Polyesters, as a class of high-performance and versatile polymer materials, often suffer from some drawbacks, such as hydrophobicity and brittleness due to their single structure nature. Thus, modifications have attracted much attention for enhancing their desirable properties, of which one efficient way is incorporating the aliphatic polyether segment into the main chain of the polyester. However, this approach is of much challenge because the obtained polyesters are problematic in either low alternating degree or low molecular weight. Herein, we describe an efficient strategy to incorporate polyether fragment into polyester by developing a novel Co-AI based heterodinuclear complex for mediating the copolymerization of propylene oxide (PO) with ε-caprolactone (CL). The tracking experiments reveal that PO and CL convert into the polymer chain throughout the polymerization process. Especially, the linear increase in the molecular weight with conversion of CL indicates the controllable nature of the copolymerization. The competition polymerization, offering the monomer reactivity ratios of r_CL = 0.96 and r_PO = 1.04, suggests that the tendency of self-propagation or incorporation of monomers is nearly identical. Interestingly, the obtained polymers with different ether contents exhibit tunable thermal properties with enhanced decomposition temperature for the polymer with higher ether content. The newly developed heterodinuclear complex for new polymerization provides an idea to synthesize new functional polymeric materials.

聚酯作为一类高性能且用途广泛的聚合物材料，由于其单一的结构性质，经常会遭受一些缺点，例如疏水性和脆性。因此，为了提高其所需的性能而进行的修饰引起了极大的关注，其中一种有效的方法是将脂族聚醚链段引入聚酯的主链中。但是，该方法面临很大挑战，因为所获得的聚酯在低交替度或低分子量方面都是有问题的。在这里，我们描述了一种有效的策略，通过开发一种新型的基于Co-AI的异双核络合物来介导环氧丙烷（PO）与ε-己内酯（CL）的共聚反应，将聚醚片段掺入聚酯中。跟踪实验表明，PO和CL在整个聚合过程中都转化为聚合物链。特别地，分子量随着CL的转化而线性增加表明共聚的可控制性质。竞争聚合，提供的单体反应比为r _CL = 0.96和r _PO = 1.04，表明单体的自蔓延或掺入趋势几乎相同。有趣的是，对于醚含量较高的聚合物，所获得的醚含量不同的聚合物表现出可调节的热性能，并且分解温度提高。新开发的用于新聚合的异双核配合物为合成新的功能聚合材料提供了一个思路。