CN112794981A - 一种乙烯基全氟聚乙二醇改性弹性聚氨酯及其应用 - Google Patents

一种乙烯基全氟聚乙二醇改性弹性聚氨酯及其应用 Download PDF

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CN112794981A
CN112794981A CN202110026791.5A CN202110026791A CN112794981A CN 112794981 A CN112794981 A CN 112794981A CN 202110026791 A CN202110026791 A CN 202110026791A CN 112794981 A CN112794981 A CN 112794981A
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Abstract

本发明涉及一种乙烯基全氟聚乙二醇改性弹性聚氨酯，其特征在于，按重量份数计，其制备方法为：在氮气保护下，在反应器中加入50‑60份含乙烯基全氟聚乙二醇、6‑14份二异氰酸酯单体、12‑25份有机溶剂，开启搅拌将物料搅拌均匀，加热至60‑90℃反应2‑3h后；然后逐滴滴加0.05‑0.15份催化剂，滴加完毕后60‑90℃继续反应1‑2h，反应过程中每0.5h测量体系‑NCO百分含量，当体系达到目标‑NCO百分含量为小于0.5％后，降温至室温，然后通过减压蒸馏除去有机溶剂，即得含乙烯基全氟聚乙二醇改性弹性聚氨酯。由该聚氨酯制成的爽滑且富有弹性的有机硅离型剂能够和格拉辛纸粘贴紧密，同时具有更加易于剥离的优点。

