CN1040997A - 能通过脱除水交联成弹性体的硅氧烷树脂基水分散体 - Google Patents
能通过脱除水交联成弹性体的硅氧烷树脂基水分散体 Download PDFInfo
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- CN1040997A CN1040997A CN89106643A CN89106643A CN1040997A CN 1040997 A CN1040997 A CN 1040997A CN 89106643 A CN89106643 A CN 89106643A CN 89106643 A CN89106643 A CN 89106643A CN 1040997 A CN1040997 A CN 1040997A
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- IJJNTMLAAKKCML-UHFFFAOYSA-N tribenzyl borate Chemical compound C=1C=CC=CC=1COB(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 IJJNTMLAAKKCML-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- BOOITXALNJLNMB-UHFFFAOYSA-N tricyclohexyl borate Chemical compound C1CCCCC1OB(OC1CCCCC1)OC1CCCCC1 BOOITXALNJLNMB-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical group COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical class C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
脱除水后能交联成弹性体的硅氧烷水分散体,它含有100份α,ω-(二羟基)聚二有机硅氧烷乳水包油型乳浊液(A),1~100份羟基化硅氧烷树脂,其每分子至少含有两种选自下式:R3SiO0,5,R2SiO,RSiO1,5和RiO2单元,其中羟基重量含量为0.1~10%,0~250份非硅无机填料,0.01~3份金属固化催化剂化合物,所说乳浊液的pH值一般为4~13,固含量至少为40%。用这种乳液可生产硅氧烷弹性体密封材料。
Description
本发明涉及能通过脱除水交联成弹性体的硅氧烷树脂基水分散体。
美国专利2,891,920描述了一种在有阴离子、阳离子或非离子表面活性剂存在下用酸或碱催化剂乳液聚合聚二有机硅氧烷的方法。此专利透露所得乳液贮藏稳定,加入填料之后可用来制备油漆,通过脱除水可形成连续涂层。
美国专利3,294,725特别描述了用十二烷基苯磺酸乳液聚合聚二有机硅氧烷。该专利谈到,为了获得稳定的乳液,最好将这些乳液的PH值调节到约7。该专利还讲述,用这些加入了胶体二氧化硅和聚烷氧基硅烷的中性乳液可制取弹性体涂料。
美国专利3,360,491的论述与美国专利3,294,725的类似,不同的是用月桂基硫酸氢盐代替了十二烷基苯磺酸。
美国专利3,355,406特别描述了一种硅氧烷胶乳,它含有α,ω-(二羟基)聚二有机硅氧烷的水胶悬体;呈胶悬体的必要的填料(含硅倍半氧烷),选自无机酸、强碱,二丙烯酸二烷基锡和有机或无机过氧化物的催化剂。
美国专利3,697,469描述了一种乳液聚合聚二有机硅氧烷的具体方法,它还指出为了通过蒸除水制得弹性体涂层,可在此乳浊液中加入胶态二氧化硅和锡盐。
法国专利2,110,358描述了一种PH为6.5~9的硅氧烷乳浊液,加入碳黑和蒸除水之后,这种乳浊液可交联成导电的弹性体。另外含锡盐和聚烷氧基硅烷的乳浊液在贮藏的过程中不稳定,必须分两份单独包装来贮藏(两组分乳液)。
美国专利4,221,688和美国专利4,244,849和法国专利2,463,163描述了可稳定贮藏的硅氧烷乳浊液,它们含有α,ω-(二羟基)聚二有机硅氧烷聚合物的阴离子化稳定的乳浊液;硅质填料;锡盐;选含非增强填料。
硅质填料可以是胶态二氧化硅(美国专利4,221,688)硅酸钠(美国专利4,244,849)或粉状无定形二氧化硅(法国专利2,463,163)。
与先有技术公知的水乳浊液相比,这三篇专利指出,一方面为了获得可稳定贮藏的单组分乳液必须将乳浊液保持在PH值高于8.5或9,最好高于10的碱性条件下,另一方面乳浊液中须加入锡盐以使乳浊液所需的熟化期缩短到几天,得到可交联的乳液。
在酸性或中性PH条件下贮藏的公知的填充硅氧烷乳浊液至少具有以下缺点之一:
