氨基三乙氧基硅烷对脱酸型RTV硅橡胶催化作用的研究
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摘要
由100份端羟基聚二甲基硅氧烷(HTPDMS)和8份甲基三乙酰氧基硅烷构成的脱醋酸型单组份室温硫化硅橡胶中,分别加入3-氨丙基三乙氧基硅烷(APTES)、3-(2-氨基乙胺基)丙基三乙氧基硅烷(AATS)和二乙胺基甲基三乙氧基硅烷(DMTS)三种氨基硅烷,并改变用量为0.5、1.0、1.5、2.0和2.5份。从胶料固化过程中的粘弹性行为、表干时间和交联度等方面研究三种氨基硅烷的催化作用,并与二月桂酸二丁基锡(DBTDL)进行对比。胶料固化过程中损耗系数(tanδ)与复数粘度变化结果表明:三种氨基硅烷在该胶料中的催化作用与它们的碱性直接相关,碱性最强的AATS在低于1.5份用量下,表现出最高的催化效率,但由于其易自缩合成低聚物,在用量高于1.5份后,催化效率降低;DMTS的碱性强于APTES,在各用量下,其催化效果均好于APTES,通过增加DMTS的用量可获得接近于DBTDL的催化效果。各胶料固化12 h后的交联度结果表明氨基硅烷在胶料中主要起催化作用,交联作用不明显。
3-aminopropyltriethoxysilane(APTES), 3-(2-aminoethylamino)propyltriethoxysilane(AATS) and diethylaminomethyltriethoxysilane(DMTS) were added to deacidi fied room temperature vulcanized silicone rubber(RTV silicone rubber) respectively, which was consisted of 100 phr hydroxyfunctionalized poly(dimethylsiloxane)(HTPDMS) and 8 phr methyltriacetoxysilane. The amounts varied in 0.5, 1.0, 1.5, 2.0, and 2.5 phr. Their catalysis efficiency in the curing process of rubber stocks was studied by the viscoelastic behavior, tack free time and cross-linking degree. A comparison was performed with dibutyltin dilaurate(DBTDL). The results shows that the catalysis efficiency of three amino silanes is related to their alkalinity directly. Due to the strongest alkalinity, AATS shows the highest catalysis efficiency under 1.5 phr amount. However, more than 1.5 phr AATS will lead to decline of catalysis efficiency because of sel f-condensation. As the stronger alkalinity, DMTS exhibits higher catalysis efficiency than APTES. Furthermore, DMTS and DBTDL have a closer catalysi s efficiency to DMTS. The results of cross-linking degree after curing for 12 h reveals that the amino silanes mainly play a catalytic role in the rubber stocks, instead of cross-link effects.
3-aminopropyltriethoxysilane(APTES), 3-(2-aminoethylamino)propyltriethoxysilane(AATS) and diethylaminomethyltriethoxysilane(DMTS) were added to deacidi fied room temperature vulcanized silicone rubber(RTV silicone rubber) respectively, which was consisted of 100 phr hydroxyfunctionalized poly(dimethylsiloxane)(HTPDMS) and 8 phr methyltriacetoxysilane. The amounts varied in 0.5, 1.0, 1.5, 2.0, and 2.5 phr. Their catalysis efficiency in the curing process of rubber stocks was studied by the viscoelastic behavior, tack free time and cross-linking degree. A comparison was performed with dibutyltin dilaurate(DBTDL). The results shows that the catalysis efficiency of three amino silanes is related to their alkalinity directly. Due to the strongest alkalinity, AATS shows the highest catalysis efficiency under 1.5 phr amount. However, more than 1.5 phr AATS will lead to decline of catalysis efficiency because of sel f-condensation. As the stronger alkalinity, DMTS exhibits higher catalysis efficiency than APTES. Furthermore, DMTS and DBTDL have a closer catalysi s efficiency to DMTS. The results of cross-linking degree after curing for 12 h reveals that the amino silanes mainly play a catalytic role in the rubber stocks, instead of cross-link effects.
引文
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[3]冯圣玉,张洁,李美江,等.有机硅高分子及其应用[M].北京:化学工业出版社,2004.
[4]陈欣,曾小波.单组分室温硫化硅橡胶制备及应用[J].化工生产与技术,2012,19(2):49-51.
[5]幸松民,王一璐.有机硅合成工艺及产品应用[M].北京:化学工业出版社,2000.
[6]Weij F W V D.The action of tin compounds in condensation-type RTVsilicone rubbers[J].Macromol Chem Phys,1980,181(12):2541-2548.
[7]董志磊.不同催化体系RTV-1硅橡胶粘合剂的研究[D].天津:天津大学材料科学与工程学院,2012.
[8]屈裴,刘波,黄强,等.影响脱醇型RTV-1硅橡胶硫化速度的因素[J].有机硅材料,2015,22(4):309-312.
[9]陈晓燕.α-氨基硅烷偶联剂与PDMS自催化交联体系的研究[D].广州:中山大学化学与化学工程学院,2007.
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[11]Yin Yigao,Zhang Yi,Chi Zhenguo,et al.Self-catalytic cross-linking reaction and reactive mech anism studies of α-aminomethyl triethoxysilanes forα,ω-dihydroxy poly(dimethylsiloxane)[J].Eur Polym J,2008,44(7):2284-2294.
[12]Tang Y,Tsiang R.Rheological,extractive and thermal studies of the room temperature vulcanized polydimethylsiloxane[J].Polymer,1999,40(22):6135-6146.
[13]盘文辉,张艳华.流变方法分析氰酸酯预聚体及其固化体系的凝胶化[C]//第十八届中国覆铜板技术·市场研讨会论文集.东莞:中国电子材料行业协会覆铜板材料分会,2017:242-245.
[14]Zhao Qian,Liu Qingyang,Bei Yiling,et al.Preparation and characterization of room temperature vulcanized silicone rubber usingα-amine ketoximesilanes as auto-catalyzed cross-linkers[J].RSC Adv,2016,6(44):38447-38453.
[15]Li Bo,Zhang Zhida,Ma Depeng,et al.Preparation and kinetic analysis of room-temperature vulcanized methylethylsilicone rubbers[J].J Appl Polym Sci,2015,132(41):42656-42663.