钛酸四丁酯催化制备聚碳酸(1,6-己二醇)酯二醇  

Preparation of Poly(1,6-Hexanediol) Carbonate Diols Catalyzed by Ti(OBu)_4

作　　者：郝俊松[1] 杜娟[1,2] 左琳[1] 刘少勇 李再峰[1] 

机构地区：[1]生态化工教育部重点实验室,青岛科技大学化学与分子工程学院,山东青岛266042 [2]宝鸡文理学院化学化工系,陕西宝鸡721013 [3]烟台华大化学工业有限公司,山东烟台264002

出　　处：《高分子材料科学与工程》2010年第12期12-15,共4页Polymer Materials Science & Engineering

基　　金：山东省自然科学基金资助项目(Y2008B08);山东省中青年科学家奖励基金(2007BS04001);山东省科技攻关计(2008GG10003008)

摘　　要：以碳酸二乙酯(DEC)和1,6-己二醇(HDO)为原料,钛酸四丁酯(Ti(OBu)4)为催化剂,经常压蒸馏和减压缩聚两阶段,酯交换反应制备了分子量2000g/mol的聚碳酸(1,6-己二醇)酯二醇(PCDL)。研究了不同催化剂、减压反应温度、减压时间对聚合过程的影响,优化出最佳合成工艺。实验结果表明,Ti(OBu)4用量为0.05%(占碳酸二乙酯(DEC)的质量分数)时,表现出最好的催化效果;升高减压温度能够有效提高反应速度;调整减压反应时间长短可有效控制PCDL的分子量及分布系数。用红外光谱(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、差示扫描量热(DSC)等分析表征了合成产物,并提出了Ti(OBu)4的催化机理。Poly（1,6-hexanediol） carbonate diols （PCDL） was synthesized using 1,6-hexanediol （HDO） and diethyl carbonate（DEC） in the presence of Ti（OBu）4 as catalyst. The polymerization reaction was carried out in a two-stage process,including atmospheric pressure and vacuum. All reaction conditions were investigated based on Ti（OBu）4. The experiment results show that it exhibits the best catalytic activity with Ti（OBu）4 accounting for 0.05 weight percent of HDO. PCDL of expected number average molecular weight is prepared rapidly with raising the reaction temperature. It is available for controlling the molecular weight and polydispersity of PCDL to alter the vacuum time. The characters of PCDL were determined by Fourier transform infrared spectrum（FT-IR）,1H nuclear magnetic resonance spectrum（1H-NMR）,gel permeation in chromatography（GPC） and differential scanning calorimetry （DSC）. It is concluded that Ti（OBu）4 is evidenced to be an effective catalyst for transesterification. The possible reaction mechanism of Ti（OBu）4 was offered.

关 键 词：聚碳酸(1 6-己二醇)酯二醇 钛酸四丁酯 酯交换 

分 类 号：TQ314.242[化学工程—高聚物工业]