CN107236130B - 一种uv光固化氟硅离型剂及其制备方法 - Google Patents
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Abstract
Description
技术领域
本发明涉及高分子材料制备领域,具体涉及一种UV光固化氟硅离型剂及其制备方法。
背景技术
离型剂是表面具有分离效果,与特定的材料在一定条件下接触不具有粘附力或者具有轻微粘附力的涂层。目前,聚硅氧烷是市场用量最大的离型剂。然而,有机硅离型剂对有机硅胶粘剂的离型效果显著。而引入氟素基团后,利用氟硅之间的不相容性,可以大幅度提高离型剂的离型效果。因此,氟硅离型剂是用于保护特种胶粘剂(特别是耐高温胶粘剂、有机硅胶粘剂)表面的离型涂层,也用于有机硅橡胶的过程保护。
目前的氟硅离型剂主要是采用热固化的方式,即在铂金催化剂作用下利用硅氢加成反应进行固化。然而,这种传统的固化方式需要在较高的温度(通常为150~170℃)下进行;采用的铂金催化剂价格相当昂贵。
发明内容
针对上述现有技术中存在的缺陷,本发明提供一种UV光固化氟硅离型剂及其制备方法。本发明的UV光固化氟硅离型剂,其制备方法简单,可以解决高温固化、催化剂昂贵的问题。
即,本发明提供一种UV光固化氟硅离型剂,其结构式如下:
其中,R1为CnH2n+1,n=1~9;
R3为C2H4CnF2nC2H4,n=1~9;R4为C2H4Rf,Rf为氟醚基团或者氟烷基;x=1~5000、y=1~5000、z=0~5000、w=1~5000。
本发明还提供一种如上所述的UV光固化氟硅离型剂的制备方法,其以物质的量计,由下述各成分聚合而成:
其中,
其中,3≤u+v≤6,1≤t≤10,R为CnH2n+1,Rf为CnF2n+1或O(CF2CFCF3)nF,Rf1为C2H4CnF2nC2H4,n=1~9。
此外,
R为含有环氧基的基团。
此外,
此外,有机硅封端剂为硅氧烷的二聚体或者短链的硅油。
此外,
此外,所述催化剂为强酸、强碱或者暂时性催化剂。
此外,其特征在于,将除催化剂外所有成分加入到反应釜中,减压至-0.09MPa,通入氮气,在50℃恒温条件下脱水,然后升温至70~100℃,加入催化剂,反应4~10h,加入酸或碱中和催化剂后,升温至150~200℃拔除低沸点硅油后,冷却过滤得到无色透明的UV光固化氟硅离型剂。
本发明还提供一种根据如上所述的UV光固化氟硅离型剂的应用,其将阳离子光固化剂与UV光固化氟硅离型剂混合均匀后涂布于PET膜上,UV光固化后得到离型涂层。其中,所述阳离子光固化剂优选BF3的络合物或HPF6。
本发明的UV光固化氟硅离型剂在保证了优异的离型性等性能。并且本发明的UV光固化氟硅离型剂的制备方法,不需高温固化,不需要昂贵的催化剂,具有环保、经济、高效、节能和适用性广的优点,因此该技术可以广泛地适用于涂层、胶粘剂行业。
附图说明
图1是实施例1中制得的UV光固化氟硅离型剂的红外谱图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅是本发明的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
离型膜的离型力根据GB/T 2792-2014,拉力机拉伸速率为300mm/min;残余粘着率测试根据GB/T25256-2010,拉力机拉伸速率为300mm/min。接触角的测试:将氟素离型膜放置在接触角测试仪平台上,滴加去离子水和二碘甲烷两种液体,测试其在表面摊开后的接触角。
实施例1
将五甲基全氟辛基环三硅氧烷10mol,八甲基环四硅氧烷40mol,缩水甘油醚丙基七甲基环四硅氧烷5mol,缩水甘油醚丙基四甲基二硅氧烷0.2mol加入到反应釜中,减压,通入氮气,在50℃恒温条件下脱水,然后升温至75℃,加入0.1mol三氟磺酸,反应10h,加入碱中和催化剂后,升温至150℃拔除低沸点硅油后,冷却过滤得到无色透明的UV光固化氟硅离型剂。红外谱图如图1所示,结构式如下:
