Aluminum Porphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO2/Epoxides
Foldamer catalysts have been extensively applied in the synthesis of small molecules due to the"enzyme-like"secondary structure,while their contributions in polymer synthesis were rarely reported.Based on the polycondensation reaction of aluminum bis-aminoporphyrin and 2,5-diacylchloropyridine,we reported an aluminum porphyrin aromatic amide foldamer catalyst(AAF),and its foldamer structure was verified by the circular dichroism spectrum.The foldamer catalyst AAF effectively(turnover frequency,TOF=300-1250 h-1)catalyzed the copolymerization of carbon dioxide and epoxides with high polymer selectivity(99％).It is worth mentioning that,this catalyst can realize the copolymerization of carbon dioxide and propylene oxide even in the absence of cocatalyst with a TOF of 525 h-1 and polymer selectivity of 95％,which also exhibits an enzyme-like optimum temperature of 80 ℃.Additionally,it could also catalyze the copolymerization of carbon dioxide and cyclohexane oxide,the catalytic activity(TOF=550-1250 h-1)was linearly positively correlated with carbon dioxide pressure(1-7 MPa),and the polymer selectivity and carbonate units were all over 99％.Herein,we reported an aluminum porphyrin based aromatic amide foldamer catalyst,which broadens the application of foldamer catalysis in polymers and opens up new avenues for the study of aromatic amide foldamers in the field of catalysis.
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