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

与普遍接受的含大取代基的1，1-二取代乙烯不愿均聚的方面相反，一些含大取代基的α-取代的丙烯酸酯单体产生了相应的聚合物。我们选择了α-(烷氧基甲基)丙烯酸酯和一种新的含氟单体--α-(氟烷氧甲基)丙烯酸酯，对这些单体的合成和聚合进行了研究。以α-(溴甲基)丙烯酸甲酯为原料，高产率地合成了含C_2-C_2-烷氧基的α-(烷氧甲基)丙烯酸甲酯。类似的方法还引入了含C_2-C_3氟烷基链的氟烷氧甲基。所有的单体都很容易自由基聚合到高相对分子质量。烷氧甲基丙烯酸酯和氟烷氧甲基丙烯酸酯的Q值和e值表明，这些单体属于共轭和弱电子接受单体。烷氧基甲基和氟烷氧基甲基的吸电子特性提高了聚合和共聚反应活性。支化的烷氧基降低了反应活性。由于碳-碳双键和自由基中心附近的空间位阻，这些单体的聚合似乎很容易受到空间位阻的影响，所得均聚物的玻璃化温度和降解温度都低于聚甲基丙烯酸甲酯。氟烷氧甲基衍生物的聚合物和某些烷氧甲基衍生物的聚合物分别溶于甲醇和不溶于正己烷。接触角测试表明，含氟聚合物表现出水和油的反弹性。

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.