-单包装贮藏不稳定(单组分组分物),
-固化成弹性体的时间过长
-无触变性
-对普通底基粘合微弱
以硅氧烷树脂为基础且通过脱除水能交联成弹性体的水乳浊液已有介绍。
例如,已作参考的美国专利3,355,406讲述了一种由α,ω(二羟基)聚二有机硅氧烷构成的硅氧烷胶乳(最好通过乳液聚合加以制备)和由RSiO1.5(R是羟基)构成的硅倍半氧烷胶乳。这种胶乳可另外含有金属固化催化剂和烷基三烷氧基硅烷。
在美国专利4,554,187中,与α,ω-(二羟基)聚二有机硅氧烷缔合的硅氧烷树脂是一种低分子量、含烷氧基或酰氧基的反应性树脂。
在欧洲专利申请266,729中,与α,ω-(二羟基)聚二有机硅氧烷和固化催化剂缔合的硅氧烷树脂是硅酸盐。
欧洲专利304,719(1989.3.1公告)介绍了用可溶于甲苯并以水乳浊液形式存在的高分子量硅氧烷树脂代替硅酸盐,其中颗粒(胶束)尺寸高于200纳米。
含10%(重量)羟基以下的硅氧烷树脂可与这种硅酸盐缔合。
以下所有百分比和份数均以重量计,除非另有说明。
本发明的一个目的是提供一种硅氧烷水分散体(乳浊液),它具有酸性或碱性PH值,能通过脱除水在室温下交联成弹性体,没有公知乳浊液的缺点。
本发明的另一个目的是提供上述类型的硅氧烷水分散体,它能稳定的贮藏,在室温下通过脱除水可正确、快速、充分地交联成弹性体,由此形成的弹性体的机械性能在老化后仍保持其机械性能,本发明的又一个目的是提供上述类型的硅氧烷水分散体,其熟化期可在稍高温度(20~60℃)下进行,时间为48小时以下。
本发明的又一个目的是提供上述类型的硅氧烷水分散体,这种分散体能得到进一步显示出改善了阻燃性的弹性体。
本发明的再一个目的是提供上述类型的硅氧烷水分散体,这种分散体能得到对各种底基、尤其是对玻璃、混凝土和金属(钢、铝)具有令人满意的粘附性的弹性体。
这些和其它目的可由本发明达到,实际上本发明涉及在室温条件下通过脱除水能交联成弹性体的硅氧烷水分散体,其特征在于含有:
(A)100份水包油型α,ω-(二羟基)聚二有机硅氧烷乳浊液,此乳浊液已用至少一种选自阴离子和非离子表面活性剂及其混合物的表面活性剂稳定,
(B)1~100份重量的羟基化硅氧烷树脂,这种树脂每分子含有至少两种选自式R3SiO0.5,R2SiO、RSiO1.5和SiO2的不同单元,其中R基可相同或不同,选自乙烯基、苯基和3,3,3-三氟丙基和直链或支化烷基(含1~6个碳原子),所述树脂的羟基重量含量为0.1~10%,
(C)0~250份重量的非硅质无机填料,
(D)0.01~3份重量的金属固化催化剂化合物,
所述分散体的固含量至少为40%。
α,ω-(二羟基)聚二有机硅氧烷在25℃的粘度须至少为100MpaS,最好至少为50,000Mpas。
实际上,正是粘度高于50,000Mpas,得到的弹性体才显示出合适的综合机械性能,尤其是肖氏硬度和延伸率。
此外,粘度越高,弹性体老化时机械性能就越能保持。
本发明优选的粘度于25℃是在50,000~1,500,000Mpas之间。
α,ω-(二羟基)聚二有机硅氧烷的有机基团是可用氰基或氟基选择取代的含6个以下碳原子的一价烃基。考虑到取代基在工业产品中易获性难易,一般常用的是甲基、乙基、丙基苯基、乙烯基和3,3,3-三氟丙基。这些基团中至少80%的数量是甲基。
在本发明的范围内,特别推荐使用通过上述美国专利(美国专利2,891,920,尤其是美国专利3,294,725在此作参考)介绍的阴离子聚合法制取的α,ω-(二羟基)-聚二有机硅氧烷。制取的聚合物用一种表面活性剂阴离子稳定化,按美国专利3,294,725介绍,这种表面活性剂最好是芳烃磺酸的碱金属盐,而游离酸还起到聚合催化剂的作用。
优选的催化剂和表面活性剂是十二烷基苯磺酸及其碱性金属盐,尤其是钠盐。需要的话,可以加入其它阴离子或非离子表面活性剂,但加入并不是必须的,因为按美国专利3,294,725讲述,由中和磺酸产生的阴离子表面活性剂的量便足以稳定聚合物乳浊液。此量一般是乳浊液重量的3%以下,最好低于1.5%。
这种乳液聚合方法的特殊优点是它能直接得到乳浊液(A)。而且,该方法能毫无困难的就得到了粘度很高的α,ω-(二羟基)-聚二有机硅氧烷乳浊液。
为了制备乳浊液(A),也可以开始就用已经聚合的α,ω-(二羟基)-聚二有机硅氧烷,然后再按照专家们公知的并在文献(见法国专利FR-A-2,064,563,FR-A-2,094,322,FR-A-2,114,230和EP-A-169,098)中详述的方法通过用阴离子和/或非离子表面活性剂稳定乳浊液将其转变成水乳浊液。
按照这种方法,α,ω-(二羟基)-聚二有机硅氧烷聚合物通过与阴离子或非离子表面活性剂简单地搅拌进行混合(后者可以是水溶液),然后需要的话可加水并经过常用胶体磨使全部物质成为一种细而均匀的乳浊液。
