双-(β-酮萘胺)镍(Ⅱ)/B(C_6F_5)_3/AlEt_3体系催化醋酸降冰片烯酯的聚合  

Polymerization of 5-Norbornene-2-yl-acetate Catalyzed by Bis-(β-ketonaphthylamino) Nickel(Ⅱ)/ B(C_6F_5)_3/AlEt_3 Catalytic System

作　　者：陈木青[1] 贺晓慧[1] 陈义旺[1] 周魏华[1] 石玲[1] 何福平[1] 伍青[2] 

机构地区：[1]南昌大学高分子研究所,南昌330031 [2]中山大学化学与化学工程学院高分子研究所

出　　处：《应用化学》2009年第8期923-928,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(50663002);江西省自然科学基金(2007GZC1727);江西省教育厅基金(Ganjiaojizi200713)资助项目

摘　　要：采用双-(β-酮萘胺)镍(Ⅱ)/B(C6F5)3/AlEt3体系可在20～90℃范围内在甲苯溶剂中催化醋酸降冰片烯酯聚合,得到中等分子量(Mw=7.0×103～3.1×104g/mol)和分子量分布较窄(Mw/Mn为1.8～2.0)的醋酸降冰片烯酯聚合物。采用1HNMR、13C NMR、FT-IR、DSC、TGA及广角X射线衍射(WAXD)等技术对所得聚合物进行了结构表征和性能测试。结果表明,所得的聚醋酸降冰片烯酯为加成型产物,证明此催化体系催化醋酸降冰片烯酯聚合是按乙烯基加成模式进行的;所得聚合产物为非晶态,具有短程有序长程无序的特征,分子链间的距离为1.24 nm;聚合产物具有较好的热稳定性(Td>330℃),并能够溶解在大部分普通有机溶剂中。Polymerizations of 5-norbornene-2-yl-acetate in toluene were catalyzed by a new late transition metal complex catalytic system based on bis-（β-ketonaphthylamino） nickel（Ⅱ）/B（C6F5）3/AlEt3.The above catalytic system can polymerize 5-norbornene-2-yl-acetate effectly in a range of 2090 ℃ and produced poly（5-norbornene-2-yl-acetate）s with moderate molecular mass（Mw=7.0×1033.1×104 g/mol） and relative narrow molecular mass distributions（Mw/Mn=1.82.0）.The obtained polymers were characterized by proton and carbon nuclear magnetic resonance,Fourier-transform infrared spectroscopy,differential scanning calorimetry,thermogravimetric analysis and wide-angle X-ray diffraction.Analyses of nuclear magnetic resonance and Fourier-transform infrared spectroscopy indicate that the obtained polymers are vinyl-addition poly（5-norbornene-2-yl-acetate）s,and demonstrate that the above catalytic system initiated 5-norbornene-2-yl-acetate polymerization according to the vinyl-addition mode.Wide-angle X-ray diffraction analysis result shows that poly（5-norbornene-2-yl-acetate） exhibits non-crystallinity but short-range order and long-range disorder,the interchain distance of the polymer is 1.24 nm.The polymer has a better thermal stability（Td〉330 ℃） and is soluble in many common solvents.

关 键 词：镍(Ⅱ)配合物 醋酸降冰片烯酯 催化聚合 

分 类 号：O632[理学—高分子化学]