新型嵌段苯基硅树脂的设计及制备
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摘要
有机硅树脂是一种无机-有机杂化材料,兼具无机材料和有机聚合物的特性,具有耐高低温、耐辐射、耐氧化等特点,在航空航天、汽车、电子、化工等领域有重要应用。目前液体硅树脂主要是溶剂型硅树脂,利用硅羟基缩合放出水或利用烷氧基水解缩合形成的高度交联的聚合物,无论从工艺上还是性能上,在胶粘剂和复合材料基本树脂应用方面存在极大的限制。本文在研究室的POSS液体硅树脂的基础上,通过端羟基聚二甲基硅氧烷和三甲氧基硅烷的共水解缩合,制成一种不含溶剂的室温能流动的含有柔性链段的硅树脂,以期解决液体POSS硅树脂无法增韧的难题,具有较大的创新性和实用性。
在研究的过程中,我们对此反应所用的催化剂、反应温度、反应时间以及溶剂进行了逐步的研究,制成该树脂。
1、以端羟基聚二甲基硅氧烷和苯基三甲氧基硅烷作为反应物,通过可控水解缩合反应,制备了新型嵌段苯基硅树脂。研究了原料、催化剂、反应温度、反应时间和水解度对合成嵌段苯基硅树脂的影响,制成了一种不含溶剂的室温下能流动的液体硅树脂。
2、确定了合成树脂的最佳条件为：以盐酸为催化剂,水解度为1：2.5,80℃下反应9h,升温分水,最后减压旋蒸得到产物。
3、通过FTIR,1H-NMR、29Si-NMR、GPC、XRD等分析方法表征了液体硅树脂的结构。
4、研究了新型嵌段苯基硅树脂的固化,研究了固化剂结构与凝胶时间关系,掌握了固化剂用量与凝胶时间的关系。
5、利用非等温差示扫描量热法(DSC)分析,得到了产物的热降解反应表观活化能△E=43.0KJ／mol,热降解反应的动力学方程为dβ／dt=A0·exp(-△E／RT)·(1-β)=4.0·exp(-5181.6／T)·(1-β)。
6、研究树脂拉伸强度与三官能度苯基硅树脂含量的关系,得到树脂的拉伸强度随着三官能度苯基硅树脂含量的增加先增大后减小的结论。
Polysiloxanes are organic-inorganic hybrid polymers with good high-low-temperature resistance, radiation resistance and oxidation resistance, which make them widely applicated in aerospace, automotive, electronics, chemical industry and many other fields. Currently, the commercial liquid silicon resin is mainly solvent-based, which can be highly cross-linked by condensation of silanol groups with water released or by hydrolytic condensation of alkoxy groups at higher pressure and high temperature. Many limits exist while they are applicated as adhesives or as matrix resin in composites in both techniques and performance. On the basis of the POSS liquid silicon resin invented by our laboratory, a novel solvent-free liquid silicone resin with flexible segments in the backbone, was developed by hydrolytic copolycondensation of hydroxy-terminated polydimethylsiloxane and phenyl-trimethoxysilane in order to toughen POSS silicone resin, which are both innovatively and practically.
The synthetic process parameter, such as catalyst, solvent, reaction temperature and time was studied and the properties of the cured redin were evaluated.
1. The block-phenyl silicone resin was synthesized by controllable hydrolytic condensation reaction of Hydroxy-terminated polydimethylsiloxane and phenyltrimethoxysilane under certain conditions. And influences of raw materials, catalysts, reaction temperature, reaction time and degree of hydrolysis on synthetic block-phenyl silicone resin were investigated.
2. The optimum synthetic process were found out:First, the hydrolytic condensation reaction were carried out at 80℃for 9h at the mole ratio of 1:2.5 of phenyltrimethoxysilane to water catalysed by hydrochloric acid, Then raised temperature and separate water. Finally, the product was obtained by distillation at reduced pressure rotacooling.
3. The available structure of liquid silicone resin was proposed based on the characterized by the results of FTIR,1H-NMR,29Si-NMR, GPC and XRD.
4. The curing behavior of the new type block-phenyl silicone resin and the relationship between the structure of curing agent and gel time was measured, and the relationship between the amount of curing agent and gel time was studied.