所得到的漆浆随后用适量的水进行稀释,这样便得到用阴离子或非离子表面活性剂稳定、而且能稳定贮藏的乳浊液。
阴离子或非离子表面活性剂的用量一般是乳化工艺所用的常用量,它们在上述专利和美国专利US-A-2,891,920中进行了特别描述。
在本发明的范围内,优选的阴离子表面活性剂是芳烃磺酸盐的碱金属盐,优选的非离子表面活性剂是聚氧乙烯化烷基苯酚。这些非离子表面活性剂显然与要加进所述的由乳液聚合得到的乳液(A)中的一样。
由乳液聚合或由乳化聚硅氧烷而制取的乳浊液(A)呈水包油型乳液并且优选的固含量不大于45%(重量)。
以固含量计,每100份乳浊液(A)加入1~100份、最好2~20份羟基化硅氧烷树脂(B)。
羟基化硅氧烷树脂(B)的羟基重量含量是在0.1~10%之间,优选的是在1~6%之间。
羟基化硅氧烷树脂(B)每分子含有至少两种选自式:R3SiO0.5(M单元)、R2SiO(D单元),RSiO1.5(T单元)和SiO2(Q单元)的不同单元。
可以指出的烷基的例子是甲基、乙基、异丙基、叔丁基、正己基。
这些硅氧烷树脂是公知的支化有机聚硅氧烷聚合物,制备这些硅氧烷树脂的方法在许多专利中都有描述。
可以提到的作为能使用的树脂例子是:MQ树脂、MDQ树脂、TD树脂和MD树脂。
可以使用在室温下呈固体或液体的树脂。可以水乳浊液的形式如有机溶剂溶液或硅氧烷油溶液或其它水乳浊液的形式加入这些树脂。
推荐使用的液体或固体硅氧烷树脂最好有较低而平均分子量(一般低于25,000)并可溶于甲苯溶液如某种MQ、MDQ、TD和MDT型树脂。
与EP304,719所述相反,用硅氧烷树脂不必事先乳化或根本就没必要用乳化聚合而预先制取。此外,这些树脂的水乳浊液的颗粒尺寸不必至少为200纳米(如EP304,719所说)。
例如,在美国专利US-A-4,028,339,US-A-4,023,052,331,US-A-4,056,492,US-A-4,525,502和US-A-4,717,599描述了可用的硅氧烷树脂的水乳浊液这些专利在此提出仅供参考。
按照本发明,分散体的另一种组分是加入的30~250份、最好5~200份的半增强或填充型非硅质无机填料(C)。
填料(C)的颗粒尺寸一般在1~300μm之间,BET表面积小于50m2/g。
可单独或混合使用的填料(C)的例子是,碳黑、二氧化钛、氧化铝、水合氧化铝、多孔蛭石、非多孔蛭石、碳酸钙、氧化锌、云母、滑石、氧化铁、硫酸钡和熟石灰。
将填料以粉状掺入乳浊液(A)中进行简单地混合。
按照本发明的另一种方案,已经发现,如果填料(C)基本上仅由选自水合氧化铝、多孔蛭石、非多孔蛭石的填料构成并以每100份乳液(A)5~250份、最好50~200份的比例存在,就得到了阻燃性特别高的弹性体,而这种弹性体是用上述其它种类的填料(C)、尤其是氧化铝或非水合氧化铝所不能得到的。按照EP-A-212,827所述,也可加入陶瓷或芳酰胺(al-amide)纤维。
金属固化催化剂主要是羧基酸盐和选自铅、锌、锆、钛、铁、锡、钡、钙、和锰的金属卤化物。
组分(D)最好是一种催化的锡化合物,一般是一种有机锡盐,而且最好以水乳液的形式掺入。可用的有机锡盐在Nou著的“硅氧烷化学与技术”(1968年,学术出版物第337页)中进行了具体论述。
锡盐、尤其是二羰酸锡与乙基多硅酸盐的反应产物(如美国专利US-A-3,862,919中所述)可用作催化的锡化合物。
也可用烷基硅酸盐或烷基三烷氧基硅烷与二乙酸二丁烯的反应产物(如比利时专利BE-A-842,305中所述)。
优选的锡盐是二合锡(EP-A-147,323和EP-A-235,049),二羰酸二有机锡,特别是带有支链的二烷烃羧酸的二丁锡或二辛锡(英国专利GB-A-1,289,900),二乙酸二丁锡或二辛锡和二月桂酸二丁锡或二辛锡。每100份(A),用0.01~3份,最好0.05~2份的有机锡盐。
按照另一种方案,每100份乳浊液(A),也可加入选自硅酸钠(0.3~30份)和增强或半增强硅质填料(1~150份)的硅质添加剂(E)。
这些硅质填料是选自胶态二氧化硅或焦化硅和沉淀二氧化硅粉或其混合物。优选的是焦化二氧化硅。然而也可使用半增强硅质填料诸如硅藻土和石英粉。
(C)+(E)成份总和,按每100份乳浊液(A)计,须小于300份。
焦化和沉淀硅粉是公知的尤其是它们可用作填料加到硅氧烷弹性胶料中,这种胶料通过加热可硫化成硅氧烷橡胶。这些粉末的平均颗粒尺寸一般为0.1μm以下,BET表面积高于50m2/g,优选为150~350m2/g。
用任何适当的方法,尤其用搅拌将硅质添加剂(E)加到乳液(E)中大大增加了乳浊液(A)的粘度,此时乳液自然成为浆糊状。
