CN114163630A - 一种ms胶基础树脂及其制备方法 - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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Abstract
本发明公开了一种MS胶基础树脂及其制备方法,属于化工材料技术领域,其由聚醚胺化合物与环氧硅烷化合物按照摩尔比1:2‑1:4.5,在40‑80℃反应1‑6小时制备。环氧化合物为3‑(2,3‑环氧丙氧)丙基三甲氧基硅烷、3‑(2,3‑环氧丙氧)丙基三甲乙基硅烷,醚胺化合物为官能度2或3的,分子量200‑5000之间聚醚胺。本发明的MS胶基础树脂制备方法不需要使用刺激性强的烯丙基硅氧烷、也不需要异氰酸丙基硅氧烷和含氢硅氧烷,不使用二异氰酸酯化合物,所得到的硅氧烷封端聚醚MS胶基础树脂制备工艺简单,所生产的产品性能稳定。
Description
技术领域
本发明属于化工材料技术领域,具体涉及一种MS胶基础树脂及其制备方法。
背景技术
MS是改性硅烷聚醚胶,改性硅烷modified silicone的缩写。它是继聚硫胶、硅酮胶、聚氨酯胶之后发展起来的新一代建筑密封胶。MS胶有一系列的树脂产品,综合了硅酮(市场上大部分的玻璃胶、幕墙胶)和聚氨酯(主要用于工业胶)的大部分优点而无太多缺点的一个新材料,综合性能非常突出。无溶剂、无毒害、不粘污、不发泡、可涂饰、高弹性、高粘接性等等。国外高市场占有率证明了他的价值。
MS预聚体即基础树脂,或称硅烷改性树脂预聚体,其本身强度不高,若采用MS胶基础树脂制备密封胶,必须添加能起到一定补强作用的填料。填料的种类和用量显著影响密封胶的力学性能和流变性能。
目前已知的MS预聚体,即MS基础树脂有三种合成方法:
方法一是,聚醚或聚酯多元醇与含有异氰酸酯的硅氧烷,如异氰酸丙基三乙氧基硅氧烷反应,制得硅氧烷封端聚醚或聚酯,即MS基础树脂。反应机理如下:
异氰酸酯硅氧烷化合物制备硅氧烷封端树脂
方法二是,聚醚或聚酯多元醇先与两倍物质的量的含有二异氰酸化合物,如甲苯二异氰酸酯(TDI),二苯基甲烷二异氰酸酯(MDI)或六亚甲基二异氰酸酯(HDI)等反应,制备异氰酸酯基封端的聚醚或聚酯,然后再与含氨基的硅氧烷化合物,如3-氨基丙基三乙氧基硅氧烷反应,制备硅氧烷封端聚醚或聚酯,即MS基础树脂。反应过程如下:
二异氰酸酯化合物与氨基硅氧烷制备硅氧烷封端树脂
方法三是:聚醚多元醇先与氯丙烯反应,制备烯丙基封端聚醚,然后,再与含氢硅氧烷,如三乙氧基硅烷在氯铂酸催化剂下进行加成反应,制备硅氧烷封端聚醚。美国专利US9328272、US8962716和US9969843中均介绍了这种制备硅氧烷封端聚酯的制备方法。烯丙基封端聚醚的硅氢加成路线如下所示:
烯丙基封端聚醚与含氢硅烷制备硅氧烷封端聚醚树脂
以上三种硅氧烷封端树脂的制备方法是最常规的方法,但是也各有利弊。如第一种方法所使用的异氰酸基丙基硅氧烷原料成本较高;第二种方法因在使用MDI或TDI封端时容易分子交联和扩链,造成工艺控制较难,产品质量波动;第三种方法所制备的硅氧烷,有着要使用到刺激性较大烯丙基氯,且硅氢加成所使用的氯铂酸盐价格较高,催化剂在树脂中残留等问题,同时制备的硅氧烷封端树脂中缺少极性较大的氨基甲酸酯基、芳环等结构,所制备的树脂偏软,硬度和强度较低。
本发明介绍一种全新的硅氧烷封端聚醚制备方法,其是由聚醚胺与环氧环硅烷偶联剂,如3-(2,3-环氧丙氧)丙基三甲氧基硅烷(偶联剂KH560)或3-(2,3-环氧丙氧)丙基三乙基硅烷反应制得。其中,聚醚胺分子中的每个氨基可以和2 分子的环氧环硅烷偶联剂反应,故其反应结果可能有双硅氧烷化化合物Ⅰ,三硅氧烷化化合物Ⅱ,四硅氧烷化化合物Ⅲ三种可能,其制备路线如下:
不同于普通聚醚,聚醚胺是将聚醚两端的羟基氨化而得到。已经工业化的聚醚胺有:亨斯迈公司的JEFFAMINE Polyetheramines D和ED系列,其产品有:JEFFAMINE D-230,JEFFAMINE D-400,JEFFAMINE D-2000,JEFFAMINE D-4000,JEFFAMINE ED-600JEFFAMINE HK-511,JEFFAMINE ED-900 JEFFAMINEED-2003等;国内的聚醚胺生产厂家主要有:扬州晨化新材料有限公司、无锡阿科力科技股份有限公司。阿科力科技股份有限公司其双官能产品有MA-223,MA-240,MA-2200,MA-2203ED,三个氨基的聚醚胺有MA-340;扬州晨化新材料有限公司的聚醚胺产品有:CAED-600,CAED-900, CAED-2003,CAD-230,CAD-400,CAD-2000,和三官能的CAT-5000,CAT-403。聚醚胺产品常用在环氧树脂固化剂、水性硅油等领域,在本发明是利用其与环氧硅氧烷之间的反应,制备硅氧烷封端聚醚,进而用于MS树脂密封胶。