Description

一种乙烯基全氟聚乙二醇改性弹性聚氨酯及其应用
技术领域
本发明属于聚氨酯技术领域，涉及一种乙烯基全氟聚乙二醇改性弹性聚氨酯及其应用。
背景技术
离型剂组合物涂布于纸、合成树脂膜、合成纤维或布等各种基材表面上并使其固化而形成固化层，由此可以形成对于压敏性粘接剂等粘合性物质具有剥离性的膜。作为这种离型剂组合物，已知有含有具有含氟原子的硅氧烷单元的有机聚硅氧烷的物质。有机硅涂层是目前抗粘污涂料领域的一个重要方向，由于其具有低表面张力、透明、无毒、耐高温、耐候性佳等优点，广泛应用在金属、陶瓷、纸张、塑料、纺织品表面作为防污涂料或者防粘附涂料使用。
但是，现有的离型剂组合物虽然对于有机树脂系粘合性物质的固化膜的剥离性优异，但是，存在着对于以二甲基聚硅氧烷或甲基苯基聚硅氧烷等有机聚硅氧烷为主要成分的有机硅系粘合剂的剥离性差的问题。其结果，有时因用途而对于有机硅系粘合剂的剥离性变得不充分。另外，涂布离型剂组合物并进行固化而制造带状的离型片及叠层体的情况下，通常带状的离型片等被卷绕成辊状，在卷绕体的状态下运输及保管。此时，特别是已知有在对卷绕体的中心部施加卷压，但也存在着通过施加该卷压，对于粘合性物质导致离型层重剥离化的问题。本发明增加了离型剂组合物的爽滑性和弹性，获得剥离性能优异的有机硅离型剂.
发明内容
为克服现有技术的缺点和不足，本发明旨在提供一种爽滑且富有弹性的有机硅离型剂。
本发明采取以下技术方案，一种爽滑且富有弹性的有机硅离型剂，其特征在于，其配方组成按重量份数计为：含乙烯基全氟聚乙二醇改性弹性聚氨酯20-30份，乙烯基聚硅氧烷80-100份，含氢聚硅氧烷6-12份，防粘剂2-4份，锚固剂1-3份，铂类催化剂2-10份。
所述的乙烯基聚硅氧烷为端乙烯基聚硅氧烷，粘度为2000-20000cp，乙烯基含量为0.01-0.1％；所述含氢聚硅氧烷的粘度为20-50cp，含氢量为0.3-1.2％。
所述的锚固剂为乙烯基三甲氧基硅烷、乙烯基三-(β-甲氧基乙氧基)硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的至少一种。
所述的铂类催化剂为氯铂酸-二乙烯基四甲基二硅氧烷，氯铂酸-异丙醇，氯铂酸-邻苯二甲酸二乙酯中的至少一种。
所述的防粘剂为4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯、乙二醇二缩水甘油酯、季戊四醇四缩水甘油醚中的至少一种。
按重量份数计，所述的含乙烯基全氟聚乙二醇改性弹性聚氨酯制备方法为：
在氮气保护下，在反应器中加入50-60份含乙烯基全氟聚乙二醇、6-14份二异氰酸酯单体、12-25份有机溶剂，开启搅拌将物料搅拌均匀，加热至60-90℃反应2-3h后；然后逐滴滴加0.05-0.15份催化剂，滴加完毕后60-90℃继续反应1-2h，反应过程中每0.5h测量体系-NCO百分含量，当体系达到目标-NCO百分含量为小于0.5％后，降温至室温，然后通过减压蒸馏除去有机溶剂，即得含乙烯基全氟聚乙二醇改性弹性聚氨酯。
所述的含乙烯基全氟聚乙二醇为烯丙基全氟聚乙二醇、异戊烯基全氟聚乙二醇中的至少一种，其相对分子量为600-2000；二异氰酸酯单体为MDI、HDI、TDI中的至少一种；所述的有机溶剂为乙酸乙酯、丙酮、乙酸丁酯丁酮、乙酸丙酯中的至少一种；所述的催化剂为二月桂酸二丁基锡、辛酸亚锡、环烷酸锡、环烷酸钴中的至少一种。
所述的爽滑且富有弹性的有机硅离型剂，其制备方法为：把配方量的含乙烯基全氟聚乙二醇改性弹性聚氨酯、乙烯基聚硅氧烷、含氢聚硅氧烷、防粘剂、锚固剂加入至混合装置中，搅拌15-30min；再加入配方量的铂类催化剂，搅拌1～5min，即得所述的爽滑且富有弹性的有机硅离型剂。
将本发明爽滑且富有弹性的有机硅离型剂涂布在基材上，在155-180℃下固化，即得离型纸。
相对于现有技术，本发明具有以下优点或有益结果：
(1)含乙烯基全氟聚乙二醇改性弹性聚氨酯的加入，全氟聚乙二醇结构增加了所述有机硅离型剂的疏油性、疏水性，使得其更加易于剥离；
(2)聚氨酯结构弹性增加了所述有机硅离型剂的韧性，提高了其抗冲击性、耐拉伸性能，进而使其用于离型纸的使用过程中，能够紧密贴合的同时，无挪动移位现象，且不会被拉断；
(3)锚固剂与含氢聚硅氧烷反应参与反应，增加了离型剂对离型纸的结合性。
具体实施方式
下面结合实施例对本发明的一种爽滑且富有弹性的有机硅离型剂做进一步的描述。可以理解的是，此处所描述的具体实施例仅仅用于解释相关发明，而非对该发明的限定。
实施例1
一种含乙烯基全氟聚乙二醇改性弹性聚氨酯X，按重量份数计，其制备方法为：
在氮气保护下，在反应器中加入54份异戊烯基全氟聚乙二醇、9份MDI、18份丙酮，开启搅拌将物料搅拌均匀，加热至78℃反应3h后；然后逐滴滴加0.10份辛酸亚锡，滴加完毕后78℃继续反应2h，反应过程中每0.5h测量体系-NCO百分含量，当体系达到目标-NCO百分含量为小于0.5％后，降温至室温，然后通过减压蒸馏除去有机溶剂，即得含乙烯基全氟聚乙二醇改性弹性聚氨酯X。
实施例2
一种爽滑且富有弹性的有机硅离型剂，其特征在于，其配方组成按重量份数计为：含乙烯基全氟聚乙二醇改性弹性聚氨酯X30份，端乙烯基聚硅氧烷(粘度为5000cp，乙烯基含量为0.04％)80份，含氢聚硅氧烷(粘度为50cp，含氢量为0.3％)12份，乙二醇二缩水甘油酯2份，乙烯基三-(β-甲氧基乙氧基)硅烷3份，氯铂酸-二乙烯基四甲基二硅氧烷2份。
实施例3
一种爽滑且富有弹性的有机硅离型剂，其特征在于，其配方组成按重量份数计为：含乙烯基全氟聚乙二醇改性弹性聚氨酯X20份，端乙烯基聚硅氧烷(粘度为20000cp，乙烯基含量为0.01％)100份，含氢聚硅氧烷(粘度为20cp，含氢量为1.2％)6份，4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯4份，γ-(甲基丙烯酰氧)丙基三甲氧基硅烷1份，氯铂酸-邻苯二甲酸二乙酯10份。
实施例4
一种爽滑且富有弹性的有机硅离型剂，其特征在于，其配方组成按重量份数计为：含乙烯基全氟聚乙二醇改性弹性聚氨酯X24份，端乙烯基聚硅氧烷(粘度为2000cp，乙烯基含量为0.1％)86份，含氢聚硅氧烷(粘度为40cp，含氢量为0.7％)8份，季戊四醇四缩水甘油醚3份，乙烯基三甲氧基硅烷2份，氯铂酸-异丙醇4份。
实施例2-4爽滑且富有弹性的有机硅离型剂的制备方法为：把配方量的含乙烯基全氟聚乙二醇改性弹性聚氨酯、乙烯基聚硅氧烷、含氢聚硅氧烷、防粘剂、锚固剂加入至混合装置中，搅拌15-30min；再加入配方量的铂类催化剂，搅拌1～5min，即得所述的爽滑且富有弹性的有机硅离型剂。
相同条件下将本发明实施例2-4爽滑且富有弹性的有机硅离型剂和市售离型剂(对比例)涂布在格拉辛纸上，155-180℃下固化，即得离型纸，实施例2-4和对比例所得离型纸的性能数据如下表1。
表1离型剂的性能表
实施例2 实施例3 实施例4 对比例
常温剥离力g/mm 2.5 1.6 1.7 8.5
老化剥离力g/mm 2.9 1.9 2.4 11.3
纸张和离型剂的贴合度 紧密 紧密 紧密 紧密
由表1可以看出实施例和对比例均能和格拉辛纸粘贴紧密，同时实施例更加易于剥离。
尽管本发明已作了详细说明并引用了实施例，但对于本领域的普通技术人员，显然可以按照上述说明而做出的各种方案、修改和改动，都应该包括在权利要求的范围之内。

