氧化羰化法直接合成双酚A型聚碳酸酯(英文)  

Direct Synthesis of Bisphenol A-based Polycarbonate by Oxidative Carbonylation

作　　者：王庶[1] 梅付名[1] 李光兴[1] 朱志刚[1] 代庆伟[1] 

机构地区：[1]华中科技大学化学系,湖北武汉430074

出　　处：《合成化学》2004年第1期73-76,88,共5页Chinese Journal of Synthetic Chemistry

摘　　要：使用Pd系氧化还原催化体系氧化羰化双酚A和CO直接合成了聚碳酸酯。在PdCl20 .0 1 6mmol,n(Pd)∶n(Cu)∶n(对苯醌 )∶n(四丁基溴化铵 ) =1∶4∶40∶40 ,双酚A 2 2mmol,CH2 Cl25 0mL ,4A分子筛 4g ,CO 5 .5MPa ,O2 0 .5MPa ,反应温度 1 0 0℃ ,搅拌速度 80 0rpm的条件下反应 1 2h ,得到的聚碳酸酯重均分子量Mw 为 2 4 5 0。探索了杂多酸和杂多酸的四丁基铵盐对氧化羰化双酚A直接合成聚碳酸酯的促进作用。使用Pd Mn (TBA) 8SiW1 2 O42 催化剂体系 ,在上述相同的实验条件下反应 8h ,得到的聚碳酸酯重均分子量Mw 为 2 2 2 5 ,好于Pd Cu 苯醌催化体系的结果 (Mw=1 72 0 )。对合成得到的聚碳酸酯进行了IR光谱分析 ,并通过与相同条件下得到的商品聚碳酸酯 (Mw=2 2 0 0 0 )的IR光谱对照 ,对实验结果进行了确认。Direct synthesis of polycarbonate by oxidative carbonylation of bisphenol A and CO was carried out using Pd-based redox catalyst systems. Under the following condition: PdCl 2 0.016mmol, the molar ratio of Pd ∶Cu ∶p -benzoquinone ∶tetrabutylammoniun bromide=1 ∶4 ∶40 ∶40, bisphenol A 22mmol, CH 2Cl 2 50mL, 4A molecular sieves 4g, CO 5.5MPa, O 2 0.5MPa, reaction temperature 100℃, reaction time 12h and stirring speed 800rpm, a polycarbonate with M w=2450 was obtained. The selected heteropolyacids and their tetrabutylammonium salts were explored as a promoter in the oxidative carbonylation of bisphenol A. The polymer with M w=2225 was obtained over Pd-Mn-(TBA) 8SiW 12 O 42 catalyst system under the same reaction condition mentioned above for just 8h polymerization, which is better than that obtained in Pd-Cu-benzoquinone catalyst system(M w=1720). The synthesized polycarbonate was analyzed in details using FT-IR, and a comparative IR analysis with commercial polycarbonate sample(M w=22000) carried for the polymer identification confirmed the polycarbonate formation.

关 键 词：聚碳酸酯 氧化羰化 双酚A 杂多酸 合成 

分 类 号：O633.14[理学—高分子化学]