CN106674450A - 三嵌段杂合氟硅聚合物及其制备方法 - Google Patents
三嵌段杂合氟硅聚合物及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种三嵌段杂合氟硅聚合物，其特征在于：结构式如下：；其中：Rf为含氟链段，Rsi为含硅链段，R1为异氰酸酯中两个NCO的间隔基团。本发明所制备三嵌段杂合氟硅涂层固化后具有良好的附着力和优异的表面惰性，可用于超轻离型剂，也可以作为船舶保护涂层。
Description
技术领域
本发明涉及高分子化合物技术领域，尤其是一种三嵌段杂合氟硅聚合物，及其制备方法。
背景技术
有机硅涂层具有许多独特的性能，如耐候、耐老化、耐臭氧、憎水、难燃等，这些优异性能为其他的有机高分子涂层所不能比拟和替代。因此，有机硅涂层在航空航天、电子电气、化工纺织、医疗卫生、机械建筑等领域均已得到了广泛的应用。然而，有机硅涂层在有机溶剂、燃烧油、润滑油的溶胀度较大。另外，有机硅涂层的表面能尽管已经很小，为21～22mN/m，但还不够理想。这些都大大限制了有机硅涂层的应用。目前最为有效的方法是将含氟基团引入有机硅涂层中，全氟烷表面能为10mN/m，表面能远远小于有机硅树脂。将氟烷基引入到硅氧烷链，可以得到柔性、超低表面能、低摩擦系数的涂层，使得有机硅涂层应用于更多的领域。
目前，文献报道的将含氟基团引入有机硅涂层主要采用两种途径：一是有机硅合成的过程中，加入含氟硅烷进行共聚；二是利用有机硅树脂中的α氢，将含氟单体接枝到有机硅树脂中。这两种方法均是将氟烷基引入到有机硅树脂的侧链上，且采用的均是含有氟烷基的小分子。利用现有的含氟大分子进行有机硅树脂的共聚改性未见报道。
发明内容
本发明针对现有技术的不足，提出一种三嵌段杂合氟硅聚合物，能解决有机硅涂层在有机溶剂和燃烧油中膨胀系数较大，表面能不够理想的问题。
为了实现上述发明目的，本发明提供以下技术方案：一种三嵌段杂合氟硅聚合物，其特征在于：结构式如下：
；
其中：Rf为含氟链段，Rsi为含硅链段，R1为异氰酸酯中两个NCO的间隔基团。
进一步地，含氟链段为、、、、、或,分子量为100～5000。
进一步地，含硅链段为，其中X为CH3、C2H5、OCH3、OC2H5、C6H5、F、Cl、Br、I的一种。
进一步地，R1为如下结构中的一种：
一种如上所述三嵌段杂合氟硅聚合物的制备方法，包括以下步骤：
⑴、按照重量份配比称取各组分：
端羟基氟聚合物 50
异氰酸酯 1～10
2-羟基-2-甲基-1-苯基-1-丙酮 0.1～5
有机锡类催化剂 0.01～1
溶剂 200～300
硅烷乙烯单体 1～100；
⑵、将端羟基氟聚合物、异氰酸酯、2-羟基-2-甲基-1-苯基-1-丙酮、有机锡类催化剂溶于部分溶剂中，部分溶剂占溶剂总重量的50%～70%；搅拌并升温至50～90℃，恒温反应3～8h；
⑶、降至30～60℃后，加入硅烷乙烯单体和余下溶剂的混合溶液，通入氮气，在紫外等照射下反应1～24h，得到三嵌段杂合氟硅聚合物。
进一步地，端羟基氟聚合物为偏氟乙烯-六氟丙烯共聚物、偏氟乙烯-六氟丙烯-四氟乙烯共聚物、偏氟乙烯-全氟甲基乙烯基醚共聚物、偏氟乙烯-全氟正丙基乙烯基醚共聚物、四氟乙烯-全氟甲基乙烯基醚共聚物、四氟乙烯-全氟正丙基乙烯基醚共聚物、全氟聚醚中的一种，且聚合物端基为羟基。
进一步地，异氰酸酯为六亚甲基二异氰酸酯、4，4'-亚甲基双(异氰酸苯酯)、异佛尔酮二异氰酸酯、4,4'-二异氰酸基-3,3'-二甲基联苯、2,4-甲基苯异氰酸酯、2,6-甲基苯异氰酸酯中的一种。
进一步地，溶剂是苯类、酯类、酮类中的一种。
进一步地，有机硅单体的结构式为：，其中，X可以为CH3、C2H5、OCH3、OC2H5、C6H5、F、Cl、Br、I的一种。
与现有技术相比，本发明具有以下优点：三嵌段杂合氟硅涂层固化后具有良好的附着力和优异的表面惰性，可用于超轻离型剂，也可以作为船舶保护涂层，加入二胺、二酚、硅烷偶联剂等固化剂后得到氟硅杂合涂层。
具体实施方式