事实上已经发现,按照本发明,加入硅质添加剂(E)足以把或多或少地明显的触变特性赋予了分散体。例如,当把乳浊液从储存筒中取出时,乳浊液即使粘附在铅直底基上也不流淌,且在环境温度下通过蒸除水而固化成弹性体。不流淌的乳浊液也可通过平均颗粒尺寸小于0。1μm的填料(C)碳酸钙得到。显然,对胶料稍加热(加热大约至40~80℃)以加速蒸除水也包括在本发明范围之内。
按照本发明,也可将能改进乳浊液的性质和经脱除乳液的水形成的弹性体的特性的各种添加剂加入分散体中。也能以每100份乳浊液(A)0。1~20份粘附促进剂的比例加进粘附促进剂(F),最好是有机三烷氧基硅烷类,例如,r-氨丙基三乙氧基硅烷,N-(氨乙基)-r-氨丙基三甲氧基硅烷,乙烯基三甲氧基硅烷,烷基硅酸烷基酯如硅酸甲酯或硅酸乙酯或它们的部分水解产物,亦即聚硅酸烷基酯如聚硅酸甲酯和聚硅酸乙酯。
有机三烷氧基硅烷和硅酸烷基酯最好符合下列通式:
R′aSi(OR)4-a
式中R含1~4个原子的烷基,R′是R或乙烯基、r-氨丙基、N-(氨乙基)-r-氨丙基,a为1或0。
本发明的分散体的PH值通常为4~13。该值取决于构成分散体的成份的性质,尤其是取决于乳浊液(A)中表面活性剂和催化剂的含量和填料(C)的含量。
根据预想的应用情况,通过加进无机或有机酸、优选为氧化了的硼衍生物可以制备出PH值为4~7的分散体;而加进有机或无机碱可制备出PH值为7~13的分散体,更详细的描述如下。
其它可以提及的添加剂的例子是杀菌剂和消泡剂以及触变剂,如羧甲基纤维素,黄原酸胶和聚乙烯醇。
按照本发明的分散体尤其可以用于建筑业生产腻子胶和密封材料。
按照本发明的分散体可以用以下方法制取:
出发点是乳浊液(A),它既可用乳液聚合的方法且将乳浊液用阴离子表面活性剂稳定,(若需要也可用非离子表面活性剂稳定)而制取,也可用乳化α,ω-(二羟基)聚二有机硅氧烷的方法且将乳浊液用阴离子和/或非离子表面活性剂稳定而制备。
为了制取本发明的分散体,推荐先在室温下将金属固化催化剂化合物(D)(最好呈水乳浊液形式)加进乳液(A)中,然后用无机碱或有机碱(最好是用强碱金属氢氧化物如氢氧化钠氢氧化钾)将混合物的PH值调节到大于7且一般低于13,或者通过加进适量选自氧化硼,硼酸和硼酸盐的氧化硼衍生物将PH值调到小于7且大于4。
伯胺诸如二乙基胺可以用作有机碱。然而,按照本发明的优选实施方案,利用适量的水溶液形式引入的无机碱(最好选自碱金属和碱土金属氢氧化物如氢氧化钠、氢氧化钾的溶液和氢氧化钙、氢氧化钡和氢氧化镁的溶液)可将PH值调整。然而,碱土金属氢氧化物可直接以固态掺入。
公知的氧化硼又叫硼酐。可提到的硼酸有厚硼酸、亚硼酸和四硼酸。三有机硼酸酯和无机硼酸酯可用作硼酸盐。在本发明的范围内,可使用的有硼酸三乙酯、硼酸三苯基酯盐,硼酸三苄基酯、硼酸三环己酯、硼酸三甲基甲硅烷基酯,硼酸三丁酯、四硼酸二铵,五硼酸铵、四硼酸钠十水合物(硼砂),五硼酸钾、二硼酸镁、单硼酸钙,三硼酸钡,偏硼酸锌。也可用这些硼酸盐的部分水解产物。
以100份乳浊液(A)加0。1~5份的氧化的硼衍生物一般足以使分散体的最终PH值调到4~7。
若需要(E)的话,可加入填料(C),然后加入呈有机溶剂或硅氧烷油溶液或其它水乳浊液状的树脂(B)。
25℃粘度为100~5000Mpas的三甲基甲硅烷基嵌段的聚二甲基硅氧烷可用作硅氧烷油。
把最后得到的乳浊液均匀化,然后脱气并封装在与大气氧和水蒸汽隔绝的密封箱中。
组份(A)、(B)、(C)、(D)(若需要,(E)和(F))以这样的量混合以使最终乳浊液的固含量大于40%,最好高于60%,但一般低于90%。
本发明的分散体可用作可交联的薄层油漆。此时的固含量最好为40~70%。
为了测定固含量,将2g分散体放在铝制标重盘中并在空气强制循环的烘箱中加热1小时,使温度达到150℃。冷却之后,再称一下盘的重量,余下的物料定为初始2g分散体的百分含量,表示为固含量。
按照最佳的替换形式,制备后,按本发明的分散体要在环境温度下经过一段熟化期即在温度为20~90℃熟化几小时乃至几天。
该熟化期仅包括加热,若需要,也包括在使用前把分散体静置在无大气氧的地方。
以下实施例中,百分比和份数均以重量计,除非另加标明。
实施例1
制取乳浊液(A):在十二烷基苯磺酸存在下,通过乳液聚合20℃粘度为100Mpas的α,ω-(二羟基)聚二甲基硅氧烷油而得到乳浊液(A)。
在25℃油粘度达到106Mpas时,中和催化剂使聚合中止。
得到的乳浊液(A)的固含量为59%。
将含37%(重量)二月桂酸二辛锡的1.5份水乳浊液搅拌地加到100份的乳浊液(A)中。然后加入1。2份的二乙胺和60份平均颗粒尺寸为0.07μm沉积CaCO3填料(C)。
将含1%(重量)的羟基且由2%(重量)的CH3SiO1.5单元、61.5%(重量)的(CH3)2SiO单元和36.5%(重量)的(CH3)3SiO0.5单元构成的8.3份可溶于甲苯溶液的羟基化硅氧烷树脂(B)(分子量为4000,R/Si=1.77)加到所得乳浊液(A)中。
