The anionic alternating ring-opening copolymerizations of three bio-based aromatic monomers, eugenol glycidyl ether (EGE), dihydroeugenol glycidyl ether (DEGE) and vanillin glycidyl ether (VGE), were carried out with renewable N-acetyl homocysteine thiolactone (NHTL) using benzyl alcohol and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) as the initiating system. This polymerization is a rare example of synthesis of linear polyesters using eugenol-based monomers. Alternating poly(ester-alt-thioether)s are obtained with number-average molar masses (M_n) ranging from 1.1 to 10.8 kg mol⁻¹ and dispersities as low as 1.20. The copolymer structures were carefully characterized by ¹H, ¹³C, COSY, HSQC, and ¹H–¹⁵N NMR. It was found that the alternating copolymers were obtained selectively at different monomer feed ratios. In addition, the use of EGE and VGE monomers allows the preparation of multi-functional poly(ester-alt-thioether)s respectively bearing allyl or aldehyde groups in each repeating unit. The copolymers display only clear glass transition temperatures higher than the ambient temperature. This alternating copolymerization method offers a new chemical pathway for the valorization of bio-based aromatic compounds and expands the scope of renewable polyesters.

中文翻译：

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通过丁香酚基环氧化物和 N-乙酰高半胱氨酸硫内酯的有机催化开环共聚合成生物基聚（酯-alt-硫醚）

三种生物基芳香族单体丁香酚缩水甘油醚 (EGE)、二氢丁香酚缩水甘油醚 (DEGE) 和香草醛缩水甘油醚 (VGE) 的阴离子交替开环共聚反应是使用可再生的N-乙酰高半胱氨酸硫内酯 (NHTL) 进行的。苯甲醇和 2-叔丁基亚氨基-2-二乙氨基-1,3-二甲基全氢-1,3,2-二氮杂膦 (BEMP) 作为引发系统。这种聚合是使用丁香酚基单体合成线性聚酯的罕见例子。交替的聚（酯- ALT -thioether）类与数均摩尔质量而获得（中号_Ñ）范围为1.1至10.8公斤摩尔^-1分散度低至 1.20。共聚物结构通过¹ H、¹³ C、COSY、HSQC 和¹ H– ¹⁵ N NMR进行了仔细表征。发现在不同的单体进料比下选择性地获得交替共聚物。另外，使用EGE和VGE单体的允许多官能的聚（酯-的制备中ALT -thioether）S分别轴承烯丙基或醛基在每个重复单元。共聚物仅显示出高于环境温度的清晰玻璃化转变温度。这种交替共聚方法为生物基芳香族化合物的增值提供了新的化学途径，并扩大了可再生聚酯的范围。