Three renewable, linear, aliphatic polyesters were prepared by Acyclic diene metathesis (ADMET) polymerization of α,ω‐dienes derived from fatty acids. Condensation of 9‐decenoic acid with allyl 9‐decenoate, ethylene glycol, and 9‐decen‐1‐ol proceeded in high conversion (≥94%) and purity (>99%) to give α,ω‐dienes suitable for subsequent polycondensation. Polymerization was achieved using 1.0 mol% Hoveyda‐Grubbs second‐generation metathesis catalyst in combination with 2.0 mol% 2,6‐dichloro‐1,4‐benzoquinone as an isomerization inhibitor under vacuum to drive equilibria toward polymer formation via ethene removal. Polymerization in the presence of solvent promoted ring‐closing metathesis (RCM) at the expense of polymer, with cyclization increasing as the concentration of monomer decreased. Thus, ADMET polymerizations were performed in bulk to mitigate RCM. The resulting polymers with M _n and Ð that ranged from 6.6 to 8.9 kDa and 1.75–2.14, respectively, contained 76% or more of renewable carbon content and exhibited atom and carbon economies of greater than 84%. Melt (T _m) and crystallization (T _c) temperatures were 20.8–48.4 °C and 3.8–37.6 °C, respectively, and increased as ester density decreased within polymer structures. Sub‐ambient glass transitions ranged from −10.3 to −50.0 °C. Lastly, the polymers were thermally stable below 320 °C, as 10% mass loss (T₁₀) occurred above 340 °C, which indicated that they existed as liquids for at least 319 °C (T₁₀ − T _m) before decomposing.

中文翻译：

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脂肪二烯通过无环二烯复分解缩合制备可再生脂肪族聚酯

通过无环二烯复分解（ADMET）聚合衍生自脂肪酸的α，ω-二烯制备了三种可再生的线性脂肪族聚酯。9-癸烯酸与9-癸烯酸烯丙酯，乙二醇和9-癸烯-1-醇的缩合反应以高转化率（≥94％）和纯度（> 99％）进行，得到适合后续缩聚的α，ω-二烯。使用1.0 mol％的Hoveyda-Grubbs第二代复分解催化剂与2.0 mol％的2,6-二氯-1,4-苯并醌作为异构化抑制剂，在真空下驱动平衡，以通过聚合物形成平衡乙烯去除。在存在溶剂的情况下，聚合促进了闭环复分解（RCM），但以聚合物为代价，随着单体浓度的降低，环化增加。因此，ADMET聚合被大量进行以减轻RCM。所得的M _n和Ð范围分别为6.6至8.9 kDa和1.75–2.14的聚合物包含76％或更多的可再生碳含量，并且原子和碳经济性大于84％。熔体（T _m）和结晶（T _c ）温度分别为20.8–48.4°C和3.8–37.6°C，并且随着聚合物结构中酯密度的降低而升高。低于室温的玻璃转变温度范围为−10.3至−50.0°C。最后，该聚合物在320°C以下具有热稳定性，因为在340°C以上发生10％的质量损失（T ₁₀），这表明它们在分解前至少以319°C（T ₁₀ -T _m）的液体存在。