Monomodal Ultrahigh-Molar-Mass Polycarbonate Homopolymers and Diblock Copolymers by Anionic Copolymerization of Epoxides with CO 2 .

Whatever the chemistry used for the synthesis of aliphatic polycarbonates, in particular, those of high molar mass, the adventitious presence of water leads to bimodal GPC traces and affords polycarbonate samples of uncontrolled and unpredictable molar masses. It appears that among all reagents used in the copolymerization of CO 2 and epoxides, CO 2 is the most difficult one to dry. To address this issue, triisobutylaluminum (TiBA) was employed in this work to dry CO 2 through a bubbling method; its drying capability was investigated in the context of the copolymerization of CO 2 with epoxides initiated by onium chloride in the presence of triethylborane (TEB). It was then compared to the efficiency of other already reported drying agents such as phosphorus pentoxide, molecular sieves and commercially available CO 2 purifiers. With TiBA-dried CO 2 , its copolymerizations respectively with propylene oxide (PO) and cyclohexene oxide (CHO) could be successfully achieved in a wide range of degrees of polymerization (DP), with the value of DP as high as 16000. Diblock copolymers poly(propylene carbonate- b -cyclohexene carbonate) (PPC- b -PCHC) could also be prepared through sequential addition of epoxide monomers. The polycarbonates obtained under the conditions were all well-defined as characterized by NMR, GPC, triple detector-GPC, and differential scanning calorimetry (DSC).