CN106554749A - 一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶及其制备方法 - Google Patents
一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶及其制备方法 Download PDFInfo
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Abstract
本发明公开一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶,有以下重量份的原料组成:α,ω‑二羟基聚二甲基硅氧烷55‑70,纳米SiO2 5‑9,环氧丙醇10‑18,聚醚多元醇20‑30,2,4‑甲苯二异氰酸酯12‑18,二月桂酸二丁基锡1‑2,γ‑氨丙基三乙氧基硅烷7‑16,无水甲醇适量,0.4mol/L甲醇钠溶液适量,乙醇适量,四正丁基钛酸酯2‑5,羟基清除剂1‑3。本发明在SiO2纳米粒子表面原位接枝聚环氧丙醇,之后将其复合到聚氨酯预聚体中,在胶料中引入聚氨酯预聚体,使得复合密封胶兼具聚氨酯与硅酮密封胶二者的优点,密封胶具有更高的力学强度和粘结强度,同时提高胶体的低温柔韧性、耐黄变性能。
Description
技术领域
本发明涉及硅橡胶制备技术领域,具体涉及一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶及其制备方法。
背景技术
硅酮密封胶是以聚二甲基硅氧烷为主要原料,辅以交联剂、填料、增塑剂、偶联剂、催化剂在真空状态下混合而成的膏状物,在室温下通过与空气中的水发生应固化形成弹性硅橡胶。单组份脱醇型室温硫化硅橡胶硫化过程中释放出醇,相比于脱酸型、和脱酮肟型,具有环保、无腐蚀的优点,可广泛应用于建筑、电子电气、航天航空、汽车工业等行业,作为一种绿色环保的胶黏剂醇型密封胶将是未来市场应用的趋势。
谢桂荣、姜宏伟等人在其《聚氨酯改性端硅烷聚醚密封胶的研究》一文中,研究了端异氰酸酯基聚氨酯和端硅烷氧基聚氨酯与端硅烷聚醚复合制备的密封胶,经聚氨酯改性后的密封胶材料具有更好的透明性和力学性能,同时还展现出良好低温柔韧性、耐黄变性能。
本发明采用阴离子聚合法,在SiO2纳米粒子表面原位接枝聚环氧丙醇,改善了其与胶料间的结合力,之后将其复合到聚氨酯预聚体中,通过利用γ-氨丙基三乙氧基硅烷与-NCO封端的聚氨酯预聚体反应,在胶料中引入聚氨酯预聚体,使得复合密封胶兼具聚氨酯与硅酮密封胶二者的优点,密封胶具有更高的力学强度和粘结强度,同时提高胶体的低温柔韧性、耐黄变性能。
发明内容
针对现有技术的不足,本发明提供一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶及其制备方法。
一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶,有以下重量份的原料组成:α,ω-二羟基聚二甲基硅氧烷55-70份,纳米SiO2 5-9份,环氧丙醇10-18份,聚醚多元醇20-30份,2,4-甲苯二异氰酸酯12-18份,二月桂酸二丁基锡1-2份,γ-氨丙基三乙氧基硅烷7-16份,无水甲醇适量,0.4mol/L甲醇钠溶液适量,乙醇适量,四正丁基钛酸酯2-5份,羟基清除剂1-3份。
具体步骤如下:
(1)纳米SiO2表面原位接枝聚环氧丙醇:
①、取0.4mol/L甲醇钠溶液,加入纳米SiO2,超声震荡8-14分钟,继续反应50-70分钟,停止反应后,采用无水甲醇洗涤,再经干燥、研磨得到表面醇钠处理的纳米SiO2;