发明内容
本发明的目的在于提供一种MS胶基础树脂及其制备方法,以解决上述背景技术中提出的问题,本发明所制备的硅氧烷封端聚醚用的原料为聚醚胺和环氧硅烷化合物;本发明所制备的硅氧烷封端聚醚为具有以下三种结构化合物的混合物:
R为甲基、乙基,
n代表聚醚胺的聚合度,为5-68的自然数。
更优选本发明的硅氧烷封端聚醚树脂(MS胶基础树脂)具有如下所示结构式:
所述的硅氧烷封端聚醚树脂,其制备方法是:在干燥无水的反应器中,氮气保护下,将聚醚胺化合物与环氧硅烷化合物按照摩尔比1:2-1:4.5进行,在 40-80℃下反应1-6小时得到。反应方程式如下:
所述的,所述的聚醚胺为2-3官能度的聚醚胺,分子量在200-5000之间,如:D-230,D-400,D-2000, D-4000,ED-600HK-511,ED-900 ED-2003,阿科力科技股份有限公司的MA-223,MA-240,MA-2200,MA-2203ED,三个氨基的聚醚胺有MA-340,扬州晨化新材料有限公司的CAED-600,CAED-900, CAED-2003,CAD-230,CAD-400,CAD-2000,和三官能的CAT-5000,CAT-403。
所述的,环氧硅氧烷为:3-(2,3-环氧丙氧)丙基三甲氧基硅烷或3-(2,3-环氧丙氧)丙基三甲乙基硅烷,其结构式分别如下:
所述的,硅氧烷封端聚醚树脂方法是聚醚胺化合物与环氧硅烷化合物按照摩尔比1:2-1:4.5进行。
所述的,硅氧烷封端聚醚树脂方法是反应温度为40-80℃下,反应时间为 1-6小时。
不同于三种常见的硅氧烷封端树脂(MS胶基础树脂)制备方法聚醚,本发明的硅氧烷封端树脂(MS树脂)及其制备方法至少具有以下的好处:
1.本发明制备的硅氧烷封端聚醚,不需要使用刺激性强的烯丙基硅氧烷、也不需要使用成本较高的异氰酸丙基硅氧烷和含氢硅氧烷;
2.本发明制备的硅氧烷封端聚醚制备方法简单,不需要高温反应和氯铂酸盐催化剂;
3.本发明制备的硅氧烷封端聚醚制不需要使用二异氰酸酯化合物,如甲苯二异氰酸酯(TDI),二苯基甲烷二异氰酸酯(MDI)或六亚甲基二异氰酸酯(HDI)等;
4.本发明制备的硅氧烷封端聚醚MS胶基础树脂制备工艺简单,所生产的产品性能稳定。
附图说明
图1为实施例1中产品1#的1HNMR图谱;
图2为实施例1中产品1#的IR图谱;
图3为实施例2中产品2#的1HNMR图谱;
图4为实施例2中产品2#的IR图谱;
图5为实施例3中产品3#的1HNMR图谱;
图6为实施例3中产品3#的IR图谱。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述。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他实施例,都属于本发明保护的范围。
实施例1
在装有搅拌器和氮气保护的1000ml的无水干燥的四口反应瓶中,加入D-230(亨斯迈产,分子量230,聚合度n=3)230g(1mol),室温(25℃)下边搅拌边加入472.68g(2mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到40℃,反应6小时,出料装入试剂瓶中密封,编号产品1#。产品1#的 1HNMR测试结果见图1,IR测试结果见图2。
实施例2
在装有搅拌器和氮气保护的5L的无水干燥的四口反应瓶中,加入D-2000(亨斯迈产,分子量2000,聚合度n=33)2000g(1mol),室温(25℃)下边搅拌边加入945.36g(4mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到60℃,反应8小时,出料装入试剂瓶中密封,编号产品2#。产品 2#的1HNMR测试结果见图3,产品2#的IR测试结果见图4。
实施例3
在装有搅拌器和氮气保护的5L的无水干燥的四口反应瓶中,加入D-4000(亨斯迈产,分子量4000,聚合度n=68)2000g(0.5mol),室温(25℃)下边搅拌边加入827.19g(3.5mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到80℃,反应1小时,出料装入试剂瓶中密封,编号产品3#。产品3#的1HNMR测试结果见图5,产品3#的IR测试结果见图6。
实施例4
在装有搅拌器和氮气保护的2L的无水干燥的四口反应瓶中,加入 CAED-2003(扬州晨化产,分子量900,聚合度n=20,PO:EO=7:13)900g(1mol),室温(25℃)下边搅拌边加入973.4g(3.5mol)3-(2,3-环氧丙氧)丙基三乙氧基硅烷,升温到75℃,反应2.5小时,出料装入试剂瓶中密封,编号产品4#。
实施例5
