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以聚醚多元醇、二缩三乙二醇或季戊四醇作为分子量调节剂,用Zn-Co双金属氰化物(DMC)高效催化CO2和环氧丙烷(PO)调节共聚合成了数均分子量为3000~8000的多官能度脂肪族聚碳酸酯多元醇,共聚物的分子量基本符合设计要求。几种分子量调节剂均能成功合成两官能度或四官能度的共聚产物,产物中碳酸酯键含量最高可达60%,催化效率最高达663 g/g催化剂,副产物最低可控制到4%。文中还考察了温度、压力、调节剂及催化剂用量对共聚反应的影响,发现60℃的低温更有利于CO2和环氧丙烷的共聚反应,而且要获得碳酸酯键含量较高的产物,需控制调节剂和催化剂的比例。

A group of multi-functional aliphatic polycarbonate polyols(APC),molecular weight between 3000 and 6000,was synthesized by regulated copolymerization of carbon dioxide and propylene oxide(PO) on double metal cyanide complex(Co-Zn DMC)catalyst with polyether alcohol,pentaerythritol(PER) or triethylene glycol as regulators.The molecular weight of the copolymer complied with the design requirements.All the regulators could successfully produce copolymers with two or four functionality.In the mean time the highest carbonate content of the copolymer is up to 60% and the highest catalystic efficiency could get to 663g of polymer /g of catalyst,with cyclic carbonate is only 4%.In this paper we also examined the effect of the temperature,pressure and the dosage of regulator on reaction.The results reveal that 60 ℃ is in favor of the copolymerization.The regulator and catalyst should be controlled in certain proportion to get high carbonate content.

参考文献

[1] Sun XK;Zhang XH;Liu F;Chen S;Du BY;Wang Q;Fan ZQ;Qi GR .Alternating copolymerization of carbon dioxide and cyclohexene oxide catalyzed by silicon dioxide/Zn-Co-III double metal cyanide complex hybrid catalysts with a nanolamellar structure[J].Journal of Polymer Science, Part A. Polymer Chemistry,2008(9):3128-3139.
[2] In Kyu Lee;Ju Young Ha;Chengang Cao .Effect of complexing agents of double metal cyanide catalyst on the copolymerizations of cyclohexene oxide and carbon dioxide[J].Catalysis Today,2009(3/4):389-397.
[3] Chen S;Hua ZJ;Fang Z;Qi GR .Copolymerization of carbon dioxide and propylene oxide with highly effective zinc hexacyanocobaltate(III)-based coordination catalyst[J].Polymer: The International Journal for the Science and Technology of Polymers,2004(19):6519-6524.
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