[1]全志龙,王献红,赵晓江,等.稀土催化CO2和环氧丙烷的共聚合(Ⅰ)配体对活性中心缺电性及聚合反应的影响[J].华侨大学学报(自然科学版),2010,31(3):292-296.[doi:10.11830/ISSN.1000-5013.2010.03.0292]
　QUAN Zhi-long,WANG Xian-hong,ZHAO Xiao-jiang,et al.Copolymerization of CO2 and Propylene Oxide under Rare-Earth Ternary Catalyst(Ⅰ) Influence of the Ligands on the Electron Density of the Active Species and Reaction Mechanism[J].Journal of Huaqiao University(Natural Science),2010,31(3):292-296.[doi:10.11830/ISSN.1000-5013.2010.03.0292]
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稀土催化CO2和环氧丙烷的共聚合(Ⅰ)配体对活性中心缺电性及聚合反应的影响()
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《华侨大学学报（自然科学版）》[ISSN:1000-5013/CN:35-1079/N]

卷:
第31卷
期数:
2010年第3期
页码:
292-296
栏目:
出版日期:
2010-05-20

文章信息/Info

Title:
Copolymerization of CO2 and Propylene Oxide under Rare-Earth Ternary Catalyst(Ⅰ) Influence of the Ligands on the Electron Density of the Active Species and Reaction Mechanism
文章编号:
1000-5013(2010)03-0292-05
作者:
全志龙; 王献红; 赵晓江; 王佛松
华侨大学材料科学与工程学院; 中国科学院长春应用化学研究所高分子国家重点实验室
Author(s):
QUAN Zhi-long1; 2;  WANG Xian-hong2;  ZHAO Xiao-jiang2;  WANG Fo-song2
1.College of Material Science and Engineering, Huaqiao University, Quanzhou 362021, China; 2.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
关键词:
二氧化碳;  聚丙撑碳酸酯;  缺电性;  稀土催化剂
Keywords:
carbon dioxide;  poly(propylene carbonate);  electronic deficient;  rare-earth catalyst
分类号:
O631.5
DOI:
10.11830/ISSN.1000-5013.2010.03.0292
文献标志码:
A
摘要:
将不同配位方式的稀土羧酸盐/稀土磺酸盐-甘油-二乙基锌两类稀土催化剂用于CO2-PO的共聚合反应,探讨中心金属Y3+或Zn2+的缺电子性与催化剂活性的关系.结果表明,磺酸类稀土三元催化体系的活性高于相应的羧酸类稀土催化体系,所得聚合物的相对分子质量分布较宽(11.2~20.6).1H-NMR表明,萘磺酸钇催化聚合产物中碳酸酯单元含量减少近6%; UV-vis和XPS能谱显示,缺电性增强的中心金属Y3+或Zn2+有利于环氧丙烷(PO)和单体的配位活化,产物收率提高30%.此外,配体与中心金属间配位隙孔也是影响催化活性的重要因素,由此推断稀土催化CO2-PO的共聚反应可能是双活性中心过程.
Abstract:
Sulfonate and carbonate yttrium-based ternary catalysts were employed for the copolymerization of CO2 and epoxide.It has been found that the catalystic activity of sulfonate yttrium-based ternary catalyst is higher than that of the corresponding carbonate ones,and the molecular weight distribution of the copolymers obtained from sulfonate yttrium-based ternary catalyst is broader(11.2~20.6).1H-NMR spectra shows that the ether unit in the resulting copolymer obtained from the carbonate yttrium-based ternary catalyst is 6% high than of sulfonate yttrium-based ternary catalyst.Based on the ultraviolet visible spectra and X-ray photoelectron spectroscopy(XPS) technique,it seems that the electron deficient of the central metal Y3+ or Zn2+,as well as the thicker leap between the central metal and ligand are beneficial to facilitate the insertion of propylene oxide and CO2 to produce polycarbonate,leading a 30% increase of the catalytic activity.A bimetallic active species mode was proposed to interpret this phenomenon.

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备注/Memo

备注/Memo:
国家自然科学基金资助项目(20225414)
更新日期/Last Update: 2014-03-23