Abstract：
The present research article delves into the preparation of a new class of bio-based polyesters from α,ω-diene furandicarboxylate monomers. In particular, it exploits the use of acyclic diene metathesis polymerisation (ADMET) on 2,5-furandicarboxylic acid (FDCA)-derived compounds. First, a library of furan-based α,ω-diene monomers was prepared via acid- or base-catalyzed transesterification of 2,5-furandicarboxylic acid dimethyl ester (FDME) with commercially available alcohols incorporating terminal olefins, i. e., allyl alcohol, but-3-en-1-ol, hex-5-en-1-ol and dec-9-en-1-ol. Then, the novel monomers were subjected to ADMET polymerisation employing different catalysts and reaction conditions. Interestingly, first-generation Grubbs catalyst was found to be the best promoter for ADMET polymerisation. This catalyst allowed the preparation of a new family of bio-based polyesters with molecular weights up to 26.4 kDa, with good thermal stability, and adaptable cis-trans conformations. Results also revealed that the monomer structure had a direct impact on the polymerisation efficiency and the resulting thermal properties. The effect of green bio-based solvents such as Cyrene™, dimethyl isosorbide (DMI) and γ-valerolactone (GVL) on the polymerisation process was also studied. Data collected showed that the solvent concentration influenced both the yield and length of polymers formed. Furthermore, some co-polymerisation experiments were conducted; the successful integration of different monomers in the resulting copolymer was shown to affect the glass transition temperature (Tg) of the resulting materials.
摘要：
本研究文章深入研究了从α，ω-呋喃二甲酸二烯单体。特别是,它利用了在2,5-呋喃二甲酸衍生的单体上使用无环二烯易位聚合。首先,呋喃基α的库，ω-二烯单体是通过酸或碱催化的2,5-呋喃二甲酸二甲酯（FDME）与包含末端烯烃的市售醇的酯交换反应制备的，然后，使用不同的催化剂和反应条件对新型单体进行ADMET聚合。有趣的是,发现第一代Grubbs催化剂是ADMET聚合的最佳促进剂。该催化剂允许制备具有高分子量的新聚酯家族，优异的热稳定性，和适应性的顺式-反式构象。结果还表明，单体结构对聚合效率和所得的热性能有直接影响。绿色生物基溶剂如Cyrene™的效果，还研究了二甲基异山梨醇（dmi）和γ-戊内酯（GVL）对聚合过程的影响。收集的数据表明,溶剂浓度影响所形成的聚合物的产率和长度。此外，进行了一些共聚实验;不同单体在所得共聚物中的成功整合被证明会影响所得材料的玻璃化转变温度(Tg)。
