乳液聚合法制备含乙烯基聚硅氧烷大分子及其性能研究

发布时间：2018-04-20 16:40

  本文选题：乳液聚合 + 乙烯基聚硅氧烷乳液　； 参考：《湖北大学》2011年硕士论文

【摘要】：有机硅聚合物是一类兼具有机/无机材料双重特性的特种高分子,其具有许多优异的理化性能,如耐高低温性、耐候性、疏水性、生理惰性等,因而具有广泛的用途。其中,有机硅乳液已经被广泛应用于纺织印染、医药、交通等行业作为后整理剂、光亮剂、消泡剂、化妆品添加剂、药物载体等。近20年来,八甲基环四硅氧烷(D4)开环乳液聚合制备线型聚二甲基硅氧烷(PDMS)的报道很多,而有关D4与其他含乙烯基有机硅单体的乳液共聚很少报道,特别是以碱催化开环乳液共聚制备含乙烯基聚硅氧烷(Vi-PDMS)大分子的研究鲜见报道。本文以氢氧化钾(KOH)为催化剂,十六烷基三甲基溴化铵(CTAB)和辛基酚聚氧乙烯(10)醚(OP-10)为复合乳化剂,采用四甲基四乙烯基环四硅氧烷(D4Vi)、Y-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)与D4共聚制备Vi-PDMS大分子乳液。 在D4/D4Vi的乳液共聚中,研究了复合乳化剂用量[E]及配比、KOH用量、环硅氧烷用量[M]及配比、反应温度对乳液性能(乳胶粒粒径及其分布、乳胶粒子的ζ电位、聚合物的摩尔质量、乳液稳定性等)的影响。结果表明,聚合较佳条件为：复合乳化剂用量为乳液质量的5.72%,CTAB与OP-10的质量比为1：6,KOH用量为乳液质量的0.191%,环硅氧烷用量为乳液质量的30%以下,D4与D4Vi的质量比为9：1,反应温度为80℃,反应时间为8.5h；此条件下的表观动力学方程为Rp=k[E]0.18[KOH]0.59[M]0.75,表观活化能为Ea=52.77kJ/mol; FTIR证明了D4和D4Vi发生了共聚反应；TEM对乳胶粒子的形貌进行了表征；TGA对共聚物的热稳定性进行了表征；共聚物中乙烯基含量随D4Vi用量的增大而增大。 在D4/MPS的乳液共聚中,研究了加料方式、复合乳化剂用量、KOH用量、D4用量、MPS用量、反应温度对乳液性能的影响。结果表明,采用单体连续滴加法可以提高共聚物的稳定性；聚合较佳条件为：当复合乳化剂用量为D4质量的4%,CTAB与OP-10的质量比为1：2,KOH用量为D4质量的0.2-0.4%,D4用量为乳液质量的20%,MPS用量为D4用量的2-4%,MPS在单体D4加完并恒温反应2-3小时后加入,反应温度为80℃；FTIR证明了D4和MPS发生了共聚反应；TGA表明聚二甲基硅氧烷中接枝一定含量的MPS在一定范围内能提升聚合物的热稳定性；共聚物中乙烯基含量随MPS用量的增大而增大,相对误差也相应增大。
[Abstract]:Silicone polymer is a kind of special polymer with dual properties of organic / inorganic materials. It has many excellent physical and chemical properties, such as high and low temperature resistance, weather resistance, hydrophobicity, physiological inertia and so on, so it has a wide range of applications. Silicone emulsion has been widely used as finishing agent, brightener, defoamer, cosmetic additive, drug carrier and so on. In the past 20 years, there have been many reports on the preparation of linear polydimethylsiloxane (PDMS) by ring-opening emulsion polymerization of octamethylcyclotetrasiloxane (D4), while the emulsion copolymerization of D4 with other vinyl silicone monomers has been rarely reported. In particular, the preparation of vinyl polysiloxane Vi-PDMS macromolecules by alkali catalyzed ring-opening emulsion copolymerization is rarely reported. In this paper, using potassium hydroxide (Koh) as catalyst, cetyltrimethylammonium bromide (CTAB) and octylphenol polyoxyethylene (10) ether as composite emulsifiers, Vi-PDMS macromolecular emulsion was prepared by copolymerization of tetramethyltetravinylcyclotetrasiloxane (tetramethyl tetravinylcyclotetrasiloxane) (D4ViO4) and D4 (methacryloxy) propyl trimethoxysilane (MPSs). In the emulsion copolymerization of D4/D4Vi, the amount of compound emulsifier [E] and the ratio of Koh, cyclosiloxane [M] and ratio, reaction temperature on emulsion properties (size and distribution of latex particles, 味 potential of latex particles, molar mass of polymer) were studied. Effects of emulsion stability, etc. The results showed that the optimum polymerization conditions were as follows: the mass ratio of compound emulsifier to OP-10 was 1: 6 Koh = 0.191% of emulsion mass, the mass ratio of cyclosiloxane to D4Vi was 9: 1, the mass ratio of cyclosiloxane to D4Vi was 9: 1, and the reaction temperature was 80 鈩，

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