聚2,5-呋喃二甲酸1,8-辛二酯的聚合反应  

Synthesis of Poly( octylene 2,5-furandicarboxylate)

作　　者：李连贵[1] 李洋[1] 叶冲[2] 张强[2] 姜敏[2] 周光远[2,3] 

机构地区：[1]长春工业大学化学与生命科学学院,长春130012 [2]中国科学院长春应用化学研究所生态环境高分子材料重点实验室,长春130022 [3]常州储能材料与器件研究院,常州213002

出　　处：《应用化学》2013年第6期661-666,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金青年科学基金资助项目(51103152)

摘　　要：以可再生资源2,5-呋喃二甲酸(FDCA)和1,8-辛二醇(1,8-ODO)为原料,钛酸四丁酯为催化剂,采用直接酯化法制得聚2,5-呋喃二甲酸1,8-辛二酯(1,8-POF)。考察了原料配比、催化剂用量、酯化温度、缩聚温度及缩聚时间对聚合反应的影响,结果表明,当n(FDCA)∶n(1,8-ODO)=1∶1.2,钛酸四丁酯摩尔分数为0.3%,酯化温度为240℃,缩聚温度为260℃,缩聚时间为300 min时,缩聚产物的比浓粘度最高(2.1 dL/g),端羧基含量最低(5.8 mol/t)。与乙二醇相比,采用1,8-辛二醇为单体降低了酸醇的摩尔比,减少了醇的消耗,同时得到了较高分子量的聚合物。气质联用仪对酯化馏出液和缩聚产物真空抽出物进行了分析,结果表明,酯化馏出液的主要成分是水,并含有少量的1,8-ODO;缩聚产物真空抽出物的组成为环己酮(56%)、顺式-3-辛烯醇(18%)、4-甲基-3-戊烯-2-酮(17%)和4-羟基-4-甲基-2-戊酮(9%)。Poly（octylene 2,5-furandicarboxylate）（POF） was synthesized via the direct esterification method starting from 2,5-furandicarboxylic acid（FDCA） and 1,8-octylene glycol（1,8-ODO）, in which tetrabutyl titanate was chosen as catalyst. Effect of the molar ratio of F-DCA to 1,8-ODO, dosage of tetrabutyl titanate, esterification temperature, polycondensation temperature on the esterification and polycondensation processes were studied in details. The optimized process conditions are：n（FDCA）∶n（1,8-ODO）=1∶1.2, tetrabutyl titanate dosage is 3×10-3 mol/mol FDCA, esterification temperature is 240 ℃, polycondensation temperature is 260 ℃, polycondensation time is 300 min. The relative molecular mass of the condensation product is the highest（ηSP/ρ=2.1 dL/g）, and the carboxylic group content is the lowest（5.8 mol/t）. Compared with ethylene glycol, using the 1,8-ODO reduced the molar ratio of FDCA to 1,8-ODO, and reduced the consumption of alcohol, meanwhile we got a high molecular mass polymer. The results of gas chromatography mass spectrometry（GC-MS） confirmed the composition of the esterification distillate and polycondensation product extractives. The results were found to be： the main ingredient of esterification distillate is H2O, and the other component is 1,8-ODO; polycondensation product extractives are composed of cyclohexanone （56%）, （Z）-3-octene alcohol（18%）, 4-methyl-3-amylene-2-ketone（17%）, 4-hydro-xy-4-methyl-2-pentan-one（9%）.

关 键 词：聚呋喃二甲酸辛二酯 呋喃二甲酸 直接酯化法 可再生资源 

分 类 号：O633.1[理学—高分子化学]