Sablong Rafaël, Duchateau Robbert, Koning Cor E, de Wit Gert, va Es Daan, Koelewijn Roelof, van Haveren Jacco
Laboratory of Polymer Chemistry, Eindhoven University of Technology, Den Dolech 2, PO Box 513, 5600 MB Eindhoven, The Netherlands.
Biomacromolecules. 2008 Nov;9(11):3090-7. doi: 10.1021/bm800627d. Epub 2008 Oct 7.
The biomass-based monomer isosorbide was incorporated into poly(butylene terephthalate) (PBT) by solid-state polymerization (SSP) using the macrodiol monomer BTITB-(OH) 2, which consists of isosorbide (I), terephthalic acid (T), and 1,4-butandiol (B) residues. This macromonomer can be synthesized by a simple one-pot, two-step reaction. Polymers with number-average molecular weights up to 100,000 g x mol (-1) were readily synthesized from various ratios of PBT/BTITB-(OH) 2. Their molecular weights, thermal properties, and colors were compared with corresponding copolyesters that were obtained by melt polycondensation. We found that T m, T c, and especially T g were superior for materials that were obtained by SSP. This is ascribed to differences in the microstructures of both types of copolyesters; the SSP products exhibit a more blocky structure than do the more random melt-polymerized counterparts. The SSP method resulted in much higher molecular weights and much less colored polymers, and it seems to be the preferred route for incorporating biobased monomers that exhibit limited thermal stability into engineering plastics.
通过固态聚合（SSP），使用由异山梨醇（I）、对苯二甲酸（T）和1,4 - 丁二醇（B）残基组成的大分子二醇单体BTITB-(OH)₂，将生物质基单体异山梨醇引入聚对苯二甲酸丁二醇酯（PBT）中。这种大分子单体可通过简单的一锅两步反应合成。由不同比例的PBT/BTITB-(OH)₂很容易合成数均分子量高达100,000 g·mol⁻¹的聚合物。将它们的分子量、热性能和颜色与通过熔融缩聚得到的相应共聚酯进行了比较。我们发现，通过SSP得到的材料的熔点（Tₘ）、结晶温度（Tₑ），尤其是玻璃化转变温度（T₉）更优异。这归因于两种共聚酯微观结构的差异；SSP产物比更无规的熔融聚合产物呈现出更块状的结构。SSP方法产生的聚合物分子量更高且颜色更浅，对于将热稳定性有限的生物基单体引入工程塑料而言，它似乎是首选途径。