下面结合实施例对本发明进行详细描述，本部分的描述仅是示范性和解释性，不应对本发明的保护范围有任何的限制作用。
实施例1
端羟基全氟聚醚50份、异佛尔酮异氰酸酯2份、2-羟基-2-甲基-1-苯基-1-丙酮 0.1份、二月桂酸异丁烯0.02份溶于第一部分丙酮溶剂（60份）中，加入到反应釜中，80℃恒温反应一段时间，降至60℃后，迅速加入硅烷乙烯单体50份和第二部分丙酮溶剂（40份）的混合溶液，通入氮气一段时间后，在紫外等照射下进行光聚合反应，得到三嵌段杂合氟硅聚合物如下：
将其用KH550进行固化后，可得到对PET薄膜附着力良好的涂层性能如下：
实施例2
端羟基VDF-HFP橡胶50份、六亚甲基异氰酸酯3份、2-羟基-2-甲基-1-苯基-1-丙酮 0.6份、二月桂酸异丁烯0.1份溶于第一部分乙酸乙酯溶剂（50份）中，加入到反应釜中，80℃恒温反应一段时间，降至60℃后，迅速加入硅烷乙烯单体50份和第二部分丙酮溶剂（50份）的混合溶液，通入氮气一段时间后，在紫外等照射下进行光聚合反应，得到三嵌段杂合氟硅聚合物如下：
采用AF和KH550进行双重固化，得到的性能如下
实施例3
端羟基全氟聚醚50份、异佛尔酮异氰酸酯2份、2-羟基-2-甲基-1-苯基-1-丙酮 0.1份、二月桂酸异丁烯0.02份溶于第一部分丙酮溶剂（60份）中，加入到反应釜中，80℃恒温反应一段时间，降至60℃后，迅速加入含氟乙烯基硅烷单体50份和第二部分丙酮溶剂（40份）的混合溶液，通入氮气一段时间后，在紫外等照射下进行光聚合反应，得到三嵌段杂合氟硅聚合物如下：
与实施例1相比，由于含氟乙烯基硅烷的引入，使得表面降低到9mN/m。其性能如下：
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (9)
1.一种三嵌段杂合氟硅聚合物，其特征在于：结构式如下：
；其中：Rf为含氟链段，Rsi为含硅链段，R1为异氰酸酯中两个NCO的间隔基团。
2.如权利要求1所述三嵌段杂合氟硅聚合物，其特征在于：含氟链段为、、、、、或，分子量为100～5000。
3.如权利要求1所述三嵌段杂合氟硅聚合物，其特征在于：含硅链段为，其中X为CH3、C2H5、OCH3、OC2H5、C6H5、F、Cl、Br、I的一种。
4.如权利要求1所述三嵌段杂合氟硅聚合物，其特征在于：R1为如下结构中的一种：
。
5.一种如权利要求1所述三嵌段杂合氟硅聚合物的制备方法，其特征在于：包括以下步骤：
⑴、按照重量份配比称取各组分：
端羟基氟聚合物 50
异氰酸酯 1～10
2-羟基-2-甲基-1-苯基-1-丙酮 0.1～5
有机锡类催化剂 0.01～1
溶剂 200～300
硅烷乙烯单体 1～100；
⑵、将端羟基氟聚合物、异氰酸酯、2-羟基-2-甲基-1-苯基-1-丙酮、有机锡类催化剂溶于部分溶剂中，部分溶剂占溶剂总重量的50%～70%；搅拌并升温至50～90℃，恒温反应3～8h；
⑶、降至30～60℃后，加入硅烷乙烯单体和余下溶剂的混合溶液，通入氮气，在紫外等照射下反应1～24h，得到三嵌段杂合氟硅聚合物。
6.如权利要求5所述制备方法，其特征在于：端羟基氟聚合物为偏氟乙烯-六氟丙烯共聚物、偏氟乙烯-六氟丙烯-四氟乙烯共聚物、偏氟乙烯-全氟甲基乙烯基醚共聚物、偏氟乙烯-全氟正丙基乙烯基醚共聚物、四氟乙烯-全氟甲基乙烯基醚共聚物、四氟乙烯-全氟正丙基乙烯基醚共聚物、全氟聚醚中的一种，且聚合物端基为羟基。
7.如权利要求5所述制备方法，其特征在于：异氰酸酯为六亚甲基二异氰酸酯、4，4'-亚甲基双(异氰酸苯酯)、异佛尔酮二异氰酸酯、4,4'-二异氰酸基-3,3'-二甲基联苯、2,4-甲基苯异氰酸酯、2,6-甲基苯异氰酸酯中的一种。
8.如权利要求5所述制备方法，其特征在于：溶剂是苯类、酯类、酮类中的一种。
9.如权利要求5所述制备方法，其特征在于：有机硅单体的结构式为：，其中，X可以为CH3、C2H5、OCH3、OC2H5、C6H5、F、Cl、Br、I的一种。
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