Abstract We have designed photocurable, telechelic macromonomers consisting of random oligo(e-caprolactone-co-p-dioxanone), oligo(CL-co-DX), and demonstrated their suitability for preparing pliable polyester networks whose properties resemble those of gels. A versatile and effective metal-free co-oligomerization, catalyzed by diphenyl phosphate, was developed in bulk and at room temperature. A high rate of conversion of monomers was achieved and oligo(CL-co-DX)s with different composition and topology were obtained with controlled molar mass, approx. 2000 g mol−1, low dispersity and a random distribution of the two monomeric units. Kinetics analysis of the reaction disclosed a faster incorporation rate for the p-dioxanone (DX) than e-caprolactone (CL). The extrapolated rate constant, kDX, was 0.030 min−1 against a kCL of 0.013 min−1. The reactivity ratios were respectively 2.7 (rDX) and 0.28 (rCL). A detailed NMR analysis was performed to elucidate the structure of the co-oligomers, which could be precisely controlled by varying the monomer feed ratio and initiator. Depending on the composition, amorphous to semicrystalline oligomers with melting points close to room temperature were obtained, which after acrylation of the chain-end gave polyester networks with high swelling capacity up to 700%, and water uptake up to 70%.

中文翻译：

---

遥爪寡核苷酸（ε-己内酯-co-p-二恶烷酮）的有机催化策略：聚酯网络的光固化大分子单体

摘要 我们设计了由随机低聚体（ε-己内酯-co-p-二恶烷酮）、低聚体（CL-co-DX）组成的可光固化遥爪大单体，并证明它们适用于制备性质类似于凝胶的柔韧聚酯网络。一种多功能且有效的无金属共低聚反应，由磷酸二苯酯催化，在室温下批量开发。实现了单体的高转化率，并以受控的摩尔质量获得了具有不同组成和拓扑结构的低聚（CL-co-DX）。2000 g mol-1，低分散性和两个单体单元的随机分布。该反应的动力学分析表明，对二恶烷酮 (DX) 的掺入速率比ε-己内酯 (CL) 更快。外推速率常数 kDX 为 0.030 min-1，而 kCL 为 0.013 min-1。反应性比分别为 2.7 (rDX) 和 0.28 (rCL)。进行了详细的 NMR 分析以阐明共聚低聚物的结构，这可以通过改变单体进料比和引发剂来精确控制。根据组成，获得熔点接近室温的无定形至半结晶低聚物，在链端丙烯酸化后得到具有高达 700% 的高溶胀能力和高达 70% 的吸水率的聚酯网络。