将所制备的UV光固化氟硅离型剂与HPF6混合均匀后涂布于PET薄膜上,通过UV光固化后得到离型涂层。其性能测试如下:
表1、接触角和表面能测试
表2、离型性能及耐热性测试
离型力(g/25mm) | 残余附着力(%) | |
数值 | 2 | 95 |
实施例2
将五甲基全氟醚三硅氧烷30mol,短链氟硅油10mol,八甲基环四硅氧烷10mol,缩水甘油醚丙基六甲基环四硅氧烷10mol,缩水甘油醚丙基四甲基硅油0.1mol加入到反应釜中,减压至0.09MPa,通入氮气,在50℃恒温条件下脱水,然后升温至120℃,加入0.1mol KOH,反应10h,加入酸中和催化剂后,升温至200℃拔除低沸点硅油后,冷却过滤得到无色透明的氟硅氧烷。
将所制备的氟硅氧烷与HPF6混合均匀后涂布于PET薄膜上,通过UV光固化后得到离型涂层。其性能测试如下:
表3、接触角和表面能测试
水 | 二碘甲烷 | |
接触角/表面能 | 120° | 89° |
表4、离型性能及耐热性测试
实施例3
将五甲基全氟辛基环三硅氧烷60mol,短链氟硅油40mol,缩水甘油醚丙基七甲基环四硅氧烷20mol,缩水甘油醚丙基四甲基二硅氧烷5mol加入到反应釜中,减压,通入氮气,在50℃恒温条件下脱水,然后升温至75℃,加入0.01mol三氟磺酸,反应10h,加入碱中和催化剂后,升温至150℃拔除低沸点硅油后,冷却过滤得到无色透明的UV光固化氟硅离型剂。
将所制备的UV光固化氟硅离型剂与HPF6混合均匀后涂布于PET薄膜上,通过UV光固化后得到离型涂层。其性能测试如下:
表5、接触角和表面能测试
水 | 二碘甲烷 | |
接触角/表面能 | 118° | 88° |
表6、离型性能及耐热性测试
离型力(g/25mm) | 残余附着力(%) | |
数值 | 3 | 97 |
实施例4
将五甲基全氟醚三硅氧烷80mol,短链氟硅油20mol,八甲基环四硅氧烷20mol,缩水甘油醚丙基六甲基环四硅氧烷15mol,缩水甘油醚丙基四甲基硅油10mol加入到反应釜中,减压至0.09MPa,通入氮气,在50℃恒温条件下脱水,然后升温至120℃,加入0.1mol KOH,反应10h,加入酸中和催化剂后,升温至200℃拔除低沸点硅油后,冷却过滤得到无色透明的氟硅氧烷。
将所制备的氟硅氧烷与HPF6混合均匀后涂布于PET薄膜上,通过UV光固化后得到离型涂层。其性能测试如下:
表7、接触角和表面能测试
水 | 二碘甲烷 | |
接触角/表面能 | 120° | 87° |
表8、离型性能及耐热性测试
离型力(g/25mm) | 残余附着力(%) | |
数值 | 4 | 96 |
Claims (10)
2.一种权利要求1所述的UV光固化氟硅离型剂的制备方法,其特征在于,以物质的量计,由下述各成分聚合而成:
氟硅环体 10~80份、
短链氟硅油 0~80份、
烷烃基有机硅环体 0~80份、
环氧基有机硅环体 5~20份、
有机硅封端剂 0.1~10份、
催化剂 0.01~0.1份。
6.根据权利要求2所述的制备方法,其特征在于,有机硅封端剂为硅氧烷的二聚体或者短链的硅油。
8.根据权利要求2所述的制备方法,其特征在于,所述催化剂为强酸、强碱或者暂时性催化剂。
9.根据权利要求2-8中任意一项所述的制备方法,其特征在于,将除催化剂外所有成分加入到反应釜中,减压至-0.01~0.09MPa,通入氮气,在50℃恒温条件下脱水,然后升温至70~100℃,加入催化剂,反应4~10h,加入酸或碱中和催化剂后,升温至150~200℃拔除低沸点硅油后,冷却过滤得到无色透明的UV光固化氟硅离型剂。
10.一种根据权利要求1所述的UV光固化氟硅离型剂的应用,其特征在于,将阳离子光固化剂与UV光固化氟硅离型剂混合均匀后涂布于PET膜上,UV光固化后得到离型涂层。
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