Terpolymerization of carbon dioxide (CO 2 ), propylene oxide (PO), and epoxide with bulky side groups (styrene oxide (SO), cyclohexylethylene oxide (CyEO), tert -butylethylene oxide ( t BuEO), or 1-adamantylethylene oxide (AdEO)) was conducted by using a tetraphenylporphyrinatocobalt(III) chloride ((TPP)CoCl)/4-dimethylamino pyridine (DMAP) catalyst system. Compared with the copolymerizations of CO 2 and epoxides with bulky side groups, it took less than half (AdEO) or even one-third (CyEO and t BuEO) of the polymerization time to synthesize polycarbonates with degrees of polymerization of 100 or above. In this (TPP)CoCl/DMAP system, a highly random terpolymer of CO 2 , PO, and SO was realized for the first time, which has not been observed in other catalyst systems, such as cobalt salen complex systems. In contrast, gradient terpolymers were formed in the cases of CyEO, t BuEO, and AdEO. The glass transition temperatures ( T g s) of these terpolymers are tunable between that of the copolymer of CO 2 with PO (34 °C) and that of the copolymer of CO 2 with the corresponding epoxide with bulky side groups by changing the initial ratio of PO to epoxide with bulky side groups. A highly random terpolymer of CO 2 , styrene oxide (SO), and propylene oxide (PO) was realized by using a tetraphenylporphyrinatocobalt(III) chloride ((TPP)CoCl)/4-dimethylamino pyridine (DMAP) catalyst system. In contrast, gradient terpolymers were formed in the cases of CO 2 , cyclohexylethylene oxide (CyEO), tert -butylethylene oxide ( t BuEO) or 1-adamantylethylene oxide (AdEO), and PO. The glass transition temperatures ( T g s) of these terpolymers are tunable between that of the copolymer of CO 2 with PO (34 °C) and that of the copolymers of CO 2 with the corresponding epoxide with bulky side groups.

中文翻译：

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二氧化碳、环氧丙烷和各种具有庞大侧基的环氧化物交替三聚以调节热性能

二氧化碳 (CO 2 )、环氧丙烷 (PO) 和具有庞大侧基的环氧化物（氧化苯乙烯 (SO)、环己基环氧乙烷 (CyEO)、叔丁基环氧乙烷 (t BuEO) 或 1-金刚烷基环氧乙烷 (AdEO)）的三聚反应)) 是通过使用氯化四苯基卟啉钴 (III) ((TPP)CoCl)/4-二甲氨基吡啶 (DMAP) 催化剂体系进行的。与CO 2 和具有庞大侧基的环氧化物共聚相比，合成聚合度100以上的聚碳酸酯只需不到一半（AdEO）甚至三分之一（CyEO和t BuEO）的聚合时间。在该 (TPP)CoCl/DMAP 体系中，首次实现了 CO 2 、PO 和 SO 的高度无规三元共聚物，这在其他催化剂体系（如钴萨伦络合物体系）中尚未观察到。相比之下，在 CyEO、t BuEO 和 AdEO 的情况下形成梯度三元共聚物。这些三元共聚物的玻璃化转变温度 (T gs) 可在 CO 2 与 PO 的共聚物 (34 °C) 和 CO 2 与相应的具有庞大侧基的环氧化物的共聚物之间通过改变初始比例进行调节PO 到具有庞大侧基的环氧化物。通过使用氯化四苯基卟啉钴 (III) ((TPP)CoCl)/4-二甲氨基吡啶 (DMAP) 催化剂体系实现了 CO 2 、氧化苯乙烯 (SO) 和氧化丙烯 (PO) 的高度无规三元共聚物。相反，在CO 2 、环己基环氧乙烷(CyEO)、叔丁基环氧乙烷(t BuEO)或1-金刚烷基环氧乙烷(AdEO)和PO的情况下形成梯度三元共聚物。