含氟三元丙烯酸酯乳液共聚物的合成及性能

Syntheses and Properties of Fluorine-containing (Meth)acrylate Copolymer Latex

由甲基丙烯酸甲酯 (MMA)、丙烯酸丁酯 (BA)和含氟丙烯酸酯合成了含氟三元共聚乳液。FT IR、1HNMR、13 CNMR和19FNMR对产物的组成和结构进行了分析。研究了含氟单体用量、增溶剂 β 环糊精(β CD)用量和聚合条件对乳液聚合动力学、粒径和粒径分布的影响 ,以及这些因素对三元共聚物性能的影响。结果表明 ,聚合反应温度在 5 5～ 6 5℃范围 ,升高温度 ,使聚合反应速率明显加快。热分析表明 ,聚合温度对共聚物的组成几乎没有影响。增加含氟单体用量 (摩尔分数 0～ 3 0 % ) ,使聚合反应速率略有降低。加入少量增溶剂 β CD使共聚物的玻璃化温度 (Tg)升高。与不含氟的共聚物P(MMA co BA)膜性能比较 ,三元含氟共聚物乳液涂膜的表面接触角明显增大 。

Meth)acrylate copolymer latexes containing fluorine have been prepared via emulsion copolymerization of methyl methacrylate(MMA), butyl acrylate(BA) and fluorinated monomers, 2,2,2-trifluoroethyl methacrylate(TFEMA) and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate(HFBMA). FT-IR, ^(1)H NMR, (^( 13)C NMR) and ^(19)F NMR results confirmed the incorporation of fluorinated methacrylate units in the copolymers. The effect of amount of TFEMA, solubilization agent β-cyclodextrin, and polymerization conditions on the reaction rate, particle size and size distribution of latex, as well as on the copolymer properties have been investigated. The results indicated that the reaction rate increased with the increase of the reaction (temperature) in the range of 55 to 65 ℃. DSC and TGA results showed the reaction temperature hardly affected the copolymer composition. The contact angles of the copolymer films with fluorine were greater than that of the film without any fluorine moiety, suggesting that the fluorine-containing units in the copolymers are in favor of (improvement) of the film property.