Fadlallah Sami, Carboué Quentin, Mouterde Louis M M, Kayishaer Aihemaiti, Werghi Yasmine, Peru Aurélien A M, Lopez Michel, Allais Florent
URD Agro-Biotechnologies Industrielles (ABI), CEBB, AgroParisTech, 3 Rue des Rouges-Terres, 51110 Pomacle, France.
Polymers (Basel). 2022 May 20;14(10):2082. doi: 10.3390/polym14102082.
Recently, a renewable five-membered lactone containing citronellol (HBO-citro) was synthesized from levoglucosenone (LGO). A one-pot two-step pathway was then developed to produce a mixture of 5- and 6-membered Lactol-citro molecules (5ML and 6ML, respectively) from HBO-citro. Proton nuclear magnetic resonance (H NMR) of a mixture of 5ML and 6ML at varying temperatures showed that the chemical shifts of the hydroxyls, as well as the 5ML:6ML ratio, are temperature-dependent. Indeed, a high temperature, such as 65 °C, led to an up-field shielding of the hydroxyl protons as well as a drop in the 5ML:6ML ratio. The monomers 5ML and 6ML were then engaged in polycondensation reactions involving diacyl chlorides. Renewable copolyesters with low glass transition temperatures (as low as -67 °C) and cross-linked citronellol chains were prepared. The polymers were then hydrolyzed using a commercial lipase from (Lipopan 50 BG). A higher degradation rate was found for the polymers prepared using Lactol-citro molecules, compared to those obtained by the polycondensation reactions of diacyl chlorides with Triol-citro-a monomer recently obtained by the selective reduction of HBO-citro.
最近，从左旋葡聚糖酮（LGO）合成了一种含有香茅醇的可再生五元内酯（HBO-香茅醇）。然后开发了一种一锅两步法，从HBO-香茅醇生产5元和6元内酯-香茅醇分子的混合物（分别为5ML和6ML）。5ML和6ML混合物在不同温度下的质子核磁共振（H NMR）表明，羟基的化学位移以及5ML:6ML的比例都与温度有关。实际上，高温（如65°C）会导致羟基质子的高场屏蔽以及5ML:6ML比例的下降。然后，单体5ML和6ML参与了涉及二酰氯的缩聚反应。制备了具有低玻璃化转变温度（低至-67°C）和交联香茅醇链的可再生共聚酯。然后使用来自（Lipopan 50 BG）的商业脂肪酶对聚合物进行水解。与通过二酰氯与最近通过HBO-香茅醇的选择性还原获得的单体三醇-香茅醇的缩聚反应得到的聚合物相比，发现使用内酯-香茅醇分子制备的聚合物具有更高的降解速率。
