CN115216042B - 一种疏水疏油ptfe复合膜的制备方法 - Google Patents

一种疏水疏油ptfe复合膜的制备方法 Download PDF

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CN115216042B
CN115216042B CN202210820234.5A CN202210820234A CN115216042B CN 115216042 B CN115216042 B CN 115216042B CN 202210820234 A CN202210820234 A CN 202210820234A CN 115216042 B CN115216042 B CN 115216042B
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许建民
王丽华
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Tianjin Rijin New Materials Co ltd
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Abstract

本发明提供了一种疏水疏油PTFE复合膜的制备方法,其特征在于,包括以下步骤:将四氟乙烯树脂、航空煤油、纳米二氧化硅混合搅拌均匀,挤出、压制、拉伸得到PTFE膜;将含氟丙烯酸酯、增强剂、溶剂混合均匀,氮气保护下,滴加引发剂,之后加热至反应完全,降温减压蒸馏,得到疏水疏油涂料;将疏水疏油涂料与稀释剂混合后,涂敷于PTFE膜上,烘烤,得到所需疏水疏油PTFE复合膜。本发明所述的疏水疏油PTFE复合膜的制备方法不使用含C8氟单体,对环境更加友好,同时增强剂能够与PTFE膜中的纳米二氧化硅形成化学键合作用,增加疏水疏油涂料与PTFE膜的结合率,使PTFE复合膜具有稳定的疏水疏油性能。

