在α-二亚胺型催化剂BDIE·[Zn-Al]催化下采用新的工艺进行CO2与氧化环己烯共聚反应,催化效率得到较大地提高.这些新的工艺包括在反应前用与催化剂摩尔比为1.5:1的氧化环已烯进行数小时陈化;采用二氧化碳与氧化环已烯分批加料的聚合工艺.在25%温度下陈化4h,采用分批加料的方式反应,BDIE-[Zn-AI]的催化效率提高到69.9g/s.
The complex of BDIE· [ Zn-Al] is a cheap catalyst for copolymerizatrion of carbon dioxide, which was prepared by using zinc acetate anhydrous, aluminum isopropoxide and precursor N, N'-bis(2,6-diisopropylphenyl)- 2,4-ethyldiimine (BDIE). It is nonsensitive to moisture and easy to handle in the copolymerization. However, its low catalytic efficiency limited its application. In this paper novel technologies for the copolymerization of CO2 and cyclohexene oxide were developed using BDIE· [Zn-A1] catalyst. These new processes include: (1) aging BDIE· [ Zn-A1] with an appropriate amount of cyclohexene oxide (CHO) as a catalyst; and (2) CO2 and cyclohexene oxide are fed in three batches during whole reaction. Effects of aging conditions such as aging time and temperature, the molar ratio of CHO/BDIE · [ Zn-Al ] were investigated in detail. The highest catalytic efficiency 69.9 g/g was obtained with feeding monomers in three batches, molar ratio of CHO/BDIE· [ Zn-Al ] = 1.5:1, aging time of g h, aging temperature of 25 ℃, reaction temperature of 80℃, catalyst concentration of 0. 1 g/mL and CO2 pressure of 2 MPa.