Anionic polymerization of fluorine-substituted phenyl methacrylates  

作　　者：Bin Li Pan Zhou Yuefei Chen Biao Jiang Hongping Zhu 

机构地区：[1]State Key Laboratory of Physical Chemistry of Solid Surfaces [2]National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters [3]College of Chemistry and Chemical Engineering, Xiamen University

出　　处：《Science China Chemistry》2015年第1期107-113,共7页中国科学（化学英文版）

基　　金：supported by the National Basic Research Program of China(2012CB821704);the National Natural Science Foundation of China(20972129);the Innovative Research Team Program(IRT1036,J1310024)

摘　　要：Synthesis and anionic polymerization of the fluorine-substituted phenyl methacrylates are herein reported. A series of monodi-, and multi-substituted fluorophenyl methacrylates H2C=C（CH3）C（O）OC6H4F-4 （M^1a）, H2C=C（CH3）C（O）OC6H4F-3 （M^1b）, HEC=C（CH3）C（O）OC6H3F2-2,4 （M^2）, H2C=C（CH3）C（O）OC6H2F3-2,3,4 （M^3）, H2C=C（CH3）C（O）OC6HF4-2,3,5,6 （M^4）, and H2C=C（CH3）C（O）OC6F5 （M^5） were synthesized and characterized. Initially, the polymerization was carded out on the monomer M^1a by using nBuLi, tBuLi, and KH as the respective catalysts; this approach produced the polymers in yields of 12%-50%, but with lower molecular weights. Similar results were obtained by using tBuLi for catalytically polymerizing the other five monomers. By introducing a co-catalyst MeAl（BHT）2, the catalysts Nail, LiH, and tBuOLi each were tested to polymerize M^1a, which gave the polymers in very low yields （3%-7%）. Polymer yields of 13%-27% were obtained by each of the catalysts LiAlH4, nBuLi, PhLi, and tBuLi in connection with MeAI（BHT）2, but a better yield （61%） was achieved with KH/MeAl（BHT）2. The KH/MeAl（BHT）2 catalyst system was further employed to polymerize M^1b and M^2, which afforded respective polymer yields of 12%-63% and 10%-53%, depending on the molar ratios of KH：MeAl（BHT）2 as well as on the monomer concentrations. All of the polymers produced were syndiotactically rich in structure, as indicated by either ^1H or ^19F NMR data. The polymerization mechanism by the combined catalyst system is proposed.Synthesis and anionic polymerization of the fluorine-substituted phenyl methacrylates are herein reported.A series of mono-,di-,and multi-substituted fluorophenyl methacrylates H2C=C(CH3)C(O)OC6H4F-4(M1a),H2C=C(CH3)C(O)OC6H4F-3(M1b),H2C=C(CH3)C(O)OC6H3F2-2,4(M2),H2C=C(CH3)C(O)OC6H2F3-2,3,4(M3),H2C=C(CH3)C(O)OC6HF4-2,3,5,6(M4),and H2C=C(CH3)C(O)OC6F5(M5)were synthesized and characterized.Initially,the polymerization was carried out on the monomer M1a by using n Bu Li,t Bu Li,and KH as the respective catalysts;this approach produced the polymers in yields of12%–50%,but with lower molecular weights.Similar results were obtained by using t Bu Li for catalytically polymerizing the other five monomers.By introducing a co-catalyst Me Al(BHT)2,the catalysts Na H,Li H,and t Bu OLi each were tested to polymerize M1a,which gave the polymers in very low yields(3%–7%).Polymer yields of 13%–27%were obtained by each of the catalysts Li Al H4,n Bu Li,Ph Li,and t Bu Li in connection with Me Al(BHT)2,but a better yield(61%)was achieved with KH/Me Al(BHT)2.The KH/Me Al(BHT)2 catalyst system was further employed to polymerize M1b and M2,which afforded respective polymer yields of 12%–63%and 10%–53%,depending on the molar ratios of KH:Me Al(BHT)2 as well as on the monomer concentrations.All of the polymers produced were syndiotactically rich in structure,as indicated by either 1H or 19F NMR data.The polymerization mechanism by the combined catalyst system is proposed.

关 键 词：fluorophenyl methacrylates the combined catalyst system anionic polymerization syndiotactic polymer ^1H and ^19F NMR data 

分 类 号：O631.5[理学—高分子化学]