Description

一种疏水疏油PTFE复合膜的制备方法
技术领域
本发明属于疏水疏油材料领域,尤其是涉及一种疏水疏油PTFE复合膜的制备方法。
背景技术
PTFE膜在电子防水防油污方面应用广泛,随着电子行业不断发展,PTFE膜的性能越来越不能适用现在市场发展的需要,对PTFE膜改性的研究越来越深入,其中对PTFE膜进行表面处理来提高其疏水疏油性,由于其超低表面性能与其它物质相溶性极差,对其表面改性多数为含氟聚合物进行后处理,这种常规的防水拒油剂在PTFE膜表面形成物理粘覆作用,无法达到长久稳定的效果,另外含氟聚合物是由含氟单体和一些功能单体进行共聚而得。但目前世界环保组织对含氟单体十分敏感,具有优异防水性能的C8(或者8个碳以上)单体被列为禁止生产和销售,而且近几年替代品C6也将要被限制。
公开号为CN 113072654 A的专利公开了一种含有全氟聚醚结构的高疏水疏油乳液的制备方法,专利含有短链全氟烷基的高疏水疏油乳液的制备方法,以水为溶剂,不含全氟长链烷基结构的全氟聚醚有优良的防水效果且原料安全,但其为水性溶剂与PTFE膜相溶性不好,不适用于PTFE膜处理;公开号为CN 112126327 B的专利公开了一种全氟聚醚型疏水疏油涂层组合物,是由全氟聚醚基团和硅氧烷基团组合而成,为了增加与材料之间的结合力,增加相应的硅氧烷基团,同时硅氧烷水解而成的羟基留在表层影响疏水疏油性,从而使PTFE膜的耐油污效果差,不易清洁。
发明内容
有鉴于此,本发明旨在提出一种疏水疏油PTFE复合膜的制备方法,不使用含C8氟单体,以得到具有稳定高效的疏水疏油效果的PTFE复合膜。
为达到上述目的,本发明的技术方案是这样实现的:
一种疏水疏油PTFE复合膜的制备方法,包括以下步骤:
S1:将四氟乙烯树脂、航空煤油、纳米二氧化硅混合搅拌并超声分散均匀,将混料通过挤出机挤出、压延机压制,得到膜片,将膜片加热去除航空煤油,之后横向及纵向拉伸得到PTFE膜;
S2:将含氟丙烯酸酯、增强剂、溶剂混合均匀,氮气保护下,在适当温度下缓慢滴加引发剂,滴加完毕之后加热至一定温度进行反应,反应完全后将反应液降温减压蒸馏,得到疏水疏油涂料;
S3:将疏水疏油涂料与稀释剂混合后,通过浸渍工艺涂敷于PTFE膜上,在适当温度下烘烤一定时间,得到所需疏水疏油PTFE复合膜;优选地,烘烤温度为50-80℃,烘烤时间为1-10min。
进一步地,四氟乙烯树脂、航空煤油、纳米二氧化硅的质量比为50-70:20-30:10-20;优选地,纳米二氧化硅的粒径为50-100nm。
进一步地,步骤S2中反应温度为55-75℃,反应时间为6-12h,减压蒸馏温度为40-50℃。
进一步地,所述增强剂为硅氧烷偶联剂;优选为A-171、A-172、A-151中的一种或多种;进一步优选为A-151。
进一步地,含氟丙烯酸酯、增强剂的质量比为2-4:1;优选为4:1。
进一步地,所述溶剂为四氢呋喃;优选地,溶剂的加入量为含氟丙烯酸酯、增强剂质量和的0.7-3;优选为1.2。
进一步地,所述引发剂为偶氮二异丁腈;优选地,引发剂的加入量为含氟丙烯酸酯、增强剂质量和的0.5%-5%;优选为1%。
进一步地,所述稀释剂为氢氟醚或全氟环醚;优选地,稀释后的疏水疏油涂料的浓度为0.1%-5%;进一步优选为0.5%。
进一步地,所述含氟丙烯酸酯为全氟聚醚丙烯酸酯或全氟烷基丙烯酸酯;优选地,所述全氟烷基丙烯酸酯包括全氟烷基乙基丙烯酸酯、全氟丁基乙基丙烯酸酯、全氟己基乙基丙烯酸酯、全氟辛基乙基丙烯酸酯、全氟癸基乙基丙烯酸酯一种或几种。
进一步地,所述全氟聚醚丙烯酸酯的制备方法包括以下步骤:
将三乙胺与过量的甲基丙烯酸羟乙酯混合后,氮气保护下滴加全氟聚醚酰氟得到混合液,搅拌加热至回流反应,得到反应液,去离子水洗反应液至中性,加入甲醇萃取除去水分,减压蒸馏得到全氟聚醚丙烯酸酯;优选地,全氟聚醚酰氟与甲基丙烯酸羟乙酯的摩尔比为1:1.05;优选地,三乙胺在混合液中的质量分数为0.1%-0.5%。
根据上述制备方法制得的疏水疏油PTFE复合膜。
相对于现有技术,本发明所述的疏水疏油PTFE复合膜的制备方法具有以下优势:
本发明所述的疏水疏油PTFE复合膜的制备方法不使用含C8氟单体,对环境更加友好,同时增强剂能够与PTFE膜中的纳米二氧化硅形成化学键合作用,增加疏水疏油涂料与PTFE膜的结合率,使PTFE复合膜具有稳定的疏水疏油性能。
具体实施方式
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。
下面结合实施例来详细说明本发明。
实施例1
步骤1:将聚四氟乙烯树脂粉末、航空煤油混合搅拌后,加入纳米二氧化硅粉末(粒径为50nm)继续混合搅拌并超声,聚四氟乙烯树脂粉末、航空煤油、纳米二氧化硅粉末的质量比为50:30:20,将混料通过挤出机挤出、经过压延机制成聚四氟乙烯膜片后,加热,去除航空煤油,进行横向及纵向拉伸,制得PTFE膜;
步骤2:称重甲基丙烯酸羟乙酯2.9g、三乙胺0.01g加入50ml三口烧瓶内,密封抽真空;通氮气,将7.1g全氟聚醚酰氟进行滴加,滴加完毕后,搅拌加热至一定温度回流反应,反应产物直接用去离子水洗除去过量的甲基丙烯酸羟乙酯和反应产物铵盐,重复多次至体系为中性,加入甲醇摇晃萃取除去水分,70℃减压蒸馏,得到全氟聚醚丙烯酸酯,加入2g硅氧烷偶联剂A-151,加入14.4g四氢呋喃搅拌均匀,通氮气情况下,在恒温60℃缓慢滴加偶氮二异丁腈;滴加完毕后,升温到75℃反应6小时待反应结束,将溶液降温至50℃减压蒸馏,得到全氟聚醚疏水疏油涂料;
步骤3:将得到的全氟聚醚疏水疏油涂料用稀释剂稀释为0.5%浓度的溶液,通过浸渍工艺涂于步骤1制得的PTFE膜,在50~80℃烘烤1-10min,得到疏水疏油PTFE复合膜。
实施例2
与实施例1的区别在于,将步骤1中的二氧化硅添加量改为10%,其它条件同实施例1;
实施例3
与实施例1的区别在于,步骤1中二氧化硅粉末的粒径为100nm,其它条件同实施例1;
实施例4
与实施例1的区别在于,将步骤2中的硅氧烷偶联剂改为A-171,其它条件同实施例1;
实施例5
与实施例1的区别在于,将步骤2中的硅氧烷偶联剂A-151添加量改为4g,其它条件同实施例1;
对比例1
与实施例1的区别在于,将步骤1中未加入二氧化硅粉末,其它条件同实施例1;
对比例2
与实施例1的区别在于,步骤1中二氧化硅粉末的粒径为200nm,其它条件同实施例1;
对比例3
与实施例1的区别在于,步骤2中未加入硅氧烷偶联剂A-151,其它条件同实施例1。
将实施例1-5、对比例1-3制得的PTFE复合膜及实施例1步骤1制得的PTFE膜分别进行水和正十六烷接触角检测,并测量摩擦后的水和正十六烷接触角,摩擦方法为:339型摩擦试验仪,负载500g,频次50次/min,摩擦1分钟,依据标准GB/T 10006-1988,检测结果如下表所示。
Figure SMS_1
Figure SMS_2
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,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 (13)