Claims (10)

1.一种乙烯基全氟聚乙二醇改性弹性聚氨酯，其特征在于，按重量份数计，其制备方法为：在氮气保护下，在反应器中加入50-60份含乙烯基全氟聚乙二醇、6-14份二异氰酸酯单体、12-25份有机溶剂，开启搅拌将物料搅拌均匀，加热至60-90℃反应2-3h后；然后逐滴滴加0.05-0.15份催化剂，滴加完毕后60-90℃继续反应1-2h，反应过程中每0.5h测量体系-NCO百分含量，当体系达到目标-NCO百分含量为小于0.5％后，降温至室温，然后通过减压蒸馏除去有机溶剂，即得含乙烯基全氟聚乙二醇改性弹性聚氨酯。
2.根据权利要求1所述的一种乙烯基全氟聚乙二醇改性弹性聚氨酯，其特征在于，所述的含乙烯基全氟聚乙二醇为烯丙基全氟聚乙二醇、异戊烯基全氟聚乙二醇中的至少一种，其相对分子量为600-2000；二异氰酸酯单体为MDI、HDI、TDI中的至少一种。
3.根据权利要求1所述的一种乙烯基全氟聚乙二醇改性弹性聚氨酯，其特征在于，所述的有机溶剂为乙酸乙酯、丙酮、乙酸丙酯中的至少一种；所述的催化剂为二月桂酸二丁基锡、辛酸亚锡、环烷酸锡、环烷酸钴中的至少一种。
4.一种如权利要求1至权利要求3中任一项的乙烯基全氟聚乙二醇改性弹性聚氨酯的应用，其特征在于，所述的乙烯基全氟聚乙二醇改性弹性聚氨酯应用于爽滑且富有弹性的有机硅离型剂。
5.根据权利要求4所述的应用，其特征在于，所述的爽滑且富有弹性的有机硅离型剂，其配方组成按重量份数计为：含乙烯基全氟聚乙二醇改性弹性聚氨酯20-30份，乙烯基聚硅氧烷80-100份，含氢聚硅氧烷6-12份，防粘剂2-4份，锚固剂1-3份，铂类催化剂2-10份。
6.根据权利要求5所述的应用，其特征在于，所述的乙烯基聚硅氧烷为端乙烯基聚硅氧烷，粘度为2000-20000cp，乙烯基含量为0.01-0.1％；所述含氢聚硅氧烷的粘度为20-50cp，含氢量为0.3-1.2％。
7.根据权利要求5所述的应用，其特征在于，所述的防粘剂为4,5-环氧环己烷-1,2-二甲酸二缩水甘油酯、乙二醇二缩水甘油酯、季戊四醇四缩水甘油醚中的至少一种。
8.根据权利要求5所述的应用，其特征在于，所述的锚固剂为乙烯基三甲氧基硅烷、乙烯基三-(β-甲氧基乙氧基)硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷中的至少一种。
9.根据权利要求5所述的应用，其特征在于，所述的铂类催化剂为氯铂酸-二乙烯基四甲基二硅氧烷、氯铂酸-异丙醇、氯铂酸-邻苯二甲酸二乙酯中的至少一种。
10.根据权利要求5所述的应用，其特征在于，爽滑且富有弹性的有机硅离型剂的制备方法为：把配方量的含乙烯基全氟聚乙二醇改性弹性聚氨酯、乙烯基聚硅氧烷、含氢聚硅氧烷、防粘剂、锚固剂加入至混合装置中，搅拌15-30min；再加入配方量的铂类催化剂，搅拌1～5min，即得所述的一种爽滑且富有弹性的有机硅离型剂。
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