含氟聚硅氧烷及功能性有机硅化合物的研究

发布时间：2018-03-13 18:34

  本文选题：含氟硅氧烷　切入点：氟硅橡胶　出处：《烟台大学》2017年硕士论文　论文类型：学位论文

【摘要】：有机硅材料具有优异的耐高低温、耐辐射、耐腐蚀、电气绝缘、憎水等性能,因此被广泛应用于电子电气、纺织、医疗、建筑、机械等各行各业。随着时代的发展,对有机硅材料也提出了更高的要求,从而推动了有机硅材料的发展。本文基于有机硅材料,在前人研究的基础上,开展了以下三部分研究内容:(1)进行了含氟硅氧烷的合成、聚含氟硅氧烷的合成、氟硅橡胶的硫化。利用FT-IR、1H-NMR、29Si-NMR对所得化合物进行了结构表征,并探索了含氟硅烷最佳合成单体比例、不同氟含量聚氟硅氧烷的聚合、氟硅橡胶最佳硫化条件,考察了硫化后氟硅橡胶力学性能、耐老化性能、耐溶剂性能。结果表明,通过硅氢加成的方法将含氟烯丙基醚接到八甲基环四硅氧烷中,在n氟单体:n硅单体=10:1,溶剂为反应体系的两倍时,有利于硅氢加成反应的进行。经FT-IR、1H-NMR、29Si-NMR分析,Si-H键完全消失,产物收率高达99%以上。将含氟环硅氧烷、八甲基环四硅氧烷、四乙烯基四甲基环四硅氧烷通过四甲基氢氧化铵硅醇盐作为催化剂进行开环聚合,当四甲基氢氧化铵为0.03%时有利于聚合物分子量达到最大值。聚氟硅氧烷的硫化需在硫化剂双二五与DCP共同作用下于150~160℃,20~25min完成。其含氟硅氧烷链节达到5%时,表面能最低。将有无进行二段硫化的氟硅橡胶进行力学性能对比测试,经验证得二段硫化有利于橡胶力学性能的提高。(2)端含氢硅油硅氢加成反应活性。通过FT-IR、1H-NMR、29Si-NMR表征确认了不同链节长度端含氢结构的基础上,采用固化反应、示差扫描量热分析(DSC)等方法研究了系列含氢低聚硅氧烷产物的硅氢加成反应活性。经测定固化反应时间及DSC的方法验证,对于含不同链节数的二甲基硅基封端的二苯基硅氧烷低聚物来说,随着-Si(Ph)2-链节数目的增加,低聚物硅氢加成的反应活性逐步降低。(3)支化硅油的研究。以有机硅单体工业副产  甲基苯基二甲氧基硅烷(D)/苯基三甲氧基硅烷(T)共混物为原料,通过酸性条件下水解,碱性条件下缩合、平衡反应,合成含乙烯基的“T”型支化乙烯基硅油。根据不同批次DT副产物各单体含量不同进行单体比例调节,经FT-IR、1H-NMR、29Si-NMR等测试证明,得到了所需结构产物,合成工艺稳定。合成产物用于封装胶组份,并进行了性能测试,结果表明性能优良。
[Abstract]:Silicone materials have excellent resistance to high and low temperature, radiation resistance, corrosion resistance, electrical insulation, hydrophobicity and so on, so they are widely used in electronic and electrical, textile, medical, construction, machinery and other industries. With the development of the times, The development of organosilicon materials has been promoted. Based on silicone materials and based on previous studies, the synthesis of fluorosiloxane has been carried out in the following three parts: 1). Synthesis of polyfluorosiloxane and vulcanization of fluorosilicone rubber. The structure of the compound was characterized by FT-IRN 1H-NMR-29Si-NMR. The optimum synthetic monomer ratio of fluorosilane, polymerization of polyfluorosiloxane with different fluorine content, and optimum curing conditions of fluorinated silicone rubber were explored. The mechanical properties, aging resistance and solvent resistance of vulcanized fluorosilicone rubber were investigated. The results showed that fluoroallyl ethers were connected to octamethylcyclotetrasiloxane by hydrosilylation. When n: n monomer 10: 1, the solvent is twice as the reaction system, the addition reaction of hydrosilyl is advantageous. By FT-IRN 1H-NMR-29Si-NMR analysis, the bond of Si-H disappears completely and the yield of the product reaches more than 99%. The fluorinated cyclosiloxane, octamethylcyclotetrasiloxane, octamethylcyclosiloxane, and tetrasiloxane are obtained by FT-IR and 1H-NMR-29Si-NMR analysis. The ring-opening polymerization of tetravinyltetramethylcyclotetrasiloxane was carried out by using tetramethyl ammonium hydroxide as the catalyst. When tetramethylammonium hydroxide is 0.03, the molecular weight of polyfluorosiloxane can reach its maximum. The vulcanization of polyfluorosiloxane should be completed at 150 鈩，

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