最后得到的分散体的PH值为9.5。
对分散体均匀化30分钟,然后封装在与大气氧及水蒸汽隔绝的密封箱中。
贮存四天之后,用医用刀片将分散体涂成2mm厚的膜,在室温下让该膜干燥7天。
下面对干燥膜的平均机械性能进行测定:
按照ASTM标准D2240测定肖氏硬度
按照AFNOR标准T46002(相当于ASTM标准D412)测定拉伸强度(TS),单位Mpa
按照AFNOR标准T46002测定折断时的延伸率(EB),单位%。
按照AFNOR标准T46002测定100%时的弹性模量(EM),单位Mpa。
所得机械性能的对比列于表一
表一
实施例2到3
准确地重复实施例1的操作程序,不同的是8.3份的树脂(B)被以下代替:
-在实施例2的情况下,引入含2.2%(重量)的羟基且由70%(重量)的CH3SiO1.5单元和30%(重量)的(CH3)2SiO单元构成的8.8份可溶于甲苯和二甲苯的树脂(分子量为1300,R/Si=1.3)。最后得到的乳浊液的PH值为8.5。
-在实施例3的情况下:用含70%(重量)的甲苯溶液引入4.1份含2.2%(重量)的羟基和由73%(重量)的C6H3SiO1.5单元(以及R/Si=1.4的)和27%(重量)的(CH3)2SiO单元构成的树脂(R/Si为1.4)。最后得到的乳浊液的PH值为8.5。
机械性能的对比见表一。
实施例4~6
准确地按照实施例1的操作程序,不同的是1.2份二乙胺用以下代替:
-在实施例4的情况下:4份含20%氢氧化钾水性溶液。最后得到的乳浊液的PH值为11。
-在实施例6的情况下:4份含20%氢氧化钾的溶液和1份聚硅酸乙酯。其PH值为11。
使一股4mm粗的弹性体条沉积在一块玻璃或混凝土底基上。10天之后,人工拉下该条评价该弹性体的粘附性。
粘附性用下列三种方式定性:
-该条不能与底基上分开,为粘附性良好(记为++)。
-该条很难剥下及在小面积可剥下,为中等粘附性(记为+)。
-该条很易剥落,为无粘附性(记为O)。
机械性能和粘附性的评估列于表2。
表2
实施例7
重复实施例1的操作工序,不同的是用下列替代物:
含2%(重量)的羟基和由50%(重量)的M单元及50%(重量)的Q单元构成的于甲苯溶液中的8.8份MDT树脂与7份MQ树脂(分子量为10,000,R/Si为1.3)
1.2份的二乙胺与4份含20%(重量)的氢氧化钾的溶液。
得到的机械性能与粘附性的评估比较见表3
表3
实施例8
重复实施例7的操作工序,另外加1份聚硅酸乙酯(硅酸乙酯40R)。
所得机械性能和粘附性评价比较见表3
实施例9
准确地重复实施例2的操作工序,不同的是:
(a)用0.59份的硼酸代替1.2份的二乙胺,
(b)用1.5份含37%(重量)的锡化合物的催化乳浊液代替1.5份的催化乳浊液(D),所说的锡化合物是1摩尔氧化二丁烯与1摩尔支链烷酸脱水形成的反应产物,1摩尔量氧化二辛基与1摩尔量脱除水形成的多能酸反应生成物
(C)所得分散体经历80℃2小时30分的熟化期后装入密封箱内。
所得机械性能比较见表3
Claims (11)
1、在室温条件下通过脱除水能交联成弹性体的硅氧烷水分散体,其特征在于它含有(以重量计):
(A)100份(重量)水包油型α,ω-(二羟基)聚二有机硅氧烷,它用至少一种选自阴离子或非离子表面活性剂及其混合物的表面活性剂稳定。
(B)1~100份(重量)羟基化硅氧烷树脂,这种树脂每分子至少含两种选自式R3SiO0.5,R2SiO,RSiO1.5和SiO2的不同单元,R基是相同或不同的,选自乙烯基、苯基和3,3,3-三氟丙基和含1~6个碳原子的直链或支化的烷基,所说的树脂含0.1~10%(重量)的羟基,
(C)0~250份(重量)的非硅质无机填料,
(D)0.01~3份(重量)的金属固化催化剂化合物,所说分散体的固含量至少为40%。
2、按照权利要求1的水分散体,其特征在于树脂(B)是选自MQ、MDQ、TD和MDT树脂。
3、按照权利要求1或2的水分散体,其特征在于树脂(B)是平均分子量为25,000以下的可溶于甲苯的液体或固体树脂。
4、按照前述权利要求任一项的水分散体,其特征在于金属化合物(D)是呈水乳浊液状的有机锡盐(D)。
5、按照前述权利要求任一项的硅氧烷水分散体,其特征在于乳浊液(A)的固含量至少为45%(重量)。
6、按照前述权利要求任一项的硅氧烷水分散体,其特征在于它含有5~200份选自水合氧化铝、氧化铝、碳化钙,多孔蛭石,非多孔蛭石、碳黑、氧化锌,二氧化钛、云母、滑石、氧化铁、硫酸钡和消石灰的填料(C)。
7、按照权利要求6的硅氧烷水分散体,其特征在于碳化钙的平均粒径小于0.1μm。
8、按照前述权利要求任一项的硅氧烷水分散体,其特征在于它含有:
(A)100份水包油型a,s-(二羟基)聚二有机硅氧烷乳浊液,其粘度在25℃为50000~1,500,000Mpas,并用选自一种芳烃磺酸碱金属盐和聚氧乙烯化烷基酚的表面活性剂稳定,
(B)2~20份羟基化硅氧化树脂,
(C)50~200份无机填料,
(D)0.05~2份二羧酸二有机锡,
9、按照前述权利要求任一项的硅氧烷水分散体,其特征在于每100份乳浊液(A)另外含有选自硅酸钠(0.3~30份)和增强或半增强硅质填料(1~150份)的硅质添加剂,条件是每100份(A)(C)+(E)份数总和小于300份。
10、按照前述权利要求任一项的水分散体,其特征在于它另外含有0.01~20份(重量)的选自三烷基硅烷、硅酸烷基酯和聚硅酸烷基酯的粘合促进剂(F)。
11、按照前述权利要求任一项的水分散体,其特征在于它另含有每100份乳浊液(A)0.1~5份氧化的硼衍生物。
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ES (1) | ES2047700T3 (zh) |
FI (1) | FI894073A (zh) |
FR (1) | FR2638166B1 (zh) |
HU (1) | HUT53140A (zh) |
IE (1) | IE63399B1 (zh) |
NO (1) | NO893437L (zh) |
NZ (1) | NZ230469A (zh) |
PT (1) | PT91587A (zh) |
ZA (1) | ZA896630B (zh) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2637606B1 (fr) * | 1988-10-11 | 1990-12-14 | Rhone Poulenc Chimie | Dispersion aqueuse de silicone a base d'alcenyloxysilane reticulant en un elastomere par elimination de l'eau |
DE4026029A1 (de) * | 1989-09-07 | 1992-02-20 | Sandoz Ag | Waessrige aminopolysiloxanmikroemulsionen, deren herstellung und verwendung |
DE4217561A1 (de) * | 1992-05-27 | 1993-12-02 | Wacker Chemie Gmbh | Wäßrige Dispersionen von Organopolysiloxanen |
US5449712A (en) * | 1993-01-13 | 1995-09-12 | Thoro System Products, Inc. | Organosilicon emulsions for rendering porous substrates water repellent |
US5895794A (en) * | 1993-08-30 | 1999-04-20 | Dow Corning Corporation | Shelf stable cross-linked emulsions with optimum consistency and handling without the use of thickeners |
FR2746052B1 (fr) * | 1996-03-15 | 1998-07-03 | Procede de moulage et d'hydrofugation d'elements moules en beton, mortier, ciment, par une resine silicone | |
DE19934438B4 (de) * | 1999-07-22 | 2008-01-17 | Wacker Chemie Ag | Verfahren zur Herstellung einer wässrigen 1-Komponenten Siliconzusammensetzung |
JP4819685B2 (ja) * | 2003-10-08 | 2011-11-24 | ダウ・コーニング・コーポレイション | シリコーンmq樹脂強化シリコーンエラストマーエマルジョン |
JP4678402B2 (ja) * | 2007-11-02 | 2011-04-27 | 信越化学工業株式会社 | 皮膜形成性オルガノポリシロキサンエマルジョン組成物及び繊維用風合い改良剤 |
WO2009077389A1 (de) | 2007-12-14 | 2009-06-25 | Henkel Ag & Co. Kgaa | Härtbare zusammensetzungen enthaltend wässrige dispersionen von organopolysiloxanen |
