中文摘要：

为解决聚合物中有毒金属残留问题,选择绿色环保的金属铝作为催化剂活性中心,并通过将助催化剂季铵盐接在卟啉配体上的方法,合成了新型双官能化卟啉铝配合物,通过1H-NMR、13C-NMR、MALDI-TOF等方法对其进行了表征和确认.该催化体系可在不加助催化剂的条件下高效催化CO2/环氧丙烷（PO）共聚合,其活性显著高于传统的卟啉铝配合物/季铵盐双组份催化体系.使用配合物1b详细考察了温度、压力等因素对聚合反应的影响,在90℃,3.0 MPa的反应条件下,反应5 h后TOF（单位时间内每摩尔催化剂转化的单体数）可达1152 h-1,所得聚合物碳酸酯含量98%,数均分子量Mn=42×103,但聚合物选择性较低（68%）.配合物1b同样可以高效的催化CO2/环氧环己烷（CHO）共聚,在相同的反应条件下,TOF可达621 h-1,聚合体系中无环状副产物生成,所得聚合物碳酸酯含量81%,数均分子量Mn=8.0×103.另外,通过改变配合物中的季铵盐阴离子和轴向配体,考察了不同引发基团对催化剂活性、聚合物选择性的影响。

英文摘要：

Due to the concern on residue toxic metal in biodegradable polycarbonate,environmental friendly aluminum complexes,i. e,bifunctional aluminum porphyrin complexes were prepared by anchoring quaternary ammonium salts to the porphyrin ligand framework. The structures of all the complexes were confirmed by1H-NMR,13C-NMR and MALDI-TOF analysis. These catalysts exhibited enhanced activity and selectivity for the copolymerization of CO2and propylene oxide（ PO） compared with the aluminum porphyrin /quaternary ammonium salt binary catalyst system. Using complex 1b as catalyst,the influence of reaction conditions such as CO2pressure,reaction temperature and [PO]/[cat.] ratio etc,on copolymerization behavior was investigated. The TOF（ turnover frequency of epoxide to products） of catalyst 1b can reach 1152 h- 1in 5 h at90 ℃ under 3. 0 MPa,while the resultant copolymer showed a carbonate linkage of 98% and number average molecular weight（ Mn） of 42 × 103,though the PPC selectivity was 68%. When the copolymerization of CO2and cyclohexene oxide（ CHO） was conducted by using catalyst 1b at the same reaction condition,a TOF as high as 621 h- 1was reached,the carbonate linkage of the obtained copolymer was 81% and the number average molecular weight was 8. 0 × 103,while the polymer selectivity was 100%. Additionally,our work also indicates that variation of the quaternary ammonium anion and the axial ligand had dramatic effects on the catalytic activity of resultant complex.