CN105504224A - 一种安全鞋用电绝缘树脂材料及其制备方法 - Google Patents

一种安全鞋用电绝缘树脂材料及其制备方法 Download PDF

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CN105504224A
CN105504224A CN201610010036.7A CN201610010036A CN105504224A CN 105504224 A CN105504224 A CN 105504224A CN 201610010036 A CN201610010036 A CN 201610010036A CN 105504224 A CN105504224 A CN 105504224A
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邱溢坚
邱昭阳
丁功成
庄小兰
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Abstract

本发明公开了一种安全鞋用电绝缘树脂材料及其制备方法，其所用原料按重量份计为：芳香族异氰酸酯40～50份，脂环族异氰酸酯10～20份，聚酯多元醇20～40份，1,4－丁二醇10～20份，聚醚胺5～10份，环氧基聚倍半硅氧烷3～8份。本发明所得树脂材料具有较好的水解稳定性，能显著提高电绝缘性能和力学性能，且生产工艺简单，材料加工性能好，可用于生产电绝缘鞋鞋底及其它电工用辅助材料。

Description

一种安全鞋用电绝缘树脂材料及其制备方法
技术领域
本发明属于鞋用材料领域，具体涉及一种安全鞋用电绝缘树脂材料及其制备方法。
背景技术
安全鞋是根据世界上职业防护安全原则制定的特种鞋，其中，耐高电压的电绝缘材料制成的安全鞋是在电力部门应用最为广泛的职业防护装备，其材料的研发也成为国际研究的热点。通常认为，电绝缘鞋适用的工作环境是在50Hz、1000V以下的交流电力设备上，在实验室条件下要能耐实验电压15KV，因此，其对于材料的要求尤为严格。现有的安全鞋用电绝缘材料主要为PVC材料，欧盟及其他国家都在限制其使用；另一类主要鞋材为聚氨酯材料，虽然该材料具有优良的电绝缘性能、力学强度等优点，但其在潮湿环境下的电绝缘性能、耐水解性能等仍有待大幅提高。中国专利（CN104072714）披露了一种电绝缘鞋用树脂材料，其通过加入聚烯丙胺树脂和各类助剂提高了树脂材料的耐水解性能，但其表面电阻率还有待于进一步提升。因此，开发一种高性能聚氨酯电绝缘材料的具有十分重要的意义。
发明内容
本发明的目的在于提供一种安全鞋用电绝缘树脂材料及其制备方法，所得树脂材料具有较好的水解稳定性及优异的电绝缘性能、力学性能，可用于生产电绝缘鞋鞋底及其它电工用辅助材料。
为实现上述目的，本发明采用如下技术方案：
一种安全鞋用电绝缘树脂材料，其所用原料按重量份计为：芳香族异氰酸酯40～50份，脂环族异氰酸酯10～20份，聚酯多元醇20～40份，1,4－丁二醇10～20份，聚醚胺5～10份，环氧基聚倍半硅氧烷3～8份。
所述芳香族异氰酸酯为二苯基甲烷二异氰酸酯、萘二异氰酸酯或对苯二异氰酸酯。
所述脂环族异氰酸酯为1,4-环己烷二异氰酸酯、环己烷二亚甲基二异氰酸酯或降冰片烷二异氰酸酯。
所述环氧基聚倍半硅氧烷的分子式为(C6H11O2)n(SiO1.5)n，其中n为8、10或12；其结构式如下：
。
所述聚醚胺为分子量1000-2500的端氨基聚氧化乙烯醚和分子量为1200-2800的端氨基聚氧化丙烯醚的混合物，二者的重量比为1:0.5-1。
所述安全鞋用电绝缘树脂材料的制备方法，是先将聚酯多元醇、芳香族异氰酸酯加入反应釜中，在60～80℃下反应0.5～2小时，再加入脂环族异氰酸酯，在80～100℃下继续反应0.2～1小时，然后在60～80℃下加入1,4－丁二醇、聚醚胺、环氧基聚倍半硅氧烷，搅拌均匀后倒入模具，放入平板硫化机，在125～155℃下硫化0.2～0.6小时，再放入60～90℃的烘箱熟化10～20小时。
与现有技术相比，本发明的优点在于：
（1）本发明将芳香族异氰酸酯和脂环族异氰酸酯复合使用，能提高材料的耐候性能，特别是耐水解性能，从而获得高性能的密封材料；环氧化的聚倍半硅氧烷本身是一种很好的电绝缘、力学性能增强材料，也是很好的聚氨酯材料交联剂，它的加入可大幅提高聚氨酯电绝缘材料的电绝缘性能和力学性能；
（2）本发明生产工艺简单，材料加工性能好，所得安全鞋用电绝缘树脂材料可方便地用于生产电绝缘鞋鞋底及其它电工用辅助材料。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
所用环氧基聚倍半硅氧烷的分子式为(C6H11O2)n(SiO1.5)n，其中n为8、10或12；其结构式如下：
。
所用聚醚胺为分子量1000-2500的端氨基聚氧化乙烯醚和分子量为1200-2800的端氨基聚氧化丙烯醚的混合物，二者的重量比为1:0.5-1。
所用聚酯多元醇均为Dtepan公司的stepanol系列芳香族聚酯多元醇，其平均相对分子质量为1246，羟值为90，25℃粘度为2000mPas，牌号为stepanlPD-90LV）。
实施例1
先将聚酯多元醇20重量份、二苯基甲烷二异氰酸酯40重量份加入反应釜中，在60℃下反应0.5小时，再加入脂环族异氰酸酯1,4-环己烷二异氰酸酯10重量份，在80℃下继续反应0.2小时，然后在60℃下加入1,4－丁二醇10重量份、聚醚胺（端氨基聚氧化乙烯醚与端氨基聚氧化丙烯醚的重量比为1:0.5）5重量份、分子式为(C6H11O2)8(SiO1.5)8的环氧基聚倍半硅氧烷3重量份，搅拌均匀后倒入模具，放入平板硫化机，在125℃下硫化0.2小时，再放入60℃的烘箱熟化10小时。
实施例2
先将聚酯多元醇40重量份、萘二异氰酸酯50重量份加入反应釜中，在80℃下反应2小时，再加入环己烷二亚甲基二异氰酸酯20重量份，在100℃下继续反应1小时，然后在80℃下加入1,4－丁二醇20重量份、聚醚胺（端氨基聚氧化乙烯醚与端氨基聚氧化丙烯醚的重量比为1:1）10重量份、分子式为(C6H11O2)10(SiO1.5)10的环氧基聚倍半硅氧烷8重量份，搅拌均匀后倒入模具，放入平板硫化机，在155℃下硫化0.6小时，再放入90℃的烘箱熟化20小时。
实施例3
先将聚酯多元醇30重量份、对苯二异氰酸酯45重量份加入反应釜中，在70℃下反应1小时，再加入降冰片烷二异氰酸酯15重量份，在90℃下继续反应0.6小时，然后在70℃下加入1,4－丁二醇15重量份、聚醚胺（端氨基聚氧化乙烯醚与端氨基聚氧化丙烯醚的重量比为1:0.75）7.5重量份、分子式为(C6H11O2)12(SiO1.5)12的环氧基聚倍半硅氧烷5.5重量份，搅拌均匀后倒入模具，放入平板硫化机，在140℃下硫化0.4小时，再放入75℃的烘箱熟化15小时。
实施例4
先将聚酯多元醇20重量份、二苯基甲烷二异氰酸酯50重量份加入反应釜中，在60℃下反应1小时，再加入降冰片烷二异氰酸酯15重量份，在90℃下继续反应1小时，然后在60℃下加入1,4－丁二醇10重量份、聚醚胺（端氨基聚氧化乙烯醚与端氨基聚氧化丙烯醚的重量比为1:0.6）10重量份、分子式为(C6H11O2)10(SiO1.5)10的环氧基聚倍半硅氧烷3重量份，搅拌均匀后倒入模具，放入平板硫化机，在140℃下硫化0.5小时，再放入90℃的烘箱熟化10小时。
基于加拿大标准协会（CSA）标准按Z195-02：“防护鞋”及Z195.1-02“选拔、护理、使用防护鞋指南”，对实施例所得材料与现有产品进行性能测定，结果见表1。
表1性能测试结果
通过表1测试结果表明，本发明所得安全鞋用电绝缘树脂材料的各项指标均远远优于现有产品。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (6)

