,三氯氧磷18-25份,氯化铵3-7份,去离子水适量,氯仿适量,乙烯基三甲氧基硅烷0.2-1份,纳米二氧化硅10-20份,无水乙醇适量,环己酮适量,溴化亚铜1-2份,联吡啶2-6份,抗氧剂CA 1-2份,羟甲基纤维素钠2-4份,蒙脱土3-6份,高岭土2-5份,炭黑1-4份。
具体步骤如下:
(1)对原料纤维进行预处理:
①、使用槽式打浆机对芳纶纤维、玻璃纤维进行分散处理,加入去离子水控制打浆浓度在2-5%,置于纤维解离机中硫解3-8分钟,得到芳纶纤维/玻璃纤维混合浆粕,然后将混合纤维浆粕置于真空环境中,在98-105℃条件下燥干;
②、将上述干燥后的混合纤维浆粕置于氯仿中超声分散2-3小时,室温下加入氯磺酸搅拌反应30-50分钟,之后边搅拌边加入氯化铵,之后油浴加热至70-80℃后开始滴加三氯氧磷,加料结束后恒温搅拌反应2-4小时,静止分层,将下层的磺化油放置于冷却结晶釜中,冷却至25℃以下进行冷却、结晶,过滤将滤饼经水洗2-4次,真空干燥至恒重,得到氯磺化修饰的混合纤维浆粕;
(2)在纳米二氧化硅表面引入双键:
将乙烯基三甲氧基硅烷加入无水乙醇中混合均匀,调节溶液pH至弱碱性,加入干燥后的纳米二氧化硅搅拌10-30分钟,后放入水浴锅中加热回流,搅拌反应40-60分钟,将经过表面改性剂处理后的纳米二氧化硅取出,放入95-105℃的烘箱中干燥22-25小时,得到表面双键修饰的纳米二氧化硅;
(3)接枝改性混合纤维浆粕的制备:
将步骤(2)处理后的纳米二氧化硅加入含有环己酮的四口圆底烧瓶中,超声波振荡10-20分钟,之后向反应体系中加入步骤(1)氯磺化修饰的混合纤维浆粕以及溴化亚铜、联吡啶,在氮气保护下,25-35℃进行恒温聚合反应,反应3-5小时后离心分离,反应产物用去离子水反复洗涤多次,于70-85℃真空干燥至恒重,得到接枝改性混合纤维浆粕;
(4)将蒙脱土、高岭土以1:100的质量比例溶于无水乙醇中,在磁力搅拌器上搅拌10-20分钟,得混合溶液备用;
(5)将上述接枝改性混合纤维浆粕在去离子水中浸泡2-5小时,利用打浆机进行打浆,待浆料的打浆度到40°SR时停止打浆,加入去离子水使浆料的浓度在2%内进行机械搅拌,向其中加入步骤(4)混合溶液、炭黑、抗氧剂CA、羟甲基纤维素钠以300-500转/分进行搅拌30-50分钟,最后将纸浆悬浮液送入纸业成型设备中进行脱水干燥成型,即可得到所需绝缘纸。
其中,所述的步骤(4)中对纸浆悬浮液的干燥采用两段干燥,第一段干燥的温度为105-115℃,第二段干燥的温度为145-155℃。
与现有技术相比,本发明具有以下优点:
(1)本发明将芳纶纤维与玻璃纤维混合打浆处理,利用玻璃纤维的优异性能,制备的复合纸大大提高了其机械性能、阻燃、耐腐蚀、耐高温和强度等方面的作用,且能大幅度提高绝缘纸的绝缘性能,之后采用氯磺酸对浆粕进行氯磺化处理,在纤维表面引入-SO2Cl基团,易于在纤维表面接枝引入极性基团(-OH,-NH2,-NHNH2),达到改善纤维界面粘结性的效果。
