主链含有氟甲基/三氟甲硫基的聚丙烯酸酯类共聚物的构建

As is well-known, polymer chemistry is closely related with organic chemistry. Many milestones in polymer chemistry benefited from organic chemistry, such as living coordination polymerization (Ziegler-Natta catalyst), ROMP (Grubbs catalyst), and ATRP (from ATRA in organic chemistry). Obviously, organic chemistry can provide new functional monomer, new initiation-catalysis system, and new method of polymeric modification for polymer chemistry. In this project, through the combination of organic chemistry and polymer chemistry, on the basis of fluoro-alkylation reaction developed in recent years and effective post-polymerizaiton modification developed by our group (substitution reaction of activated alpha-methylene group neighbour to carbonyl of polyacrylates), we will partially fluorinate alpha-methylene group neighbour to carbonyl of polyacrylates so that they can be transformed into semi-fluorinated polyacrylate copolymer bearing trifluoromethyl/difluoromethyl/monofluoromethyl/trifluoromethylthio-containing backbone, which can not be directly obtained by polymerization. Through this project, we can afford new model compounds and endow current material with new property for the development of polymer science so as to promote the development of polymer science.

高分子化学与有机化学有很紧密的联系，高分子化学领域中许多里程碑式的重大成就均受益于有机化学，例如活性配位聚合(Ziegler-Natta催化剂)、开环复分解聚合(Grubbs催化剂)及原子转移自由基聚合(源于有机化学的ATRA)。有机化学显然可为高分子化学提供新的功能性单体、新的引发催化体系以及新的聚合物修饰方法。本项目拟通过有机化学与高分子化学的交叉融合，利用成熟的氟烷基化反应和被本课题组证明为切实有效的高分子官能化反应(聚丙烯酸酯的羰基α位的次甲基取代反应)，将普通的聚丙烯酸酯的羰基α位的次甲基简便高效地部分氟化，转化为无法直接通过聚合得到的主链含有三氟(二氟/一氟)甲基/三氟甲硫基的部分含氟聚丙烯酸酯类共聚物。通过本项目的研究，可为高分子科学的发展提供新的模型化合物，赋予现有材料以新的性能，从而促进高分子科学的发展。

部分含氟聚合物不仅具有全氟聚合物所具有的优异性能，而且具有良好的加工性和光透明性等优点，但由于单体的合成和聚合方面的困难，部分含氟聚合物的例子较少。我们利用成熟的有机化学反应，发展了部分含氟聚合物的合成新方法。我们用LDA拔氢和氟化试剂实现对普通聚合物主链的氟化改性，从而制得部分含氟聚合物，所得含氟聚合物表现出更疏水的特性。我们设计合成了含有二氟甲氧基和二氟甲硫基的含氟新单体，并研究了它们的活性聚合行为，所得聚合物表现出更为疏水、更低的LCST等特性。本项目制备了新的部分含氟聚合物，为高分子科学提供了新的模型聚合物，赋予了现有材料以新性能。