酯交换聚合法合成聚碳酸酯二元醇的研究
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摘要
选用碳酸二乙酯(DEC)与1,4-丁二醇(BDO)为反应物,钛酸四丁酯为催化剂,通过酯交换聚合反应合成了一系列数均分子量在1 300～2 800之间的聚碳酸酯二元醇(PCDL)。用傅里叶变换红外光谱和核磁共振波谱(NMR)表征了产物的化学结构,用羟值测定和NMR两种方法测试了产物的数均分子量,用气相色谱/质谱联用法分析了常压馏分的组成。研究表明,当反应物DEC/BDO摩尔比处在1.00～1.07范围内,PCDL的分子量随着它们的摩尔比增加而升高,常压馏分组成变化不大。
A series of polycarbonate diols( PCDL) with number average molecular weights of 1 300 ～ 2 800 were synthesized by transesterification polymerization using diethyl carbonate( DEC),1,4-butanediol( BDO) as reactants and tetrabutyl titanate as catalyst. The chemical structure of the product was characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy( NMR). The number average molecular weight of the product was measured by hydroxyl value determining method and NMR. The composition of the fraction obtained under atmospheric pressure was analyzed by gas chromatography/mass spectrometry. The results showed that,when the molar ratio of DEC/BDO was within the range of 1. 00 ～ 1. 07,the molecular weight of PCDL was raised with the increase of their molar ratio,and the composition of the fraction was not significantly changed.
A series of polycarbonate diols( PCDL) with number average molecular weights of 1 300 ～ 2 800 were synthesized by transesterification polymerization using diethyl carbonate( DEC),1,4-butanediol( BDO) as reactants and tetrabutyl titanate as catalyst. The chemical structure of the product was characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy( NMR). The number average molecular weight of the product was measured by hydroxyl value determining method and NMR. The composition of the fraction obtained under atmospheric pressure was analyzed by gas chromatography/mass spectrometry. The results showed that,when the molar ratio of DEC/BDO was within the range of 1. 00 ～ 1. 07,the molecular weight of PCDL was raised with the increase of their molar ratio,and the composition of the fraction was not significantly changed.
引文
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[11]苏义华.苯酐-吡啶法测定聚醚多元醇中羟值含量[J].化学工程师,2012,(6):25-26.
[2]冯亚凯,赵海洋,郭锦棠,等.生物相容性聚碳酸酯聚氨酯微纤维人工血管的研究[J].高分子通报,2010,(8):73-77.
[3]樊国栋,杨锐.脂肪族环状碳酸酯的合成及其开环聚合研究进展[J].化工进展,2010,29(10):1917-1922.
[4] Brignou P,Priebe M G,Casagrande O,et al. Polycarbonates derived from green acids:immortal ring-opening polymerization of seven-membered cyclic carbonates[J]. Macromolecules,2010,43(19):8007-8017.
[5] Varghese J K,Park D S,Jeon J Y,et al. Double metal cyanide catalyst prepared using H3Co(CN)6for high carbonate fraction and molecular weight control in carbon dioxide/propylene oxide copolymerization[J]. Journal of Polymer Science Part A Polymer Chemistry,2013,51(22):4811-4818.
[6]殷宁,亢茂青,刘振民. KOH/γ-Al2O3催化合成聚(碳酸三甘醇)酯二醇[J].化学推进剂与高分子材料,2014,12(2):71-75.
[7]王丽苹,萧斌,王公应.酯交换法合成聚碳酸酯二醇的研究进展[J].化学试剂,2010,32(6):513-517.
[8]李秦龙,殷雯青,王辉强,等.聚碳酸酯型聚氨酯研究进展[J].皮革与化工,2014,(1):21-24.
[9]罗智,王越,江静,等.特种精馏法分离碳酸二甲酯-甲醇共沸体系研究进展[J].天然气化工,2008,33(2):66-70.
[10]马新宾,张震,石海峰,等.碳酸二乙酯的合成方法[J].化学通报,2003,66(8):528-535.
[11]苏义华.苯酐-吡啶法测定聚醚多元醇中羟值含量[J].化学工程师,2012,(6):25-26.