Copolymerization of Carbon Dioxide and Propylene Oxide under Inorganic Oxide Supported Rare Earth Ternary Catalyst

Abstract

Recently, rare earth ternary coordination catalyst represented as Y(CCl(3)OO)(3)-Glycerin-ZnEt(2) has been used for producing poly(propylene carbonate) (PPC, an alternating copolymer of carbon dioxide and propylene oxide) in industry scale, but its catalytic activity needs further improvement. One reason for the relatively low catalytic activity lied in that only 11.7% of active center was efficient due to possible embedding of active center in the heterogeneous catalyst. In this report, supporting strategy was developed, where Y(CCl(3)OO)(3)-Glycerin-ZnEt(2) was supported on various inorganic oxides. Two supporting methods were carried out. One way was to mix Y(CCl(3)OO)(3)-Glycerin with inorganic oxide first and then ZnEt(2) was dropped to form the supported catalyst, and the other was to make Y(CCl(3)OO)(3)-Glycerin-ZnEt(2) at first and then mixing with inorganic oxides. The former showed decreasing catalytic activity compared with corresponding unsupported rare earth ternary catalyst, while an improvement of 16-36% in catalytic activity was realized in the latter. PPC with an average number molecular weight (M(n)) of over 100 kg/mol and carbonate unit (CU) content of higher than 96% was prepared by both supported catalysts. The catalytic activity of the supported catalyst depended significantly on the supports, which increased in the following order: alpha-Al(2)O(3) < MgO < ZnO approximate to SiO(2) <gamma-Al(2)O(3). gamma-Al(2)O(3) was the best support for rare earth ternary catalyst, which showed a remarkable 36% increase in catalytic activity, corresponding to the utilization of 17% of active center. Although MgO supported catalyst gave only an 8% increase in catalytic activity, the M(n) and CU content of PPC were raised to about 143 kg/mol and 99%, whereas the PPC from common rare earth ternary catalyst was about 108 kg/mol and 97%, respectively. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3797-3804, 201