Abstract Ring-opening polymerization (ROP) of macrocyclic carbonates (≥12 ring) is still challenging due to the associated low ring-strain. Although organometallic and enzyme based catalysts have been studied, disadvantages such as organometallic residue and enzymic nature limit their applications. After screening commercially available organocatalysts, we report the use of organocatalysts for ROP of disulfide-containing macrocyclic carbonates (MSS, 16 ring). It was found that organocatalysts (TBD) presented high active and living ROP of MSS, as evidenced by kinetic studies, yielding main chain disulfide-containing polycarbonates with tailor-made structures and predictable molecular weights with low molecular weight distribution. Copolymerizations with trimethylene carbonate (TMC) generated random copolymers with controlled components, regulating the density of disulfide functional groups. By comparing with the behaviors of enzyme catalysis in kinetic studies and (co-)polymerization, it is observed that organic catalyzed ROP showed more efficient (~ ten times faster), milder condition and more controlled behaviors than enzyme catalyzed ROP (N-435). Therefore, we believe this organic catalyzed strategy will provide an alternative to the current enzymatic and organometallic catalyst for ROP of macrocyclic carbonates.

中文翻译：

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二硫化物官能大环碳酸酯的有机催化开环聚合：酶催化的替代策略

摘要 由于相关的低环应变，大环碳酸酯（≥12环）的开环聚合（ROP）仍然具有挑战性。尽管已经研究了有机金属和酶基催化剂，但有机金属残留物和酶性质等缺点限制了它们的应用。在筛选了市售的有机催化剂后，我们报告了有机催化剂在含二硫化物大环碳酸酯（MSS，16 环）的 ROP 中的应用。发现有机催化剂 (TBD) 表现出 MSS 的高活性和活性 ROP，正如动力学研究所证明的那样，产生具有定制结构和可预测分子量和低分子量分布的含主链二硫化物的聚碳酸酯。与三亚甲基碳酸酯 (TMC) 共聚生成具有受控组分的无规共聚物，调节二硫化物官能团的密度。通过与动力学研究和（共）聚合中酶催化的行为进行比较，观察到有机催化的 ROP 表现出比酶催化的 ROP (N-435) 更高效（约快十倍）、更温和的条件和更可控的行为. 因此，我们相信这种有机催化策略将为当前用于大环碳酸酯 ROP 的酶和有机金属催化剂提供替代方案。