Jiang Yi, Maniar Dina, Woortman Albert J J, Alberda van Ekenstein Gert O R, Loos Katja
Department of Polymer Chemistry, Zernike Institute for Advanced Materials, University of Groningen , Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX Eindhoven, The Netherlands.
Biomacromolecules. 2015 Nov 9;16(11):3674-85. doi: 10.1021/acs.biomac.5b01172. Epub 2015 Oct 12.
Furan-2,5-dicarboxylic acid (FDCA)-based furanic-aliphatic polyamides can be used as promising sustainable alternatives to polyphthalamides (semiaromatic polyamides) and be applied as high performance materials with great commercial interest. In this study, poly(octamethylene furanamide) (PA8F), an analog to poly(octamethylene terephthalamide) (PA8T), is successfully produced via Novozym 435 (N435)-catalyzed polymerization, using a one-stage method in toluene and a temperature-varied two-stage method in diphenyl ether, respectively. The enzymatic polymerization results in PA8F with high weight-average molecular weight (M̅(w)) up to 54000 g/mol. Studies on the one-stage enzymatic polymerization in toluene indicate that the molecular weights of PA8F increase significantly with the concentration of N435; with an optimal reaction temperature of 90 °C. The temperature-varied, two-stage enzymatic polymerization in diphenyl ether yields PA8F with higher molecular weights, as compared to the one-stage procedure, at higher reaction temperatures. MALDI-ToF MS analysis suggests that eight end groups are present in the obtained PA8F: ester/amine, ester/ester, amine/amine, acid/amine, ester/acid, acid/acid, ester/amide, and no end groups (cyclic). Compared to PA8T, the obtained PA8F possesses a similar Tg and similar crystal structures, a comparable Td, but a lower Tm.
基于呋喃 - 2,5 - 二羧酸（FDCA）的呋喃 - 脂肪族聚酰胺可作为聚邻苯二甲酰胺（半芳香族聚酰胺）有前景的可持续替代品，并作为具有巨大商业价值的高性能材料应用。在本研究中，聚（辛亚甲基呋喃酰胺）（PA8F），聚（辛亚甲基对苯二甲酰胺）（PA8T）的类似物，分别通过诺维信435（N435）催化的聚合反应成功制备，在甲苯中采用一步法，在二苯醚中采用变温两步法。酶促聚合得到重均分子量（M̅(w)）高达54000 g/mol的PA8F。对甲苯中一步酶促聚合的研究表明，PA8F的分子量随N435浓度显著增加；最佳反应温度为90℃。与一步法相比，在二苯醚中变温两步酶促聚合在较高反应温度下产生分子量更高的PA8F。基质辅助激光解吸电离飞行时间质谱（MALDI - ToF MS）分析表明，所得PA8F中存在八个端基：酯/胺、酯/酯、胺/胺、酸/胺、酯/酸、酸/酸、酯/酰胺和无端基（环状）。与PA8T相比，所得PA8F具有相似的玻璃化转变温度（Tg）和相似的晶体结构，热分解温度（Td）相当，但熔点（Tm）较低。
