CN114015037B - 一种硅烷封端聚醚的合成方法及应用 - Google Patents
一种硅烷封端聚醚的合成方法及应用 Download PDFInfo
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Abstract
本发明提供了一种硅烷封端聚醚的合成方法及应用。该烷封端聚醚的合成方法包括如下步骤:将聚醚和丙烯酸酯在阻聚剂的存在下,加热进行脱醇反应,再加入氨基硅烷偶联剂,在100~150℃下反应2~10h,降温除杂,即得。使用本发明提供的合成方法得到的硅烷封端聚醚可作为制备硅烷改性聚醚密封胶的基胶使用,使用的原料价廉易得,合成的硅烷封端聚醚反应活性适中,有利于下游MS胶生产厂家根据性能要求做相应的配方调整。本发明提供的合成步骤简单,反应条件温和,适用于所有分子量的聚醚。
Description
技术领域
本发明涉及密封胶的合成技术领域,更具体地,涉及一种硅烷封端聚醚的合成方法及应用。
背景技术
硅烷改性聚醚密封胶是近年来开发的一种替代硅酮胶与聚氨酯密封胶的新型密封胶,其综合了硅酮胶与聚氨酯胶的优点,在建筑、家装等行业具有广泛的应用。硅烷改性聚醚密封胶又称硅烷封端聚醚密封胶,以烷氧基硅烷改性的硅烷化聚醚为基胶,主要以端硅烷基聚醚(MS)为主,可通过硅氢化法、加成法、异氰酸酯法、环氧开环法来制备,其中硅氢加成法制备工艺简单,封端率尚可,但以氯丙烯等封端后的烯丙基聚醚多有颜色,对应用体系不友好。异氰酸酯法以多元醇聚醚、异氰酸酯基硅烷、有机锡催化所得,需引入催化剂、且异氰酸酯基硅烷反应活性高、高毒、成本高。环氧开环法多利用伯、仲氨基化合物与环氧的开环反应将环氧基封端的聚醚与含环氧基硅烷的化合物链接起来,需要首先制备环氧封端的聚醚,但工序略复杂。也有研究采用低分子量的聚醚胺与氨基硅烷经迈克尔反应制备硅烷改性聚醚,这种硅烷改性聚醚分子链短,在链端共有12个可反应的Si-OCH3,反应活性偏高,存在在实际配制MS胶时,生产过程容易出现凝胶等问题,这些问题限制了其在市场上的应用推广。
发明内容
本发明的第一目的在于提供一种硅烷封端聚醚的合成方法,使用该方法合成得到的硅烷封端聚醚可作为制备硅烷改性聚醚密封胶的基胶使用,该合成方法步骤简单,反应条件温和。
该硅烷封端聚醚的合成方法,包括如下步骤:
将聚醚和丙烯酸酯在阻聚剂的存在下,加热进行脱醇反应,再加入氨基硅烷偶联剂,在100~150℃下反应2~10h,降温除杂,即得。
在本发明中,聚醚优选为聚乙二醇或聚丙二醇,更优选为聚丙二醇,进一步优选为分子量为1000~8000的聚丙二醇,进一步优选分子量2000~4000的聚丙二醇。在本发明一个优选实施方式中,丙烯酸酯可以为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸羟乙酯或(甲基)丙烯酸羟丙酯。当丙烯酸酯为甲基丙烯酸羟乙酯或甲基丙烯酸羟丙酯时,为了提高反应效率需要加入四氯化锡、氯化锌、三氯化氯、氯化亚锡等常见的路易斯酸,优选四氯化锡。路易斯酸的加入量可以为丙烯酸酯的1~5wt%。在本发明中丙烯酸酯更优选为甲基丙烯酸甲酯或丙烯酸乙酯,进一步优选为甲基丙烯酸甲酯。
在本发明中阻聚剂可以使用本领域中常用的酚类或胺类阻聚剂,优选为酚类阻聚剂,进一步优选为2,5-二叔丁基对苯二酚。
在本发明一个优选实施方式中,所述聚醚与丙烯酸酯的摩尔比为(2~3):1,优选为(2.1~2.5):1。阻聚剂为丙烯酸酯的0.02~2wt%,优选0.05~0.12wt%。
在本发明中,脱醇反应的终点为:加热进行脱醇反应至微回流,直至副产的甲醇蒸馏至基本无馏分,反应结束。加热的反应温度通常为80~110℃。
在本发明一个优选实施方式中,所述氨基硅烷偶联剂为伯氨基或仲氨基硅烷,优选为氨丙基三甲氧基硅烷、氨丙基三乙氧基硅烷或氨丙基甲基二甲氧基硅烷等伯氨基硅烷。其中,氨基硅烷偶联剂与聚醚的摩尔比优选为(2.1~3.5):1,进一步优选为(2.2~2.6):1。