在装有搅拌器和氮气保护的1000L的反应釜中,加入T-3000(扬州晨化产,分子量3000,聚合度n=50,三官能度)300kg(100mol),室温(25℃)下边搅拌边加入102.92kg(370mol)3-(2,3-环氧丙氧)丙基三乙氧基硅烷,升温到 60-65℃,反应8小时,出料装入干燥金属桶中密封,编号产品5#。
实施例6
在装有搅拌器和氮气保护的1000L的反应釜中,加入CAT-5000(扬州晨化产,分子量5000,聚合度n=81,三官能度)500kg(100mol),室温(25℃)下边搅拌边加入94.54kg(400mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到 60-65℃,反应8小时,出料装入干燥金属桶中密封,编号产品6#。
实施例7
在装有搅拌器和氮气保护的1000L的反应釜中,加入CAED-2003(扬州晨化产,分子量2000,聚合度n=45,二官能度)500kg(100mol),室温(25℃)下边搅拌边加入94.54kg(400mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到60-65℃,反应8小时,出料装入干燥金属桶中密封,编号产品7#。
实施例8
在装有搅拌器和氮气保护的1L的反应釜中,加入CAT-403(扬州晨化产,分子量440,聚合度n=5,三官能度)440g(1mol),室温(25℃)下边搅拌边加入1063.57g(4.5mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到50℃,反应5小时,出料装入干燥金属桶中密封,编号产品8#。
其中,x+y+z=5
实施例9
在装有搅拌器和氮气保护的5L的反应釜中,加入MA-2200(无锡阿科力科技股份有限公司产,分子量2000,聚合度n=33,二官能度)2000g(1mol),室温(25℃)下边搅拌边加入709g(4mol)3-(2,3-环氧丙氧)丙基三甲氧基硅烷,升温到60℃,反应4小时,出料装入干燥金属桶中密封,编号产品9#。
MS胶基础树脂性能测试
将实施例中所制备的MS基础树脂,按照如下方法制备成MS胶粘合剂产品,MS胶粘合剂产品制备方法如下:
第一步:先将下表1.中配方的成分,邻苯二甲酸二辛酯(DOP),纳米碳酸钙(1200目)2000g,重质碳酸钙(1000目)1000g,炭黑(1000目)1000g,抗氧剂1010、光稳定剂765、紫外吸收剂326各自10g,加入到行星式球磨机中,高速搅拌分散捏合,升温至110℃抽真空脱水120分钟;
第二步:将行星式球磨机降温至50℃以下,加入实施例中所制备的MS基础树脂2000g和除水剂乙烯基三甲氧基硅烷(WD-21)100g,再中速搅拌分散后抽真空脱泡30分钟;
第三步:加入偶联剂KH792(N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷)10g和催化剂辛酸亚锡10g,中低速搅拌20分钟出料灌装至300ml PE塑料管中,得到MS胶粘合剂产品,存样,进行性能测试。
表1.MS胶基础树脂制备MS胶粘合剂配方
按照上表1中所给配方,和上述制备MS胶粘合剂的工艺,一次将实施例中的1#,3#,6#,7#,8#,9#等MS胶基础树脂样品制备成MS胶产品,并按照标准GB/T14683-2017进行性能测试,测试结果见表2:
表2不同实施例中MS胶基础树脂制备成MS胶产品后的性能测试结果
由表2可以看出,测试样7#产品的表干时间最长,为1.2h,这与聚醚胺中 EO含量高,亲水性强有关;测试样8#的拉伸模量最大,为0.98Mpa,这是因为所采用的的聚醚胺为三官能度,且聚合度仅为5,分子结构中柔性链较短。按照不同实施例所制备的基础树脂,均可用于MS胶的制备,性能均符合GB/T 14683-2017(硅酮和改性硅酮建筑密封胶)中所规定的要求。
尽管已描述了本发明的优选实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例作出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包含这些改动和变型在内。
Claims (7)
4.根据权利要求3所述的MS基础树脂的制备方法,其特征在于:所述聚醚胺化合物与环氧硅烷化合物按照摩尔比1:2-1:4.5。
5.根据权利要求3或4所述的MS基础树脂的制备方法,其特征在于:所述聚醚胺为2-3官能度的聚醚胺,分子量在200-5000之间。
6.根据权利要求3所述的MS基础树脂的制备方法,其特征在于:所述环氧硅烷化合物为3-(2,3-环氧丙氧)丙基三甲氧基硅烷、3-(2,3-环氧丙氧)丙基三甲乙基硅烷。
7.根据权利要求3所述的MS基础树脂的制备方法,其特征在于:聚醚胺化合物与环氧硅烷化合物的反应温度为40-80℃下,反应时间为1-6小时。
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