(2)本发明将含双键的硅偶联剂(乙烯基三甲氧基硅烷)与纳米二氧化硅表面的硅氢基反应,将双键引入纳米二氧化硅离子表面,再与纤维表面的-SO2Cl基团反应,实现接枝反应,使得纳米二氧化硅粒子不易团聚,在纸浆中分散均匀,明显降低了绝缘纸的介电常数,电绝缘性能、击穿电压提高,同时提高其在耐磨性、耐老化性等方面的作用。
(3)本发明中添加蒙脱土、高岭土提高了绝缘纸的击穿电压,降低了其相对介电常数从而延缓其老化,延长使用寿命。
具体实施方式
一种高击穿强度的变压器用芳纶纤维基绝缘纸,由以下重量份的原料组成:芳纶纤维46份,玻璃纤维21份,氯磺酸65份,三氯氧磷21份,氯化铵6份,去离子水适量,氯仿适量,乙烯基三甲氧基硅烷0.7份,纳米二氧化硅15份,无水乙醇适量,环己酮适量,溴化亚铜1份,联吡啶3份,抗氧剂CA 1份,羟甲基纤维素钠4份,蒙脱土5份,高岭土4份,炭黑3份。
具体步骤如下:
(1)对原料纤维进行预处理:
①、使用槽式打浆机对芳纶纤维、玻璃纤维进行分散处理,加入去离子水控制打浆浓度在2%,置于纤维解离机中硫解5分钟,得到芳纶纤维/玻璃纤维混合浆粕,然后将混合纤维浆粕置于真空环境中,在100℃条件下燥干;
②、将上述干燥后的混合纤维浆粕置于氯仿中超声分散3小时,室温下加入氯磺酸搅拌反应40分钟,之后边搅拌边加入氯化铵,之后油浴加热至75℃后开始滴加三氯氧磷,加料结束后恒温搅拌反应3小时,静止分层,将下层的磺化油放置于冷却结晶釜中,冷却至25℃以下进行冷却、结晶,过滤将滤饼经水洗3次,真空干燥至恒重,得到氯磺化修饰的混合纤维浆粕;
(2)在纳米二氧化硅表面引入双键:
将乙烯基三甲氧基硅烷加入无水乙醇中混合均匀,调节溶液pH至弱碱性,加入干燥后的纳米二氧化硅搅拌20分钟,后放入水浴锅中加热回流,搅拌反应50分钟,将经过表面改性剂处理后的纳米二氧化硅取出,放入100℃的烘箱中干燥24小时,得到表面双键修饰的纳米二氧化硅;
(3)接枝改性混合纤维浆粕的制备:
将步骤(2)处理后的纳米二氧化硅加入含有环己酮的四口圆底烧瓶中,超声波振荡15分钟,之后向反应体系中加入步骤(1)氯磺化修饰的混合纤维浆粕以及溴化亚铜、联吡啶,在氮气保护下,30℃进行恒温聚合反应,反应4小时后离心分离,反应产物用去离子水反复洗涤多次,于80℃真空干燥至恒重,得到接枝改性混合纤维浆粕;
(4)将蒙脱土、高岭土以1:100的质量比例溶于无水乙醇中,在磁力搅拌器上搅拌15分钟,得混合溶液备用;
(5)将上述接枝改性混合纤维浆粕在去离子水中浸泡4小时,利用打浆机进行打浆,待浆料的打浆度到40°SR时停止打浆,加入去离子水使浆料的浓度在2%内进行机械搅拌,向其中加入步骤(4)混合溶液、炭黑、抗氧剂CA、羟甲基纤维素钠以400转/分进行搅拌40分钟,最后将纸浆悬浮液送入纸业成型设备中进行脱水干燥成型,即可得到所需绝缘纸。
其中,所述的步骤(4)中对纸浆悬浮液的干燥采用两段干燥,第一段干燥的温度为110℃,第二段干燥的温度为150℃。
按照本实施例制备的绝缘纸其性能测试如下:
击穿电压(空气中):21.4KV;阻燃级别:V0级;介电常数:3.1;,介电损耗因数:0.046;抗拉伸强度:纵向82Mpa,横向45Mpa;