本发明提供的合成方法还包括如下步骤:脱醇反应后除去甲醇和未反应完的丙烯酸酯,再向体系中加入氨基硅烷偶联剂。
在本发明一个优选实施方式中,加入氨基硅烷偶联剂后的反应温度为120~130℃,反应时间为3~6h。在本发明提供的合成方法中,除杂通常包括减压蒸馏除杂。
在本发明另一个优选实施方式中,硅烷封端聚醚的合成方法包括如下步骤:将聚丙二醇和甲基丙烯酸甲酯在2,5-二叔丁基对苯二酚的存在下,加热进行脱醇反应,反应结束后除去甲醇和未反应完的甲基丙烯酸甲酯,再加入氨丙基三甲氧基硅烷,在100~150℃下反应2~10h,降温除杂,即得;其中,聚醚为分子量2000~4000的聚丙二醇;丙烯酸酯为甲基丙烯酸甲酯;阻聚剂为2,5-二叔丁基对苯二酚。
在本发明另一个优选实施方式中,硅烷封端聚醚的合成方法包括如下步骤:将聚醚和丙烯酸酯在阻聚剂的存在下,加热进行脱醇反应,反应结束后除去甲醇和未反应完的丙烯酸甲酯,再加入氨基硅烷偶联剂,在100~150℃下反应2~10h,降温除杂,即得;其中,所述聚醚与丙烯酸酯的摩尔比为(2~3):1;所述阻聚剂为丙烯酸酯的0.05~2wt%;所述氨基硅烷偶联剂与聚醚的摩尔比为(2.1~3.5):1。
在本发明提供的上述合成方法中,优选在氮气的保护下进行。
本发明的另一目的在于提供上述合成方法得到的硅烷封端聚醚。
本发明的再一目的在于提供上述合成方法或由上述合成方法得到的硅烷封端聚醚在制备密封胶中应用。
本发明的有益效果为:
使用本发明提供的合成方法得到的硅烷封端聚醚可作为制备硅烷改性聚醚密封胶的基胶使用,使用的原料价廉易得,合成的硅烷封端聚醚反应活性适中,有利于下游MS胶生产厂家根据性能要求做相应的配方调整,得到的密封胶的表干时间适中,可以很好的满足市场的需求。本发明提供的合成方法,合成步骤简单,反应条件温和,适用于所有分子量的聚醚。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1
本实施例提供了一种硅烷封端聚醚,其合成方法包括如下步骤:
氮气保护下,在三口烧瓶中加入5.3g甲基丙烯酸甲酯,100g分子量4000PPG,0.043g 2,5-二叔丁基对苯二酚,80℃下反应至微回流,蒸馏收集副产的甲醇,继续升温未反应完的甲基丙烯酸甲酯,并不断升温至基本无馏分,得到不饱和双键改性聚醚,再向其中加入10.1g氨丙基三甲氧基硅烷,于120-125℃下反应3h,降温油泵-0.8MPa,真空脱除未反应的氨丙基三甲氧基硅烷,得无色至淡黄色透明硅烷封端聚醚。
实施例2
本实施例提供了一种硅烷封端聚醚,其合成方法包括如下步骤:
氮气保护下,在三口烧瓶中加入6.3g甲基丙烯酸甲酯,100g分子量4000PPG,0.006g 2,5-二叔丁基对苯二酚,85℃加热至出现微回流,蒸馏收集副产的甲醇,缓慢升温至110℃蒸馏回收未反应完的甲基丙烯酸甲酯,并不断升温至基本无馏分,得到不饱和双键改性聚醚,再向其中加入11.7g氨丙基三甲氧基硅烷,于125-130℃下反应6h,降温油泵-0.8MPa,真空脱除未反应的氨丙基三甲氧基硅烷,得淡黄色透明硅烷封端聚醚。
实施例3
本实施例提供了一种硅烷封端聚醚,其合成方法包括如下步骤:
氮气保护下,在三口烧瓶中加入7.0g甲基丙烯酸甲酯,100g分子量4000PPG,0.004g 2,5-二叔丁基对苯二酚,90℃加热至出现微回流,蒸馏收集副产的甲醇,缓慢升温至120℃蒸馏回收未反应完的甲基丙烯酸甲酯,并不断升温至基本无馏分,得到不饱和双键改性聚醚,再向其中加入13.5g氨丙基三甲氧基硅烷,于130-135℃下反应8h,降温油泵-0.8MPa,真空脱除未反应的氨丙基三甲氧基硅烷,得淡黄色透明硅烷封端聚醚。
实施例4
本实施例提供了一种硅烷封端聚醚,其合成方法包括如下步骤:
氮气保护下,在三口烧瓶中加入6g甲基丙烯酸乙酯,100g分子量4000PPG,0.005g2,5-二叔丁基对苯二酚,80℃加热至微回流,蒸馏收集副产的甲醇,缓慢升温至100℃蒸馏收集未反应完的甲基丙烯酸乙酯,并不断升温至基本无馏分,得到不饱和双键改性聚醚,再向其中加入12.2g氨丙基三乙氧基硅烷,于120-125℃下反应3h,降温真空脱除未反应的氨丙基三乙氧基硅烷,得淡黄色透明硅烷封端聚醚。
实施例5
本实施例提供了一种硅烷封端聚醚,其合成方法包括如下步骤:
氮气保护下,在三口烧瓶中加入6.9g甲基丙烯酸羟乙酯,50g分子量2000PPG,0.2g四氯化锡,0.006g 2,5-二叔丁基对苯二酚,80℃加热至微回流,蒸馏升温至115℃除杂,并不断升温至基本无馏分,得到不饱和双键改性聚醚,再向其中加入9.2g氨丙基甲基二甲氧基硅烷,于120-125℃下反应3h,降温真空除杂,得淡黄色透明硅烷封端聚醚。
实施例6
本实施例提供了一种硅烷封端聚醚,其合成方法包括如下步骤:
氮气保护下,在三口烧瓶中加入6.9g甲基丙烯酸羟乙酯,200g分子量8000PPG,0.2g三氯化铝,0.006g 2,5-二叔丁基对苯二酚,搅拌升温至出现回流,蒸馏除杂,并不断升温至基本无馏分,得到不饱和双键改性聚醚,再向其中加入9.2g氨丙基甲基二甲氧基硅烷,于120-125℃下反应3h,降温真空除杂,得淡黄色透明硅烷封端聚醚。
实验例
使用本发明实施例和对比例所得硅烷封端聚醚来制备密封胶进行性能测试。
对比例1为采用CN202010975443.8中实施例1得到的硅烷改性聚醚,将其作为硅烷封端聚醚作为本发明实施例的对比例。
本发明实验例中密封胶的制备配方与方法为:称取100份上述实施例和对比例的硅烷封端聚醚、80份分子量3000PPG、200份纳米碳酸钙、5份气相法白炭黑低速搅拌10min至均匀;在真空度为-0.1~-0.09MPa,温度100℃~120℃条件下高速搅拌,脱水1h;而后降温至35℃以下后添加5份乙烯基三甲氧基硅烷,在真空度为-0.1~-0.09MPa条件下高速搅拌10min;加入8份各实施例和对比例中对应的氨基硅烷偶联剂,在真空度为-0.1~-0.09MPa条件下高速搅拌10min;加入1份二月桂酸二丁基锡,继续在真空度为-0.1~-0.09MPa条件下高速搅拌10min后出料,即得所述的硅烷改性聚醚密封胶。测试项:按照GB/T13477.5-2002规定的A方法进行测试胶的表干时间,结果如下表1所示。
表1密封胶性能结果表
最后,本发明的方法仅为较佳的实施方案,并非用于限定本发明的保护范围。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种硅烷封端聚醚的合成方法,其特征在于,包括如下步骤:
将聚醚和丙烯酸酯在阻聚剂的存在下,加热进行脱醇反应,除去甲醇和未反应完的丙烯酸酯,再加入氨基硅烷偶联剂,在100~150℃下反应2~10h,降温除杂,即得;所述聚醚为分子量1000~8000的聚丙二醇;所述丙烯酸酯为甲基丙烯酸甲酯;所述阻聚剂为2,5-二叔丁基对苯二酚;所述聚醚与丙烯酸酯的摩尔比为(2~3):1;所述阻聚剂为丙烯酸酯的0.05~2wt%;所述氨基硅烷偶联剂为氨丙基三甲氧基硅烷;所述氨基硅烷偶联剂与聚醚的摩尔比为(2.1~3.5):1。
2.根据权利要求1所述的合成方法,其特征在于,所述聚醚为分子量2000~4000的聚丙二醇。
3.根据权利要求1或2所述的合成方法,其特征在于,所述聚醚与丙烯酸酯的摩尔比为(2.1~2.5):1。
4.根据权利要求1或2所述的合成方法,其特征在于,所述阻聚剂为丙烯酸酯的0.08~0.15wt%。
5.根据权利要求1或2所述的合成方法,其特征在于,所述氨基硅烷偶联剂与聚醚的摩尔比为(2.2~2.6):1。
6.根据权利要求1或2所述的合成方法,其特征在于,所述合成方法在氮气的保护下进行。
7.权利要求1至6中任一项所述的合成方法得到的硅烷封端聚醚。
8.权利要求7所述的硅烷封端聚醚在制备密封胶中的应用。
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