1.一种疏水疏油PTFE复合膜的制备方法,其特征在于,包括以下步骤:
S1:将四氟乙烯树脂、航空煤油、纳米二氧化硅混合搅拌均匀,挤出、压制、拉伸得到PTFE膜;
S2:将含氟丙烯酸酯、增强剂、溶剂混合均匀,氮气保护下,滴加引发剂,之后加热至反应完全,降温减压蒸馏,得到疏水疏油涂料,所述增强剂为硅氧烷偶联剂A-171、A-172、A-151中的一种或多种,所述含氟丙烯酸酯为全氟聚醚丙烯酸酯或全氟烷基丙烯酸酯;
S3:将疏水疏油涂料与稀释剂混合后,涂敷于PTFE膜上,烘烤,得到所需疏水疏油PTFE复合膜,
四氟乙烯树脂、航空煤油、纳米二氧化硅的质量比为50-70:20-30:10-20,纳米二氧化硅的粒径为50-100nm。
2.根据权利要求1所述的制备方法,其特征在于:步骤S2中反应温度为55-75℃,反应时间为6-12h,减压蒸馏温度为40-50℃。
3.根据权利要求1所述的制备方法,其特征在于:含氟丙烯酸酯、增强剂的质量比为2-4:1。
4.根据权利要求1所述的制备方法,其特征在于:所述溶剂为四氢呋喃。
5.根据权利要求4所述的制备方法,其特征在于:溶剂的加入量为含氟丙烯酸酯、增强剂质量和的0.7-3。
6.根据权利要求1所述的制备方法,其特征在于:所述引发剂为偶氮二异丁腈。
7.根据权利要求6所述的制备方法,其特征在于:引发剂的加入量为含氟丙烯酸酯、增强剂质量和的0.5%-5%。
8.根据权利要求1所述的制备方法,其特征在于:所述稀释剂为氢氟醚或全氟环醚。
9.根据权利要求8所述的制备方法,其特征在于:稀释后的疏水疏油涂料的浓度为0.1%-5%。
10.根据权利要求1所述的制备方法,其特征在于:所述全氟烷基丙烯酸酯包括全氟丁基乙基丙烯酸酯、全氟己基乙基丙烯酸酯、全氟辛基乙基丙烯酸酯、全氟癸基乙基丙烯酸酯一种或几种。
11.根据权利要求10所述的制备方法,其特征在于,所述全氟聚醚丙烯酸酯的制备方法包括以下步骤:
将甲基丙烯酸羟乙酯、三乙胺混合后,氮气保护下滴加全氟聚醚酰氟得到混合液,搅拌加热至回流反应,得到反应液,去离子水洗反应液至中性,加入甲醇萃取除去水分,减压蒸馏得到全氟聚醚丙烯酸酯。
12.根据权利要求11所述的制备方法,其特征在于:三乙胺在混合液中的质量分数为0.1%-0.5%。
13.根据权利要求1-12任一所述的制备方法制得的疏水疏油PTFE复合膜。
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