CN106702755A - 一种高性能硅/氟醚复合橡胶手套及其制备方法 - Google Patents

一种高性能硅/氟醚复合橡胶手套及其制备方法 Download PDF

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CN106702755A
CN106702755A CN201710012664.3A CN201710012664A CN106702755A CN 106702755 A CN106702755 A CN 106702755A CN 201710012664 A CN201710012664 A CN 201710012664A CN 106702755 A CN106702755 A CN 106702755A
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Abstract

本发明提供了一种高性能硅/氟醚复合橡胶手套，所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶80～120份，甲基乙烯基硅橡胶40～60份，过氧化硫化剂1～3份，氧化锌5～8份，酚醛树脂15～30份，促进剂0.5～1.5份，抗氧剂0.1～0.5份，甲基丙烯酸羟乙酯修饰石墨烯15～30份，邻苯二甲酸二辛酯3～6份，B‑萘基对苯二氨0.8～1.6份，四氢呋喃50～100份；本发明将氟醚橡胶与硅橡胶进行共混，充分结合了各自的优点，制得的材料具有优异的耐高温、耐腐蚀、耐油以及极佳的机械性能，能应用于工业极端环境，为未来工业的应用创造了条件。

Description

一种高性能硅/氟醚复合橡胶手套及其制备方法
技术领域
本发明属于橡胶制品领域，特别是涉及一种高性能硅/氟醚复合橡胶手套及其制备方法。
背景技术
在塑料制品中，手套占有很重要的位置，除用于工、农、渔和家用外，还广泛应用于医学领域。我国、美国、日本、马来西亚等国家均有手套生产，产品产量、适用范围、生产厂家、企业效益数都很可观。
硅橡胶是指主链由硅和氧原子交替构成，硅原子上通常连有两个有机基团的橡胶。普通的硅橡胶主要由含甲基和少量乙烯基的硅氧链节组成。苯基的引入可提高硅橡胶的耐高、低温性能，三氟丙基及氰基的引入则可提高硅橡胶的耐温及耐油性能。硅橡胶耐低温性能良好，一般在-55℃下仍能工作。引入苯基后，可达73℃。硅橡胶的耐热性能也很突出，在180℃下可长期工作，稍高于200℃也能承受数周或更长时间仍有弹性，瞬时可耐300℃以上的高温。硅橡胶的透气性好，氧气透过率在合成聚合物中是最高的。此外，硅橡胶还具有生理惰性，不会导致凝血的突出特性，因此在医用领域应用广泛。
氟醚橡胶是一种含有大量碳氟和氟烷基醚分子结构的高分子聚合物。因具有优异的耐高低温、耐强氧化剂及耐多种化学介质性能，被作为极端条件下的材料使用。随着我国经济发展，特别是航空航天、高端汽车行业的推动和化工仪器仪表等工业产品可靠性的要求增加，氟醚橡胶逐渐成为不可替代的密封材料。
然而，现阶段随着经济社会的快速发展，手套行业对各种应用环境的要求也逐渐提高，极端环境如高温、高腐蚀、高强度、极低温度等对手套橡胶制品的性能要求也越来越严格，单一组成的橡胶制品在某些高要求环境下并不能完全满足需求。开发具有优异性能的共混橡胶制品已越来越受到关注。CN 200810219534.8公开了一种氟橡胶与硅橡胶共混物及其制备方法，采用氟橡胶、硅橡胶、增容剂、吸酸剂及补强剂等材料通过机械共混法制备氟橡胶与硅橡胶共混物，其实施例中共混物的耐油质量变化率均超过28％，甚至达到了38.3％。CN 201210087884.X公开了一种氟橡胶、硅橡胶与氟硅橡胶三元共混耐高低温耐油材料及制备方法，同样由于硅橡胶的存在，其共混物耐油体积变化率在20％-24％。
然而，关于硅橡胶和氟醚橡胶进行共混以制备特种橡胶基复合新材料的研究和报道还较少，因此，本发明基于上述现有技术的不足以及现有橡胶制品发展的需求，开发了一种性能十分优异，能够耐受特点极端环境的高性能硅/氟醚复合橡胶手套，以满足橡胶手套现阶段和未来的发展需求。
发明内容
本发明的目的是为了解决现有技术的不足，提供一种具有优异综合性能的橡胶手套，该手套具有在极端环境下十分好的耐热、耐低温、耐气候老化、耐腐蚀、强度高等优异性能。
为解决上述问题，本发明采用的技术方案为：
一种高性能硅/氟醚复合橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述硅/氟醚橡胶层由硅/氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶80～120份，甲基乙烯基硅橡胶40～60份，过氧化硫化剂1～3份，氧化锌5～8份，酚醛树脂15～30份，促进剂0.5～1.5份，抗氧剂0.1～0.5份，甲基丙烯酸羟乙酯修饰石墨烯15～30份，邻苯二甲酸二辛酯3～6份，B-萘基对苯二氨0.8～1.6份，四氢呋喃50～100份。
其中，所述过氧化硫化剂为DCP。
所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
所述抗氧剂为抗氧剂1010、抗氧剂264、抗氧剂DSTP、抗氧剂1076、抗氧剂DLTP中的一种或其组合。
所述甲基丙烯酸羟乙酯修饰石墨烯的制备方法包括如下步骤：
(1)将氧化石墨、固体含量为25-35％的甲基丙烯酸羟乙酯胶乳与异丙醇混合，对混合物进行水浴超声处理至氧化石墨均匀分散，在不断的搅拌下将混合物进行50-70℃反应，得到甲基丙烯酸羟乙酯改性的氧化石墨产物；
(2)对(1)中产物进行还原处理，得到甲基丙烯酸羟乙酯改性的石墨烯产物。
另外，本发明还提供了所述橡胶手套的制备方法，具体包括如下步骤：
(1)按重量份数取氟醚橡胶、甲基乙烯基硅橡胶、氧化锌、酚醛树脂、抗氧剂、甲基丙烯酸羟乙酯修饰石墨烯、邻苯二甲酸二辛酯和B-萘基对苯二氨进行混合后通过混炼工艺处理得到混炼胶；
(2)将步骤(1)得到的混炼胶与重量份的过氧化硫化剂、促进剂以及四氢呋喃混合配制成混炼胶胶浆；
(3)将纤维手套衬里套于流水线模具上经过表面处理后，浸入上述配置好的混炼胶胶浆中，在温度为100-150℃条件下硫化20-40分钟，然后在于60℃-80℃温度下初固化10-15分钟，在90℃-120℃温度下充分固化20-40分钟分钟，冷却至30-60℃，如此重复两次冷却脱模即得所述复合橡胶手套。
