The incorporation of diverse macromolecular blocks into CO-based polycarbonates offers a promising approach for tailoring the properties of polycarbonates for special needs. In this work, we report for the first time the synthesis and characterization of an ABA triblock copolymer polycarbonate--polyalkenamer--polycarbonate in combination of ROCOP and ROMP a one-pot route from CO, epoxides and cycloalkenes. -2-butene-1,4-diol as the bifunctional chain transfer agent was used as a “bridge” for the combination of different blocks as well as an effective regulator for the molecular weight of the polymers. In the one-pot reaction, the conversion of cycloalkenes reached 99.9% within 0.5 h, while the conversion of CHO was initially marginal at 0.5% but gradually increased to 99.7% after 24 h. The significant discrepancy in reaction rates between the two processes enables efficient synergistic reactions within the one-pot system. Specifically, hydroxyl-telechelic polyalkenamer is initially formed ROMP and subsequently acts as an active species for ROCOP when coordinated with the porphyrin Al catalyst. This one-pot strategy provides a unique and simple method for controllably constructing functional polycarbonates with single-modal molecular weight distributions. By integrating the advantages of polyalkenamers and polycarbonates, this approach proves to be a viable solution for addressing the unsatisfactory thermal properties of aliphatic polycarbonates.

中文翻译：

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结合ROCOP和ROMP高效一锅合成CO2基功能聚碳酸酯

将不同的大分子嵌段掺入CO基聚碳酸酯中，为定制聚碳酸酯的性能以满足特殊需求提供了一种有前途的方法。在这项工作中，我们首次报道了 ABA 三嵌段共聚物聚碳酸酯 - 聚烯烃 - 聚碳酸酯结合 ROCOP 和 ROMP 的合成和表征，采用 CO、环氧化物和环烯烃的一锅法。 -2-丁烯-1,4-二醇作为双功能链转移剂，既作为不同嵌段结合的“桥梁”，又作为聚合物分子量的有效调节剂。在一锅反应中，环烯烃的转化率在0.5小时内达到99.9%，而CHO的转化率最初仅为0.5%，但在24小时后逐渐增加至99.7%。两个过程之间反应速率的显着差异使得一锅系统内能够实现高效的协同反应。具体来说，羟基-远爪聚烯烃最初形成ROMP，随后当与卟啉Al催化剂配位时充当ROCOP的活性物质。这种一锅法策略提供了一种独特而简单的方法，用于可控地构建具有单峰分子量分布的功能性聚碳酸酯。通过整合聚烯烃和聚碳酸酯的优点，该方法被证明是解决脂肪族聚碳酸酯热性能不理想的可行解决方案。