DE102008003155A1 (de) | 2008-01-03 | 2009-07-09 | Henkel Ag & Co. Kgaa | Härtbare Zusammensetzungen enthaltend wässrige Dispersionen von Organopolysiloxanen |
DE102007060919A1 (de) | 2007-12-14 | 2009-06-18 | Henkel Ag & Co. Kgaa | Härtbare Zusammensetzungen enthaltend wässrige Dispersionen von Organopolysiloxanen |
JP4678411B2 (ja) * | 2008-02-22 | 2011-04-27 | 信越化学工業株式会社 | 皮膜形成性オルガノポリシロキサンエマルジョン組成物 |
JP5608909B2 (ja) * | 2010-01-08 | 2014-10-22 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | 室温硬化性ポリオルガノシロキサン組成物 |
JP2016027069A (ja) * | 2014-06-26 | 2016-02-18 | 日東電工株式会社 | 難燃材料およびその用途 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3070560A (en) * | 1959-01-19 | 1962-12-25 | Dow Corning | Composition comprising a polysiloxane resin, silica filler, a hydroxylated siloxane, and a boron compound |
US4257932A (en) * | 1978-06-27 | 1981-03-24 | General Electric Company | Curable compositions and process |
DE3323909A1 (de) * | 1983-07-02 | 1985-01-10 | Bayer Ag, 5090 Leverkusen | Stabile siliconemulsionen |
FR2565593B1 (fr) * | 1984-06-12 | 1986-12-12 | Rhone Poulenc Spec Chim | Compositions d'emulsions aqueuses pour le traitement antiadherent et hydrofuge de materiaux cellulosiques |
JPH0639568B2 (ja) * | 1985-04-24 | 1994-05-25 | 東レ・ダウコーニング・シリコーン株式会社 | シリコ−ン水性エマルジヨン組成物の製造方法 |
DE3637836A1 (de) * | 1986-11-06 | 1988-05-19 | Wacker Chemie Gmbh | Waessrige silicondispersionen |
DE3727180A1 (de) * | 1987-08-14 | 1989-02-23 | Wacker Chemie Gmbh | Waessrige silicondispersionen |
GB8806145D0 (en) * | 1988-03-15 | 1988-04-13 | Unilever Plc | Electrical sensor & method |
-
1988
- 1988-08-31 FR FR8811609A patent/FR2638166B1/fr not_active Expired - Lifetime
-
1989
- 1989-08-25 BR BR898904277A patent/BR8904277A/pt not_active IP Right Cessation
- 1989-08-28 CA CA000609600A patent/CA1326097C/fr not_active Expired - Lifetime
- 1989-08-28 NO NO89893437A patent/NO893437L/no unknown
- 1989-08-29 DE DE89420317T patent/DE68910449T2/de not_active Expired - Lifetime