含水量:< 8.0% ;吸油率:> 15% ;热膨胀率(120℃):< 0.6。
Claims (3)
1.一种高击穿强度的变压器用芳纶纤维基绝缘纸,其特征在于,由以下重量份的原料组成:芳纶纤维38-50份,玻璃纤维13-25份,氯磺酸50-70份,三氯氧磷18-25份,氯化铵3-7份,去离子水适量,氯仿适量,乙烯基三甲氧基硅烷0.2-1份,纳米二氧化硅10-20份,无水乙醇适量,环己酮适量,溴化亚铜1-2份,联吡啶2-6份,抗氧剂CA 1-2份,羟甲基纤维素钠2-4份,蒙脱土3-6份,高岭土2-5份,炭黑1-4份。
2.根据权利要求书1所述的一种高击穿强度的变压器用芳纶纤维基绝缘纸的制备方法,其特征在于,具体步骤如下:
(1)对原料纤维进行预处理:
①、使用槽式打浆机对芳纶纤维、玻璃纤维进行分散处理,加入去离子水控制打浆浓度在2-5%,置于纤维解离机中硫解3-8分钟,得到芳纶纤维/玻璃纤维混合浆粕,然后将混合纤维浆粕置于真空环境中,在98-105℃条件下燥干;
②、将上述干燥后的混合纤维浆粕置于氯仿中超声分散2-3小时,室温下加入氯磺酸搅拌反应30-50分钟,之后边搅拌边加入氯化铵,之后油浴加热至70-80℃后开始滴加三氯氧磷,加料结束后恒温搅拌反应2-4小时,静止分层,将下层的磺化油放置于冷却结晶釜中,冷却至25℃以下进行冷却、结晶,过滤将滤饼经水洗2-4次,真空干燥至恒重,得到氯磺化修饰的混合纤维浆粕;
(2)在纳米二氧化硅表面引入双键:
将乙烯基三甲氧基硅烷加入无水乙醇中混合均匀,调节溶液pH至弱碱性,加入干燥后的纳米二氧化硅搅拌10-30分钟,后放入水浴锅中加热回流,搅拌反应40-60分钟,将经过表面改性剂处理后的纳米二氧化硅取出,放入95-105℃的烘箱中干燥22-25小时,得到表面双键修饰的纳米二氧化硅;
(3)接枝改性混合纤维浆粕的制备:
将步骤(2)处理后的纳米二氧化硅加入含有环己酮的四口圆底烧瓶中,超声波振荡10-20分钟,之后向反应体系中加入步骤(1)氯磺化修饰的混合纤维浆粕以及溴化亚铜、联吡啶,在氮气保护下,25-35℃进行恒温聚合反应,反应3-5小时后离心分离,反应产物用去离子水反复洗涤多次,于70-85℃真空干燥至恒重,得到接枝改性混合纤维浆粕;
(4)将蒙脱土、高岭土以1:100的质量比例溶于无水乙醇中,在磁力搅拌器上搅拌10-20分钟,得混合溶液备用;
(5)将上述接枝改性混合纤维浆粕在去离子水中浸泡2-5小时,利用打浆机进行打浆,待浆料的打浆度到40°SR时停止打浆,加入去离子水使浆料的浓度在2%内进行机械搅拌,向其中加入步骤(4)混合溶液、炭黑、抗氧剂CA、羟甲基纤维素钠以300-500转/分进行搅拌30-50分钟,最后将纸浆悬浮液送入纸业成型设备中进行脱水干燥成型,即可得到所需绝缘纸。
3.根据权利要求书2所述的一种高击穿强度的变压器用芳纶纤维基绝缘纸的制备方法,其特征在于,所述的步骤(4)中对纸浆悬浮液的干燥采用两段干燥,第一段干燥的温度为105-115℃,第二段干燥的温度为145-155℃。
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