1.一种安全鞋用电绝缘树脂材料，其特征在于：所用原料按重量份计为：芳香族异氰酸酯40～50份，脂环族异氰酸酯10～20份，聚酯多元醇20～40份，1,4－丁二醇10～20份，聚醚胺5～10份，环氧基聚倍半硅氧烷3～8份。
2.根据权利要求1所述安全鞋用电绝缘树脂材料，其特征在于：所述芳香族异氰酸酯为二苯基甲烷二异氰酸酯、萘二异氰酸酯或对苯二异氰酸酯。
3.根据权利要求1所述安全鞋用电绝缘树脂材料，其特征在于：所述脂环族异氰酸酯为1,4-环己烷二异氰酸酯、环己烷二亚甲基二异氰酸酯或降冰片烷二异氰酸酯。
4.根据权利要求1所述安全鞋用电绝缘树脂材料，其特征在于：所述环氧基聚倍半硅氧烷的分子式为(C6H11O2)n(SiO1.5)n，其中n为8、10或12；其结构式如下：
。
5.根据权利要求1所述安全鞋用电绝缘树脂材料，其特征在于：所述聚醚胺为分子量1000-2500的端氨基聚氧化乙烯醚和分子量为1200-2800的端氨基聚氧化丙烯醚的混合物，二者的重量比为1:0.5-1。
6.一种如权利要求1所述安全鞋用电绝缘树脂材料的制备方法，其特征在于：先将聚酯多元醇、芳香族异氰酸酯加入反应釜中，在60～80℃下反应0.5～2小时，再加入脂环族异氰酸酯，在80～100℃下继续反应0.2～1小时，然后在60～80℃下加入1,4－丁二醇、聚醚胺、环氧基聚倍半硅氧烷，搅拌均匀后倒入模具，放入平板硫化机，在125～155℃下硫化0.2～0.6小时，再放入60～90℃的烘箱熟化10～20小时。
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