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1. 中国科学院成都有机化学研究所,成都,610041
2. 中国科学院大学,北京,100049
3. 中国科学院成都有机化学有限公司,成都,610041
纸质出版日期:2014-5-20,
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刘峰, 杨先贵, 李建国, 刘绍英, 姚洁, 陈彤, 王公应. 碳酸二苯酯与1,4-丁二醇熔融酯交换法合成聚(对亚丁基)碳酸酯的研究[J]. 高分子学报, 2014,(5):628-635.
Feng Liu, Xian-gui Yang, Jian-guo Li, Shao-ying Liu, Jie Yao, Tong Chen, Gong-ying Wang. Synthesis of Poly(butylene carbonate) by Melt Transesterification of Diphenyl Carbonate and 1,4-Butanediol[J]. Acta Polymerica Sinica, 2014,(5):628-635.
刘峰, 杨先贵, 李建国, 刘绍英, 姚洁, 陈彤, 王公应. 碳酸二苯酯与1,4-丁二醇熔融酯交换法合成聚(对亚丁基)碳酸酯的研究[J]. 高分子学报, 2014,(5):628-635. DOI: 10.3724/SP.J.1105.2014.13335.
Feng Liu, Xian-gui Yang, Jian-guo Li, Shao-ying Liu, Jie Yao, Tong Chen, Gong-ying Wang. Synthesis of Poly(butylene carbonate) by Melt Transesterification of Diphenyl Carbonate and 1,4-Butanediol[J]. Acta Polymerica Sinica, 2014,(5):628-635. DOI: 10.3724/SP.J.1105.2014.13335.
利用TiO2-SiO2(PVP)凝胶基催化剂(TSP),无溶剂条件下,以碳酸二苯酯与1,4-丁二醇为单体,采用常压预聚和真空缩聚两步熔融酯交换法合成了聚(对亚丁基)碳酸酯(PBC),考察了工艺条件,并对PBC的结构及物理性质进行了表征.实验结果表明,最佳工艺条件如下:预聚时间为2 h,预聚温度为220~230 ℃(N2保护),缩聚温度为220 ℃,缩聚压力300 Pa,催化剂用量为0.15 wt%.优化条件下,PBC的特性黏数为1.12 dL/g,Mn为49000,Mw为101000,PDI为2.07,Tg为 -32.32 ℃,端羟基含量为6.210-4 mol/g,苯酚残留量为5.26 wt%.在此工艺条件下,通过控制副产物苯酚的蒸出速率及其量,可以实现产品聚合度的可控,且苯酚几乎能够完全回收.
The synthesis of poly(1
4-butylene carbonate) (PBC) catalyzed by TiO2-SiO2(PVP-gel) was studied via a two-step melt transesterification of diphenyl carbonate and 1
4-butanediol.After pre-polymerization of diphenyl carbonate and 1
4-butanediol in the standard atmosphere
the vacuum condensation reaction was operated.The PBC was characterized by IR
NMR
GPC and DSC.The experimental results showed that the optimum conditions of the reaction were as follows: the reaction time and reaction temperature were 2 h and 220~230 ℃ (N2 protection)
respectively
in the standard atmosphere pre-polymerization step.The reaction time
reaction pressure and the catalyst dosage were 2 h
300 Pa and 0.15 wt%
respectively
in the vacuum condensation step.The properties of the PBC prepared in optimum conditions
were as follows:[]was 1.12 dL/g
the Mn was 49000
the Mw was 101000
the polydispersity index was 2.07
the Tg was -32.32 ℃
the terminal hydroxyl content was 6.210-4 mol/g and the residue of the phenol was 5.26 wt%.The polymerization degree of PBC can be controlled by the evaporation rate and yield of phenol under the technological conditions.And the phenol by-product was recycled almost completely.
碳酸二苯酯聚(对亚丁基)碳酸酯熔融酯交换14-丁二醇
Diphenyl carbonatePoly(14-butylene carbonate)Melt-transesterification14-Butanediol
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