The synthesis of high-molecular-weight poly(ε-caprolactone)s (PCLs) with enhanced mechanical properties remains challenging. Here we demonstrate the heterogeneous catalysis for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL). Using a zinc-cobalt double-metal cyanide complex [Zn-Co(III) DMCC] in the presence of around 1% mol epoxides, PCLs are achieved with high number-average molecular weights (M_ns) of up to 177.7 kDa determined by the gel permeation chromatography. The [Zn]-OH active site of the complex triggers the cleavage of the epoxide at first, which is considered as the rate-determining step of the polymerization. The formed zinc-alkoxide species then initiates the ROP of ε-CL, affording most of the PCLs possessing one epoxide molecule embedded in the polymer chain and dihydroxyl terminals as revealed by the ¹H NMR and MALDI-TOF MS spectroscopy. The PCL specimen with a corrected M_n of 110.4 kDa exhibits the tensile strength and elongation at break of as high as 40.2 MPa and 1060%, respectively. This work provides a facile and practical method for the synthesis of high-molecular-weight PCLs.

具有增强的机械性能的高分子量聚（ε-己内酯）s（PCLs）的合成仍然具有挑战性。在这里，我们证明了ε-己内酯（ε-CL）的开环聚合（ROP）的非均相催化。在约1％mol的环氧化物存在下，使用锌-钴双金属氰化物配合物[Zn-Co（III）DMCC]，可以以高数均分子量（M _n通过凝胶渗透色谱法测定的s）高达177.7 kDa。络合物的[Zn] -OH活性位点首先触发环氧化物的裂解，这被认为是聚合反应的速率决定步骤。形成的烷氧基锌物质随后引发ε-CL的ROP，从而提供大多数PCL，它们具有一个嵌入聚合物链和二羟基末端的环氧化物分子，如¹ H NMR和MALDI-TOF MS光谱所揭示。校正后的M _n为110.4 kDa的PCL样品的抗张强度和断裂伸长率分别高达40.2 MPa和1060％。这项工作为合成高分子量PCL提供了一种简便实用的方法。