5. By using DSC, the activation energy E of the thermal degradation of the curred resin was 43.0KJ/mol, and order of reaction and the dynamic equation of the thermal degradation reaction was dβ/dt=A0·exp(-△E/RT)·(1-β)=4.0·exp(-5181.6/T)·(1-β).
6. The relation of tensile strength and the amount of the phenyl silicone resin was revealed out that the tensile strength increases first and then decreased with the increasing of the amount of phenyl silicone resin.
在研究的过程中,我们对此反应所用的催化剂、反应温度、反应时间以及溶剂进行了逐步的研究,制成该树脂。
1、以端羟基聚二甲基硅氧烷和苯基三甲氧基硅烷作为反应物,通过可控水解缩合反应,制备了新型嵌段苯基硅树脂。研究了原料、催化剂、反应温度、反应时间和水解度对合成嵌段苯基硅树脂的影响,制成了一种不含溶剂的室温下能流动的液体硅树脂。
2、确定了合成树脂的最佳条件为：以盐酸为催化剂,水解度为1：2.5,80℃下反应9h,升温分水,最后减压旋蒸得到产物。
3、通过FTIR,1H-NMR、29Si-NMR、GPC、XRD等分析方法表征了液体硅树脂的结构。
4、研究了新型嵌段苯基硅树脂的固化,研究了固化剂结构与凝胶时间关系,掌握了固化剂用量与凝胶时间的关系。
5、利用非等温差示扫描量热法(DSC)分析,得到了产物的热降解反应表观活化能△E=43.0KJ／mol,热降解反应的动力学方程为dβ／dt=A0·exp(-△E／RT)·(1-β)=4.0·exp(-5181.6／T)·(1-β)。
6、研究树脂拉伸强度与三官能度苯基硅树脂含量的关系,得到树脂的拉伸强度随着三官能度苯基硅树脂含量的增加先增大后减小的结论。
Polysiloxanes are organic-inorganic hybrid polymers with good high-low-temperature resistance, radiation resistance and oxidation resistance, which make them widely applicated in aerospace, automotive, electronics, chemical industry and many other fields. Currently, the commercial liquid silicon resin is mainly solvent-based, which can be highly cross-linked by condensation of silanol groups with water released or by hydrolytic condensation of alkoxy groups at higher pressure and high temperature. Many limits exist while they are applicated as adhesives or as matrix resin in composites in both techniques and performance. On the basis of the POSS liquid silicon resin invented by our laboratory, a novel solvent-free liquid silicone resin with flexible segments in the backbone, was developed by hydrolytic copolycondensation of hydroxy-terminated polydimethylsiloxane and phenyl-trimethoxysilane in order to toughen POSS silicone resin, which are both innovatively and practically.
The synthetic process parameter, such as catalyst, solvent, reaction temperature and time was studied and the properties of the cured redin were evaluated.
1. The block-phenyl silicone resin was synthesized by controllable hydrolytic condensation reaction of Hydroxy-terminated polydimethylsiloxane and phenyltrimethoxysilane under certain conditions. And influences of raw materials, catalysts, reaction temperature, reaction time and degree of hydrolysis on synthetic block-phenyl silicone resin were investigated.
2. The optimum synthetic process were found out:First, the hydrolytic condensation reaction were carried out at 80℃for 9h at the mole ratio of 1:2.5 of phenyltrimethoxysilane to water catalysed by hydrochloric acid, Then raised temperature and separate water. Finally, the product was obtained by distillation at reduced pressure rotacooling.
3. The available structure of liquid silicone resin was proposed based on the characterized by the results of FTIR,1H-NMR,29Si-NMR, GPC and XRD.
4. The curing behavior of the new type block-phenyl silicone resin and the relationship between the structure of curing agent and gel time was measured, and the relationship between the amount of curing agent and gel time was studied.
5. By using DSC, the activation energy E of the thermal degradation of the curred resin was 43.0KJ/mol, and order of reaction and the dynamic equation of the thermal degradation reaction was dβ/dt=A0·exp(-△E/RT)·(1-β)=4.0·exp(-5181.6/T)·(1-β).
6. The relation of tensile strength and the amount of the phenyl silicone resin was revealed out that the tensile strength increases first and then decreased with the increasing of the amount of phenyl silicone resin.