- 1989-08-29 NZ NZ230469A patent/NZ230469A/xx unknown
- 1989-08-29 ES ES89420317T patent/ES2047700T3/es not_active Expired - Lifetime
- 1989-08-29 EP EP89420317A patent/EP0359676B1/fr not_active Expired - Lifetime
- 1989-08-29 AT AT89420317T patent/ATE96824T1/de not_active IP Right Cessation
- 1989-08-29 JP JP1220501A patent/JPH0645756B2/ja not_active Expired - Lifetime
- 1989-08-29 AU AU40868/89A patent/AU627217B2/en not_active Expired
- 1989-08-30 PT PT91587A patent/PT91587A/pt not_active Application Discontinuation
- 1989-08-30 HU HU894502A patent/HUT53140A/hu unknown
- 1989-08-30 FI FI894073A patent/FI894073A/fi not_active IP Right Cessation
- 1989-08-30 CN CN89106643A patent/CN1030460C/zh not_active Expired - Lifetime
- 1989-08-30 ZA ZA896630A patent/ZA896630B/xx unknown
- 1989-08-30 IE IE279389A patent/IE63399B1/en not_active IP Right Cessation
- 1989-08-30 DK DK198904266A patent/DK175833B1/da not_active IP Right Cessation
- 1989-08-31 KR KR1019890012552A patent/KR930003699B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ZA896630B (en) | 1990-05-30 |
NO893437D0 (no) | 1989-08-28 |
BR8904277A (pt) | 1990-04-17 |
KR900003306A (ko) | 1990-03-26 |
EP0359676A1 (fr) | 1990-03-21 |
NZ230469A (en) | 1991-09-25 |
IE892793L (en) | 1990-02-28 |
FR2638166A1 (fr) | 1990-04-27 |
DE68910449D1 (de) | 1993-12-09 |
CA1326097C (fr) | 1994-01-11 |
KR930003699B1 (ko) | 1993-05-08 |
DE68910449T2 (de) | 1994-05-11 |
FI894073A0 (fi) | 1989-08-30 |
PT91587A (pt) | 1990-03-30 |
DK426689D0 (da) | 1989-08-30 |
ATE96824T1 (de) | 1993-11-15 |
JPH0645756B2 (ja) | 1994-06-15 |
AU627217B2 (en) | 1992-08-20 |
DK426689A (da) | 1990-03-01 |
IE63399B1 (en) | 1995-04-19 |
ES2047700T3 (es) | 1994-03-01 |
HUT53140A (en) | 1990-09-28 |
FR2638166B1 (fr) | 1991-01-11 |
EP0359676B1 (fr) | 1993-11-03 |
FI894073A (fi) | 1990-03-01 |
NO893437L (no) | 1990-03-01 |
JPH02105859A (ja) | 1990-04-18 |
AU4086889A (en) | 1990-03-08 |
DK175833B1 (da) | 2005-03-21 |
CN1030460C (zh) | 1995-12-06 |
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