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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

DOI: 10.11830/ISSN.1000-5013.2010.03.0292

Keywords: 二氧化碳, 聚丙撑碳酸酯, 缺电性, 稀土催化剂

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Abstract:

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.

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