Polymerization of New Type of Fluorine Containing Acrylic Monomer and Characterization of the Polymer

与一般认为含有大取代基的1,1-二取代乙烯不愿均聚的观点相反，一些具有大取代基的α -取代丙烯酸单体产率相应的聚合物。我们选择α -（烷基氧基甲基）丙烯酸酯和一种新的含氟单体α -（氟烷基氧基甲基）丙烯酸酯，研究了这些单体的合成和聚合。进一步对所得聚合物进行了表征。以α -（溴甲基）丙烯酸甲酯为原料，以C_2-C_<12>烷氧基为基材，高产出α -（烷氧基）丙烯酸甲酯。采用同样的方法，还引入了含C_2-C_3氟烷基链的氟烷氧甲基。所有的单体都很容易聚合成高分子量。烷氧基甲基丙烯酸酯和氟烷氧基甲基丙烯酸酯的Q值和e值表明，这些单体可分为共轭和弱电子接受单体。烷氧甲基和氟烷氧甲基的电子吸引特性增强了聚合和共聚反应的活性。支链烷氧基降低了反应活性。这些单体的聚合似乎容易受到位阻的影响，因为碳碳双键和自由基中心周围存在位阻。所得均聚物的T_g和降解温度均低于聚甲基丙烯酸甲酯。氟烷氧甲基衍生物的聚合物和组成氟烷氧甲基衍生物的一些聚合物分别可溶于甲醇和不溶于正己烷。接触角测试表明，含氟聚合物具有拒水、拒油的特性。

Contrary to generally accepted aspect that 1,1-disubstituted ethylene bearing bulky substituents is reluctant to homopolymerize, some alpha-substituted acrylic monomers with large alpha-substituent yield corresponding polymers. We chose alpha-(alkoxymethy1) acrylate and a new fluorine containing monomer, alpha-(fluoroalkoxymethy1) acrylate, to study on synthesis and polymerization of these monomers. Furthermore characterization of the resultant polymers was performed.Methyl alpha-(alkoxymethyl) acrylates bearing C_2-C_<12> alkoxy group were prepared from methyl alpha-(bromomethyl) acrylate in high yields. The fluoroalkoxymethyl group with C_2-C_3 fluoroalkyl chain were also introduced by similarly procedure. All the monomers radically polymerized readily to high molecular weight. The Q and e values of the alkoxymethyl- and fluoroalkoxymethylacrylates indicate that the these monomers are classified as conjugated and weak electron accepting monomers. Electron attracting character of the alkoxymethyl and fluoroalkoxymethyl groups enhanced the polymerization and copolymerization reactivities. The branched alkoxy group reduced the reactivities. The polymerization of these monomer seems to be susceptible to steric hindrance, because of steric congestion around the carbon-carbon double bond and the radical center.All the homopolymers obtained exhibited lower T_g and degradation temperature than poly (methyl methacrylate). The polymers from the fluoroalkoxymethyl derivatives and some polymers form the alkoxymethyl derivatives are soluble and insoluble in methanol and n-hexane, respectively. The contact angle measurement revealed that the fluorine containing polymers show water and oil repelant character.