②、将上述表面醇钠处理的纳米SiO2,分子筛除水过的环氧丙醇加入三口烧瓶内,控制搅拌速度300-500r/min,温度105-115℃,氮气保护,反应40-55分钟后离心分离,并用乙醇洗涤,经干燥得表面接枝聚环氧丙醇的纳米SiO2;
(2)纳米SiO2复合聚氨酯预聚体的制备:
在装有搅拌器和温度计的三口烧瓶中加入聚醚多元醇,在100-120℃条件下,真空减压脱水1-3小时,降温至60℃以下,改用机械搅拌,加入步骤(1)改性后的纳米SiO2搅拌均匀,之后加入2,4-甲苯二异氰酸酯和二月桂酸二丁基锡,通入N2,升温至70-90℃回流反应6-8小时,得到纳米SiO2复合聚氨酯预聚体;
(3)硅烷封端聚氨酯预聚体的合成:
在装有搅拌器和温度计的三口烧瓶中加入上述复合聚氨酯预聚体、γ-氨丙基三乙氧基硅烷,真空保护下加热至65-75℃,搅拌下反应1-3小时,制得硅烷封端聚氨酯预聚体;
(4)密封胶的制备:
将α,ω-二羟基聚二甲基硅氧烷与步骤(3)制备的硅烷封端聚氨酯预聚体、四正丁基钛酸酯、羟基清除剂,加入行星搅拌机中,保持真空度0.08-0.09MPa搅拌35-45分钟,获得脱醇型硅酮密封胶,通过压盘将该密封胶装入塑料胶瓶中密封保存。
其中,所述羟基清除剂为六甲基二硅氮烷。
与现有技术相比,本发明具有以下优点:
(1)本发明利用γ-氨丙基三乙氧基硅烷与-NCO封端的聚氨酯预聚体反应,将聚氨酯预聚体中的-NCO基全部被封端变成-Si(OC2H5)3,一方面利用硅烷封端的水解性能作为交联剂,在接触大气中的湿气时,迅速发生水解反应生成硅醇,与生胶中的Si-OH基发生缩合反应,从而导致单组分室温硫化硅橡胶的固化交联,另一方面引入聚氨酯预聚体,使得复合密封胶兼具聚氨酯与硅酮密封胶二者的优点,密封胶具有更高的力学强度和粘结强度,同时提高胶体的低温柔韧性、耐黄变性能。
(2)本发明采用阴离子聚合法,在SiO2纳米粒子表面引发环氧丙醇开环聚合,原位接枝聚环氧丙醇,接枝后纳米SiO2粒子仍呈规则球形,之后将其复合到聚氨酯预聚体中,随后通过聚氨酯预聚体的改性添加到密封胶中,增加SiO2纳米粒子与胶体的相容性,使其均匀稳定地分散在反应体系中,改善了与胶料间的结合力,使胶体的伸长率、拉伸强度、贮存稳定性等综合性能提高。
具体实施方式
一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶,有以下重量份的原料组成:α,ω-二羟基聚二甲基硅氧烷65,纳米SiO2 7,环氧丙醇15,聚醚多元醇25,2,4-甲苯二异氰酸酯16,二月桂酸二丁基锡2,γ-氨丙基三乙氧基硅烷14,无水甲醇适量,0.4mol/L甲醇钠溶液适量,乙醇适量,四正丁基钛酸酯3,羟基清除剂2。
具体步骤如下:
(1)纳米SiO2表面原位接枝聚环氧丙醇:
①、取0.4mol/L甲醇钠溶液,加入纳米SiO2,超声震荡10分钟,继续反应60分钟,停止反应后,采用无水甲醇洗涤,再经干燥、研磨得到表面醇钠处理的纳米SiO2;
②、将上述表面醇钠处理的纳米SiO2,分子筛除水过的环氧丙醇加入三口烧瓶内,控制搅拌速度400r/min,温度110℃,氮气保护,反应45分钟后离心分离,并用乙醇洗涤,经干燥得表面接枝聚环氧丙醇的纳米SiO2;
(2)纳米SiO2复合聚氨酯预聚体的制备:
在装有搅拌器和温度计的三口烧瓶中加入聚醚多元醇,在110℃条件下,真空减压脱水2小时,降温至60℃以下,改用机械搅拌,加入步骤(1)改性后的纳米SiO2搅拌均匀,之后加入2,4-甲苯二异氰酸酯和二月桂酸二丁基锡,通入N2,升温至80℃回流反应7小时,得到纳米SiO2复合聚氨酯预聚体;