引文
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[2]Azam Rahimi, Parvin Shokrolahi. Application of inorganic polymeric materials Ⅰ. Polysiloxanes[J]. International Journal of Inorganic Materials,2001(3):843-847.
[3]宁琳.有机硅聚合物导论[M].北京：科学出版社,2004：34-38.
[4]王春江.有机硅化合物的生产与发展[J].化工科技市场,2001(9)：15-17.
[5]李光亮.有机硅高分子化学[M].北京：科学出版社,1998,62-106.
[6]冯圣玉.有机硅高分子及其应用[M].北京：化学工业出版社,2004,86-102.
[7]R H Krieble, C A Burkhard. Cyclic dimethyl polymethylenedioxysilances [J]. J AMChem Sci,1947,69:2689-2696.
[8]Masayoshi Itoh, Kohji Inoue, Kenji Iwata. A heat-resistant silicon-based polymer [J]. Adv Mater,1997,9(15):1187-1190.
[9]Shigeki Kurrki, Kouichi Okita, Takeaki Kakigano. Thermosetting mechanism stu-dyofpoly[(phenylsilylene)-1,3-phenyleneethynylene] by solid-state NMRspect-roscopy and computation chemistry [J]. Macromolecules,1998,31:2804-2808.
[10]Ki-dong KiM, Jin-sung park, Hwan Kyn Kim. Blue Electroluminescence from novel silicon-containing poly(cyanoterephthalylidene) copolymer [J]. Macromolecules,1998,31: 7267-7272.
[11]Robert J P Corrius, William E Donglas, Zhi-xin Yang. Synthesis of poly (alkynylsilaneses) having various aromatic groups in the backbone [J]. Polym Sci,Part C,1990,28:431-437.
[12]王宏刚,毛绍兰,高金堂.耐热有机硅树脂研究进展[J].粘接剂,2000,21(30)：29-33.
[13]宋传洪.常温固化聚有机硅氧烷耐高温(700℃以上)涂料的研究[D].武汉：机械工业部武汉材料保护研究所,2001.
[14]Morton International, inc. Heat-resistance power coating[P]. US5422396,1995-06-06.
[15]K B DP Locker. Synthesis and photodegradation of poly2,5-bis(dimethylsilyl)-thioph-ene [J].Polym1989,21:133-140.
[16]徐健,孙长高.有机硅改性环氧树脂的研究.山东科学,1997,10(4)：22-25
[17]李杨.耐高温有机硅聚合物的研究[D].上海：华南理工大学,2002.
[18]刘宝.有机硅改性环氧树脂的合成[D].济南：山东大学,2005.
[19]Robert West. The Polysilane high Polymer [J]. J Organometallie Chem,1986,300: 327-346.
[20]方少明,王昊.α,ω-二羟基二甲基硅氧烷齐聚物的合成与研究[J].郑州轻工业学院学报,1992,7(1)：69-73.
[21]中国科学院兰州化学物理研究所：硅油[M].兰州：甘肃人民出版社,1973：134
[22]Kobayashi Kazu, Yamamoto Yokichi. Production of organopolysikoxane[P]. JP3170531, 1991
[23]Donald James Connolly, Longwood., William Franklin Gresham. Alapocas.Fluorocarbon Vinyl Ether polymers [P]. US3,282,875.1964.
[24]William G, Davies, Brian Elliott. Polymerization of siloxanes [P]. US3481898.1969.
[25]Beck James A(US), Lamont Peter(US). Siloxanyl-phosphate mixture and its use in stabilizing metal siloxates in siloxane polymers [P]. US5099051,1992.
[26]Herberg Micheal J(US), Macander.Process for the containuous manufacture of silicone gums[P]. US4551515,1985.
[27]夏毅然,宋劻远,杨兵,张蔚.用二苯基硅二醇合成苯基硅油[J].有机硅材料及应用,1998,1：4-5.
[28]陈鹤岗.甲基苯基硅油的研究[J].广州化学研究所.
[29]Sridhar Venigalla. Advanced materials & powders[J]. Amer Ceram Soc Bull,2000, 79(6):47-52.
[30]Bruce X Fu, Benjamin S Hsiao. Polym Int.2000,49,437.
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