Copolymers provide a feasible platform to extend the structures of polymeric material, and the control of architecture (such as monomer sequence and stereo sequence) plays a critical role in tailoring specific properties. Herein, a heterometallic (Salph Zn)₂-Ho complex was screened out for the synthesis of architecture-defined block terpolymers from a monomer mixture of epoxide, cyclic anhydride and l-lactide (LLA). The polymerization in one-pot firstly underwent ring-opening copolymerization reaction producing completely alternating ester linkage, and then transformed to LLA polymerization with trace stereoerrors, forming block polyesters with a semicrystalline segment and an amorphous segment. The polymerization was “immortal” with the ability to synthesize sequence-defined multiblock polyesters by sequential monomer addition. Furthermore, DSC traces revealed that the obtained block polyesters exhibited distinct thermal properties stemming from each segment. The melting temperature of block terpolymer was increased to 207.6 °C facilitated by the stereocomplexes of PLA segment.

共聚物为扩展聚合物材料的结构提供了一个可行的平台，结构的控制（如单体序列和立体序列）在定制特定性能方面起着关键作用。在此，筛选出异金属 (Salph Zn) ₂ -Ho络合物，用于从环氧化物、环酸酐和l的单体混合物中合成结构定义的嵌段三元共聚物-丙交酯（LLA）。一锅聚合首先进行开环共聚反应，产生完全交替的酯键，然后转变为具有微量立体误差的LLA聚合，形成具有半晶链段和无定形链段的嵌段聚酯。聚合是“不朽的”，能够通过连续添加单体来合成序列定义的多嵌段聚酯。此外，DSC 迹线表明，所获得的嵌段聚酯表现出源自每个片段的不同热性能。PLA 链段的立构复合物促进嵌段三元共聚物的熔化温度增加到 207.6 °C。