本发明的技术效果为：
(1)本发明创造性的将氟醚橡胶与硅橡胶进行共混，在硅橡胶中引入含氟基团，充分结合了两者各自的优点，使两者的性能协同，制得的材料即具有硅橡胶优异的耐高低温性能以及加工性，又具有氟醚橡胶优异的耐高温、耐腐蚀、耐油以及极佳的机械性能，所得的橡胶手套能够应用于工业极端环境，为未来工业的应用需求创造了条件。
(2)本发明酚醛树脂的作用主要在于增加硅橡胶和氟醚橡胶两者的共融性，使用含活泼羟基基团的甲基丙烯酸羟乙酯胶乳对石墨烯进行改性，主要在于增强石墨烯与氟醚橡胶中的碳氟分子链、硅橡胶中的-Si-O分子链的相互作用，增加石墨烯在橡胶中的分散性，从而进一步起到提升橡胶的力学性能、耐高温性和耐磨擦磨损性能。
(3)本发明制备工艺流程简单，具有十分广阔的前景。
具体实施方式
下面结合实施例对本发明的技术方案做进一步的阐述：
实施例1
一种高性能硅/氟醚复合橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述硅/氟醚橡胶层由硅/氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶80份，甲基乙烯基硅橡胶40份，过氧化硫化剂DCP1份，氧化锌5份，酚醛树脂15份，促进剂0.5份，抗氧剂1010 0.1份，甲基丙烯酸羟乙酯修饰石墨烯15份，邻苯二甲酸二辛酯3份，B-萘基对苯二氨0.8份，四氢呋喃50份；其中，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
实施例2
一种高性能硅/氟醚复合橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述硅/氟醚橡胶层由硅/氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶120份，甲基乙烯基硅橡胶60份，过氧化硫化剂DCP3份，氧化锌8份，酚醛树脂30份，促进剂1.5份，抗氧剂1010 0.5份，甲基丙烯酸羟乙酯修饰石墨烯30份，邻苯二甲酸二辛酯6份，B-萘基对苯二氨1.6份，四氢呋喃100份；其中，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
实施例3
一种高性能硅/氟醚复合橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述硅/氟醚橡胶层由硅/氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶100份，甲基乙烯基硅橡胶50份，过氧化硫化剂DCP2份，氧化锌6份，酚醛树脂24份，促进剂1份，抗氧剂DSTP 0.3份，甲基丙烯酸羟乙酯修饰石墨烯22份，邻苯二甲酸二辛酯4份，B-萘基对苯二氨1.2份，四氢呋喃75份；其中，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
实施例4
一种高性能硅/氟醚复合橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述硅/氟醚橡胶层由硅/氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶90份，甲基乙烯基硅橡胶50份，过氧化硫化剂DCP2份，氧化锌6份，酚醛树脂20份，促进剂0.8份，抗氧剂DLTP 0.2份，甲基丙烯酸羟乙酯修饰石墨烯20份，邻苯二甲酸二辛酯4份，B-萘基对苯二氨1份，四氢呋喃60份；其中，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
对比例1
一种氟醚橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述氟醚橡胶层由氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述氟醚橡胶，按重量份数计，由如下组分制成：氟醚橡胶100份，过氧化硫化剂DCP2份，氧化锌6份，酚醛树脂24份，促进剂1份，抗氧剂DSTP 0.3份，甲基丙烯酸羟乙酯修饰石墨烯22份，邻苯二甲酸二辛酯4份，B-萘基对苯二氨1.2份，四氢呋喃75份；其中，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
对比例2
一种硅橡胶手套，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅橡胶层，所述硅橡胶层由硅橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅橡胶，按重量份数计，由如下组分制成：甲基乙烯基硅橡胶50份，过氧化硫化剂DCP2份，氧化锌6份，酚醛树脂24份，促进剂1份，抗氧剂DSTP 0.3份，甲基丙烯酸羟乙酯修饰石墨烯22份，邻苯二甲酸二辛酯4份，B-萘基对苯二氨1.2份，四氢呋喃75份；其中，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
实施例1-4所述橡胶手套的制备方法，包括如下步骤：
(1)按重量份数取氟醚橡胶、甲基乙烯基硅橡胶、氧化锌、酚醛树脂、抗氧剂、甲基丙烯酸羟乙酯修饰石墨烯、邻苯二甲酸二辛酯和B-萘基对苯二氨进行混合后通过混炼工艺处理得到混炼胶；
(2)将步骤(1)得到的混炼胶与重量份的过氧化硫化剂、促进剂以及四氢呋喃混合配制成混炼胶胶浆；
(3)将纤维手套衬里套于流水线模具上经过表面处理后，浸入上述配置好的混炼胶胶浆中，在温度为130℃条件下硫化30分钟，然后在于70℃温度下初固化13分钟，在110℃温度下充分固化40分钟分钟，冷却至40℃，如此重复两次冷却脱模即得所述复合橡胶手套。
对比例1-2的制备方法同上。
性能测试
对本发明实施例1-4所得产品所得产品的性能进行测试，测试结果见下表1。
对本发明实施例3与对比例1-2所得产品的性能进行测试对比，测试结果见下表2。
从上表1可知，实施例1-4的橡胶手套具有十分优异的综合性能。
从上表1可知，实施例3的橡胶手套的综合性能远优于对比例1-2橡胶手套的性能。
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

