Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Faraday Discuss. 2017 Sep 21;202:61-77. doi: 10.1039/c7fd00057j.
A family of monomers, including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA), terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives, all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have been combined with FDCA and TA derivatives to produce a range of novel polyesters. It is shown that the use of secondary diols leads to polymers with higher glass transition temperatures (T) than those prepared from their primary diol equivalents. Two methods of polymerisation were investigated, the first employing activation of the aromatic diacids via the corresponding diacid chlorides and the second using a transesterification procedure. Longer chain diols were found to be more reactive than the shorter chain alternatives, generally giving rise to higher molecular weight polymers, an effect shown to be most pronounced when using the transesterification route. Finally, novel diesters with high degrees of branching in their hydrocarbon chains are introduced as potential monomers for possible low surface energy materials applications.
一类单体，包括 2,5-己二醇、2,7-辛二醇、2,5-呋喃二甲酸（FDCA）、对苯二甲酸（TA）和支链己二酸和壬二酸衍生物，都可以在生物质衍生的平台分子 5-（氯甲基）糠醛（CMF）中找到共同的来源。二醇单体以前在聚合化学中鲜为人知，已与 FDCA 和 TA 衍生物结合，生产出一系列新型聚酯。结果表明，使用仲二醇会导致聚合物的玻璃化转变温度（Tg）高于那些由其相应的伯二醇等当量制备的聚合物。研究了两种聚合方法，第一种方法是通过相应的二羧酸二酰氯使芳香族二酸活化，第二种方法是使用酯交换法。发现长链二醇比短链二醇更具反应性，通常会产生更高分子量的聚合物，通过酯交换路线，这种效果最为明显。最后，作为可能的低表面能材料应用的潜在单体，引入了具有高支化度的新型二酯。
