CN107955571A - 一种低粘度的硅烷改性聚醚基胶及其制备方法 - Google Patents

一种低粘度的硅烷改性聚醚基胶及其制备方法 Download PDF

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CN107955571A
CN107955571A CN201711306453.7A CN201711306453A CN107955571A CN 107955571 A CN107955571 A CN 107955571A CN 201711306453 A CN201711306453 A CN 201711306453A CN 107955571 A CN107955571 A CN 107955571A
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韩金
沈介泽
陈钦越
沈宇鹏
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种低粘度的硅烷改性聚醚基胶及其制备方法,采用异硫氰酸酯基硅烷封端聚醚,所得基胶内部含有硫代氨基甲酸酯单元;制备时,在反应器中依次加入1摩尔份端羟基的聚醚,2.1~3摩尔份的异硫氰酸酯基烷氧基硅烷,0~2摩尔份催化剂,0~100摩尔份溶剂,于‑5℃~100℃下反应1~24小时,再经纯化、干燥得到硅烷改性聚醚基胶。本发明所制得的基胶由于氢键强度低使得基胶粘度降低,有利于密封胶的生产、灌封与使用过程,有着良好的产业化前景。

Description

一种低粘度的硅烷改性聚醚基胶及其制备方法
技术领域
本发明属于有机胶领域,尤其涉及一种低粘度的硅烷改性聚醚基胶及其制备方法,具体得到一种烷氧基硅基封端的聚醚。
背景技术
密封胶广泛用于金属、玻璃,木材、硅酮树脂、加硫硅橡胶、陶瓷、天然及合成纤维,以及许多油漆塑料表面的粘接。聚氨酯密封胶含游离的异氰酸酯,且固化易产生气泡。硅酮密封胶撕裂强度低、涂饰性差、容易污染建材。硅烷改性聚醚密封胶(MS胶)是一种以端硅烷基聚醚为基础聚合物制备的高性能环保密封胶。MS胶兼具聚氨酯与硅酮密封胶的优点,克服了缺点,具有优良的力学强度、涂饰性、耐污性,且产品中无异氰酸酯及有机溶剂,是国内外新型弹性密封胶的主要发展方向。
MS胶的基胶制备技术以KANEKA与WACKER两家公司开发的技术为代表。对比两家技术,KANEKA的技术在力学性能上有优势,固化速度适中,基胶粘度低,然而,耐水性一般,基胶生产工艺复杂; WACKER的技术在力学性能、基胶粘度上不如KANEKA,固化速度过快,然而,耐水性好,基胶生产工艺相对简单。基胶粘度高会在生产、灌装、挤出时带来一系列的问题。瓦克基胶MS胶粘度高与固化速度过快的特点与端基中存在氨基甲酸酯单元有关。氨基甲酸酯单元中的酰胺部分会形成氢键作用,使得基胶变稠。
本案将采用异硫氰酸酯基烷氧基硅烷与端羟基聚醚进行反应,所生成的硫代氨基甲酸酯单元的氢键作用会弱许多,从而使基胶的粘度有所降低。
发明内容
本发明的目的是提供一种低粘度的硅烷改性聚醚基胶的高效简易制备方法。
为实现上述目的,提供以下技术方案:
一种低粘度的硅烷改性聚醚基胶,其特征在于,聚醚端基中包含如下式I的结构单元:
式中,R1、R2、R3为烷基或烷氧基,n为1-10。
表示由这里连接到分子链上。
相应的制备上述结构的硅烷改性聚醚基胶的制备方法,包括以下步骤:
在反应器中依次加入1摩尔份端羟基的聚醚,2.1~3摩尔份的异硫氰酸酯基烷氧基硅烷,0~2摩尔份催化剂,0~100摩尔份溶剂,于 -5℃~100℃下反应1~24小时,再经纯化、干燥得到硅烷改性聚醚基胶。
所谓端羟基的聚醚,是指该聚醚的两端均具有羟基。
优选的,所述的聚醚选自聚乙二醇、聚丙二醇、聚环氧丙烷、聚环氧乙烷,聚四氢呋喃、聚环氧丁烷、共聚环氧乙烷丙烷、共聚环氧乙烷四氢呋喃中的一种或几种,但不局限于此。
优选的,所述的异硫氰酸酯基烷氧基硅烷选自异硫氰酸酯丙基三甲氧基硅烷、异硫氰酸酯丙基三乙氧基硅烷、异硫氰酸酯丙基二甲氧基甲基硅烷、异硫氰酸酯甲基三甲氧基硅烷、异硫氰酸酯甲基二甲氧基甲基硅烷中的一种或几种,但不局限于此。
优选的,所述的催化剂为锡类或钛类催化剂,选自三丁基氧化锡、二月桂酸二丁锡、辛酸亚锡、钛酸四丁酯、钛酸三异丙酯中的一种或几种。
优选的,所述的溶剂选自甲苯、苯、氯仿、二氯甲烷、四氢呋喃、二噁烷、己烷、乙醚、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮中的一种或者几种的混合物,但不局限于此。
本发明的有益效果是采用异硫氰酸酯硅烷所制得基胶的粘度比采用异氰酸酯硅烷所制得基胶的粘度低,而且制备过程工艺简单、反应快速、固化时的自催化作用弱等特点,有着良好的产业化前景。
具体实施方式
本发明的原理是利用异硫氰酸酯基硅烷所生成的硫代氨基甲酸酯基所形成的氢键相互作用较低,从而使聚醚基胶的粘度降低。
下面根据实施例进一步说明本发明,本发明的目的和效果将变得更加明显。
实施例1:
在反应器中依次加入1摩尔份端羟基的聚环氧乙烷(数均分子量10000),3摩尔份的异硫氰酸酯丙基三甲氧基硅烷,0摩尔份催化剂, 0摩尔份溶剂,于100℃下反应1小时,再经纯化、干燥得到硅烷改性聚醚基胶。
实施例2:
在反应器中依次加入1摩尔份端羟基的聚环氧乙烷(数均分子量 10000),2.1摩尔份的异硫氰酸酯丙基三甲氧基硅烷,2摩尔份三丁基氧化锡,100摩尔份乙酸乙酯,于-5℃下反应24小时,再经纯化、干燥得到硅烷改性聚醚基胶。
实施例3:
在反应器中依次加入1摩尔份端羟基的聚环氧丙烷(数均分子量 20000),2.2摩尔份的异硫氰酸酯基烷氧基硅烷,0.1摩尔份三丁基氧化锡,0.2摩尔份乙酸乙酯,于25℃下反应24小时,再经纯化、干燥得到硅烷改性聚醚基胶。
基胶产品物理性质:无色透明(APHA<30),室温时基胶黏度 36000mPa.s左右。
实施例4:
在反应器中依次加入1摩尔份端羟基的环氧乙烷环氧丙烷共聚物,2.3摩尔份的异硫氰酸酯丙基二甲氧基甲基硅烷,0.2摩尔份钛酸四丁酯,1摩尔份四氢呋喃,于50℃下反应12小时,再经纯化、干燥得到硅烷改性聚醚基胶。
实施例5:
在反应器中依次加入1摩尔份端羟基的聚四氢呋喃,2.5摩尔份的异硫氰酸酯甲基三甲氧基硅烷,0.2摩尔份辛酸亚锡,于27℃下反应12小时,再经纯化、干燥得到硅烷改性聚醚基胶。
实施例6:
在反应器中依次加入1摩尔份端羟基的环氧乙烷环氧丙烷共聚物,2.3摩尔份的异硫氰酸酯丙基三乙氧基硅烷,0.2摩尔份三丁基氧化锡,1摩尔份乙酸乙酯,于25℃下反应24小时,再经纯化、干燥得到硅烷改性聚醚基胶。
实施例7:
在反应器中依次加入1摩尔份端羟基的聚环氧丙烷(数均分子量 20000),2.3摩尔份的异硫氰酸酯丙基甲基二甲氧基硅烷,,于60℃下反应12小时,再经纯化、干燥得到硅烷改性聚醚基胶。
基胶产品物理性质:无色透明(APHA<30),室温时基胶黏度 35000mPa.s左右。