(3)硅烷封端聚氨酯预聚体的合成:
在装有搅拌器和温度计的三口烧瓶中加入上述复合聚氨酯预聚体、γ-氨丙基三乙氧基硅烷,真空保护下加热至70℃,搅拌下反应2小时,制得硅烷封端聚氨酯预聚体;
(4)密封胶的制备:
将α,ω-二羟基聚二甲基硅氧烷与步骤(3)制备的硅烷封端聚氨酯预聚体、四正丁基钛酸酯、羟基清除剂,加入行星搅拌机中,保持真空度0.08-0.09MPa搅拌40分钟,获得脱醇型硅酮密封胶,通过压盘将该密封胶装入塑料胶瓶中密封保存。
其中,所述羟基清除剂为六甲基二硅氮烷。
性能测试结果:
拉伸强度:2.24MPa,剪切强度:2.08MPa,断裂伸长率:246%,硬度:43A;
耐黄变性具体性能为:密封胶从胶管挤出胶料后,马上放入120℃烘箱,24小时不发黄。
Claims (3)
1.一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶,其特征在于,有以下重量份的原料组成:α,ω-二羟基聚二甲基硅氧烷55-70份,纳米SiO2 5-9份,环氧丙醇10-18份,聚醚多元醇20-30份,2,4-甲苯二异氰酸酯12-18份,二月桂酸二丁基锡1-2份,γ-氨丙基三乙氧基硅烷7-16份,无水甲醇适量,0.4mol/L甲醇钠溶液适量,乙醇适量,四正丁基钛酸酯2-5份,羟基清除剂1-3份。
2.根据权利要求书1所述的一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶的制备方法,其特征在于,具体步骤如下:
(1)纳米SiO2表面原位接枝聚环氧丙醇:
①、取0.4mol/L甲醇钠溶液,加入纳米SiO2,超声震荡8-14分钟,继续反应50-70分钟,停止反应后,采用无水甲醇洗涤,再经干燥、研磨得到表面醇钠处理的纳米SiO2;
②、将上述表面醇钠处理的纳米SiO2,分子筛除水过的环氧丙醇加入三口烧瓶内,控制搅拌速度300-500r/min,温度105-115℃,氮气保护,反应40-55分钟后离心分离,并用乙醇洗涤,经干燥得表面接枝聚环氧丙醇的纳米SiO2;
(2)纳米SiO2复合聚氨酯预聚体的制备:
在装有搅拌器和温度计的三口烧瓶中加入聚醚多元醇,在100-120℃条件下,真空减压脱水1-3小时,降温至60℃以下,改用机械搅拌,加入步骤(1)改性后的纳米SiO2搅拌均匀,之后加入2,4-甲苯二异氰酸酯和二月桂酸二丁基锡,通入N2,升温至70-90℃回流反应6-8小时,得到纳米SiO2复合聚氨酯预聚体;
(3)硅烷封端聚氨酯预聚体的合成:
在装有搅拌器和温度计的三口烧瓶中加入上述复合聚氨酯预聚体、γ-氨丙基三乙氧基硅烷,真空保护下加热至65-75℃,搅拌下反应1-3小时,制得硅烷封端聚氨酯预聚体;
(4)密封胶的制备:
将α,ω-二羟基聚二甲基硅氧烷与步骤(3)制备的硅烷封端聚氨酯预聚体、四正丁基钛酸酯、羟基清除剂,加入行星搅拌机中,保持真空度0.08-0.09MPa搅拌35-45分钟,获得脱醇型硅酮密封胶,通过压盘将该密封胶装入塑料胶瓶中密封保存。
3.根据权利要求书1、2所述的一种单组分脱醇型硅烷封端聚氨酯改性硅酮密封胶的制备方法,其特征在于,所述羟基清除剂为六甲基二硅氮烷。
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CN110016223A (zh) * | 2019-04-15 | 2019-07-16 | 泉州邦尼生物科技有限公司 | 一种软木聚氨酯鞋底材料及其制备方法 |
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