Stereoselective polymerization can yield polymers with specific tacticity and properties,and it is an essential topic throughout polymer synthesis history.Herein,we report for the first time on a vesicular catalysis m...Stereoselective polymerization can yield polymers with specific tacticity and properties,and it is an essential topic throughout polymer synthesis history.Herein,we report for the first time on a vesicular catalysis method to realize the green stereoregular polymerization of isotactic-rich poly(methyl methacrylate)(PMMA)in water and at ambient temperature and pressure,namely by conducting the polymerization of MMA monomers in the confined 5-10 nm thick hydrophobic layers of hyperbranched polymer vesicles.The isotactic degree of the as-prepared PMMAs increases from 12% to 40% with the decrease of vesicle size from 840 to 85 nm in hydrodynamic diameter(Dh)due to the conformation confinement effect of MMA monomers inside the thin vesicle membranes through a curvature-dependent way.The present work has extended the scope of green chemistry,and it also represents a new application of polymer vesicles in stereoregular polymerization.展开更多
Polymerization of isobutyl vinyl ether(IBVE)has been studied with mononuclear half-titanocene,CpTiCl_3[1]and dinuclear half-titanocenes,[(C_5H_4)_2(CH_2)_n][(TiCl_3)_2][2(n=3),3(n=6)],and[(C_5H_4)_2(CH_2)_n[(TiCl_2OR_...Polymerization of isobutyl vinyl ether(IBVE)has been studied with mononuclear half-titanocene,CpTiCl_3[1]and dinuclear half-titanocenes,[(C_5H_4)_2(CH_2)_n][(TiCl_3)_2][2(n=3),3(n=6)],and[(C_5H_4)_2(CH_2)_n[(TiCl_2OR_2](R=2,6- diisopropylphenoxyl)[4(n=3),5(n=6)],in the presence of methyl aluminoxanes(MAO)as cocatalyst in methylene chloride.The influences of the length of polymethylene brigde and the substitution of aryloxy group at the metal center have been investigated at three polymerization temperature(...展开更多
1 Results Polymerization of butadiene,isoprene and styrene and binary copolymerization of styrene with butadiene and isoprene were investigated using the catalyst Ti(η5-C5H5)(η2-MBMP)Cl (1) (MBMP=2,2′-methylenebis(...1 Results Polymerization of butadiene,isoprene and styrene and binary copolymerization of styrene with butadiene and isoprene were investigated using the catalyst Ti(η5-C5H5)(η2-MBMP)Cl (1) (MBMP=2,2′-methylenebis(6-tert-butyl-4-methylphenoxo) activated with methylaluminoxane (MAO).Syndiotactic polystyrene, cis-1,4- polybutadiene and cis-1,4-polyisoprene were obtained in good yields at 50 °C.Binary copolymerization of styrene with butadiene yielded block copolymers containing segments of cis-1,4-polybut...展开更多
基金financially supported by the National Natural Science Foundation of China(21890730,21890733,and 51773115)the Program for Basic Research of Shanghai Science and Technology Commission(19JC1410400).
文摘Stereoselective polymerization can yield polymers with specific tacticity and properties,and it is an essential topic throughout polymer synthesis history.Herein,we report for the first time on a vesicular catalysis method to realize the green stereoregular polymerization of isotactic-rich poly(methyl methacrylate)(PMMA)in water and at ambient temperature and pressure,namely by conducting the polymerization of MMA monomers in the confined 5-10 nm thick hydrophobic layers of hyperbranched polymer vesicles.The isotactic degree of the as-prepared PMMAs increases from 12% to 40% with the decrease of vesicle size from 840 to 85 nm in hydrodynamic diameter(Dh)due to the conformation confinement effect of MMA monomers inside the thin vesicle membranes through a curvature-dependent way.The present work has extended the scope of green chemistry,and it also represents a new application of polymer vesicles in stereoregular polymerization.
基金the Korea Ministry of Commerce,Industry,and Energy(Grant RTI04-01-04,Regional Technology Innovation Program).
文摘Polymerization of isobutyl vinyl ether(IBVE)has been studied with mononuclear half-titanocene,CpTiCl_3[1]and dinuclear half-titanocenes,[(C_5H_4)_2(CH_2)_n][(TiCl_3)_2][2(n=3),3(n=6)],and[(C_5H_4)_2(CH_2)_n[(TiCl_2OR_2](R=2,6- diisopropylphenoxyl)[4(n=3),5(n=6)],in the presence of methyl aluminoxanes(MAO)as cocatalyst in methylene chloride.The influences of the length of polymethylene brigde and the substitution of aryloxy group at the metal center have been investigated at three polymerization temperature(...
文摘1 Results Polymerization of butadiene,isoprene and styrene and binary copolymerization of styrene with butadiene and isoprene were investigated using the catalyst Ti(η5-C5H5)(η2-MBMP)Cl (1) (MBMP=2,2′-methylenebis(6-tert-butyl-4-methylphenoxo) activated with methylaluminoxane (MAO).Syndiotactic polystyrene, cis-1,4- polybutadiene and cis-1,4-polyisoprene were obtained in good yields at 50 °C.Binary copolymerization of styrene with butadiene yielded block copolymers containing segments of cis-1,4-polybut...
