聚2,5-呋喃二甲酸1,8-辛二酯的聚合反应

doi:10.3724/SP.J.1095.2013.20591

摘要/Abstract

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%）。

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, 聚合反应

Abstract: 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%).

Key words: Poly(octylene furandicarboxylate), furandicarboxylic acid, direct esterification method, renewable resources, polymerization reaction

中图分类号:

O633.1

李连贵, 李洋, 叶冲, 张强, 姜敏, 周光远. 聚2,5-呋喃二甲酸1,8-辛二酯的聚合反应[J]. 应用化学, DOI: 10.3724/SP.J.1095.2013.20591.

LI Liangui1, LI Yang1, YE Chong2, ZHANG Qiang2, JIANG Min2, ZHOU Guangyuan2,3*. Synthesis of Poly(octylene 2,5-furandicarboxylate)[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2013.20591.

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