Claims (6)

1.一种低粘度的硅烷改性聚醚基胶,其特征在于:聚醚端基中包含如下式I的结构单元:
式中,R1、R2、R3为烷基或烷氧基,n为1-10。
2.一种权利要求1所述硅烷改性聚醚基胶的制备方法,其特征在于:
包括以下步骤:
在反应器中依次加入1摩尔份端羟基的聚醚,2.1~3摩尔份的异硫氰酸酯基烷氧基硅烷,0~2摩尔份催化剂,0~100摩尔份溶剂,于-5℃~100℃下反应1~24小时,再经纯化、干燥得到硅烷改性聚醚基胶。
3.根据权利要求2所述的硅烷改性聚醚基胶的制备方法,其特征在于:所述的聚醚选自聚乙二醇、聚丙二醇、聚环氧丙烷、聚环氧乙烷,聚四氢呋喃、聚环氧丁烷、共聚环氧乙烷丙烷、共聚环氧乙烷四氢呋喃中的一种或几种。
4.根据权利要求2所述的硅烷改性聚醚基胶的制备方法,其特征在于,所述的异硫氰酸酯基烷氧基硅烷选自异硫氰酸酯丙基三甲氧基硅烷、异硫氰酸酯丙基三乙氧基硅烷、异硫氰酸酯丙基二甲氧基甲基硅烷、异硫氰酸酯甲基三甲氧基硅烷、异硫氰酸酯甲基二甲氧基甲基硅烷中的一种或几种。
5.根据权利要求2所述的硅烷改性聚醚基胶的制备方法,其特征在于,所述的催化剂选自三丁基氧化锡、二月桂酸二丁锡、辛酸亚锡、钛酸四丁酯、钛酸三异丙酯中的一种或几种。
6.根据权利要求2所述的硅烷改性聚醚基胶的制备方法,其特征在于,所述的溶剂选自甲苯、苯、氯仿、二氯甲烷、四氢呋喃、二噁烷、己烷、乙醚、乙酸乙酯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基吡咯烷酮中的一种或者几种的混合物。
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WO2020094974A1 (fr) * 2018-11-09 2020-05-14 Bostik Sa Dérivés 1,3-oxathiolane-2-thione et leurs utilisations
FR3088325A1 (fr) * 2018-11-09 2020-05-15 Bostik Sa Derives 1,3-oxathiolane-2-thione et leurs utilisations
CN112969691A (zh) * 2018-11-09 2021-06-15 博斯蒂克股份公司 1,3-氧硫杂环戊烷-2-硫酮衍生物及其用途
CN112068722A (zh) * 2019-06-11 2020-12-11 Oppo(重庆)智能科技有限公司 电子装置及电子装置的装配方法
CN110845695A (zh) * 2019-11-27 2020-02-28 上海东大化学有限公司 一种遇水膨胀硅烷聚醚型树脂及其制备方法
CN110845695B (zh) * 2019-11-27 2021-10-22 上海东大化学有限公司 一种遇水膨胀硅烷聚醚型树脂及其制备方法

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