1.一种高性能硅/氟醚复合橡胶手套，其特征在于，包括纤维手套衬里，在纤维手套衬里表面涂覆有硅/氟醚橡胶层，所述硅/氟醚橡胶层由硅/氟醚橡胶胶浆采用浸浆的方式涂敷在纤维手套衬里表面；其中所述硅/氟醚复合橡胶，按重量份数计，由如下组分制成：氟醚橡胶80～120份，甲基乙烯基硅橡胶40～60份，过氧化硫化剂1～3份，氧化锌5～8份，酚醛树脂15～30份，促进剂0.5～1.5份，抗氧剂0.1～0.5份，甲基丙烯酸羟乙酯修饰石墨烯15～30份，邻苯二甲酸二辛酯3～6份，B-萘基对苯二氨0.8～1.6份，四氢呋喃50～100份。
2.根据权利要求1所述的橡胶手套，其特征在于，所述过氧化硫化剂为DCP。
3.根据权利要求1所述的橡胶手套，其特征在于，所述促进剂为促进剂ZBX和促进剂ZDEC按重量比1：1混合。
4.根据权利要求1所述的橡胶手套，其特征在于，所述抗氧剂为抗氧剂1010、抗氧剂264、抗氧剂DSTP、抗氧剂1076、抗氧剂DLTP中的一种或其组合。
5.根据权利要求1所述的橡胶手套，其特征在于，所述甲基丙烯酸羟乙酯修饰石墨烯的制备方法包括如下步骤：
(1)将氧化石墨、固体含量为25-35％的甲基丙烯酸羟乙酯胶乳与异丙醇混合，对混合物进行水浴超声处理至氧化石墨均匀分散，在不断的搅拌下将混合物进行50-70℃反应，得到甲基丙烯酸羟乙酯改性的氧化石墨产物；
(2)对(1)中产物进行还原处理，得到甲基丙烯酸羟乙酯改性的石墨烯产物。
6.一种权利要求1-5所述橡胶手套的制备方法，其特征在于，包括如下步骤：
(1)按重量份数取氟醚橡胶、甲基乙烯基硅橡胶、氧化锌、酚醛树脂、抗氧剂、甲基丙烯酸羟乙酯修饰石墨烯、邻苯二甲酸二辛酯和B-萘基对苯二氨进行混合后通过混炼工艺处理得到混炼胶；
(2)将步骤(1)得到的混炼胶与重量份的过氧化硫化剂、促进剂以及四氢呋喃混合配制成混炼胶胶浆；
(3)将纤维手套衬里套于流水线模具上经过表面处理后，浸入上述配置好的混炼胶胶浆中，在温度为100-150℃条件下硫化20-40分钟，然后在于60℃-80℃温度下初固化10-15分钟，在90℃-120℃温度下充分固化20-40分钟分钟，冷却至30-60℃，如此重复两次冷却脱模即得所述复合橡胶手套。
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