硅羟基对二氧化硅固载有机锡酯交换催化性能的影响

doi:10.11949/j.issn.0438-1157.20161517

化工学报 ›› 2017, Vol. 68 ›› Issue (5): 1892-1898.DOI: 10.11949/j.issn.0438-1157.20161517

• 催化、动力学与反应器 • 上一篇下一篇

硅羟基对二氧化硅固载有机锡酯交换催化性能的影响

张元卓^1,2, 王松林³, 肖忠良^1,2, 陈彤¹, 王公应¹

1 中国科学院成都有机化学研究所, 四川成都 610041;
2 中国科学院大学, 北京 100049;
3 河南科技学院化学化工学院, 河南新乡 453003

收稿日期:2016-10-31 修回日期:2017-01-23 出版日期:2017-05-05 发布日期:2017-05-05
通讯作者: 陈彤
基金资助:
国家高技术研究发展计划项目（2013AA031703）；四川省青年科技创新研究团队项目（2013TD0010）。

Effect of silanol content in silica support on catalytic performance of silica-anchored organotin catalyst for transesterification

ZHANG Yuanzhuo^1,2, WANG Songlin³, XIAO Zhongliang^1,2, CHEN Tong¹, WANG Gongying¹

1 Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, Sichuan, China;
2 University of Chinese Academy of Sciences, Beijing 100049, China;
3 School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang 453003, Henan, China

Received:2016-10-31 Revised:2017-01-23 Online:2017-05-05 Published:2017-05-05
Supported by:
supported by the National High Technology Research and Development Program of China (2013AA031703) and the Science and Technology Innovation Program for Youth Team of Sichuan Province (2013TD0010).

摘要/Abstract

摘要：

采用新方法制备了二氧化硅固载有机锡。以无机SnCl₄为锡源，在合成有机锡的同时制备有机锡硅烷试剂，再将其固载到二氧化硅上，用于碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的反应。通过不同的制备方法和处理方法，制得不同硅羟基含量的二氧化硅载体；研究硅羟基对锡固载量及固载有机锡催化性能的影响。TG与ICP表征显示，锡固载量与二氧化硅载体的硅羟基含量正相关。²⁹Si MAS NMR表征发现，制备的固载有机锡中含有较多的T²和T³物种，利于有机锡的稳定固载。二氧化硅硅羟基含量越高，催化剂的锡固载量越高，活性越好。介孔二氧化硅为载体制备的Sn-MSiO₂表现出最好的催化活性：用量1.0 g，在150～180℃反应9 h，苯酚转化率达50.4%，酯交换选择性高于99.9%；用0.5 g考察重复使用性能，重复使用5次，苯酚转化率由41.2%降低到35.0%。锡流失是活性下降的主要原因。

关键词: 有机锡, 固载, 硅羟基, 碳酸二苯酯, 苯酚, 酯交换

Abstract:

Silica-anchored organotin catalysts has been synthesized by a new synthetic scheme. It involves the synthesis of organotin-silane during the preparation of organotin using inorganic SnCl₄as tin precursor, which was then ahchored on the silicas for the transesterification of DMC with phenol to diphenyl carbonate. A series of silica supports containing different silanols were obtained by different preparations along with different treatments. TG and ICP characterizations showed that the Sn loading of the catalyst had positive correlation with the silanol content of the silica support. ²⁹Si MAS NMR measurements indicated that the prepared catalysts possessed many T²and T³ species, which was in favor of the stability. The more silanol the silica support contained, the more Sn the catalyst supported, and the more active the catalyst would be. Sn-MSiO₂, the catalyst with the mesoporous silica support, exhibited the best catalytic performance: with a reaction temperature of 150—180℃ for 9 h, and a catalyst amount of 1.0 g, the phenol conversion and the transesterification selectivity reached 50.4% and 99.9%, respectively; in recycle test with a catalyst amount of 0.5 g, the phenol conversion decreased from 41.2% to 35.0% after five runs. Sn leaching was the main reason for the decline of catalytic activity.

Key words: organotin, anchor, silanol, diphenyl carbonate, phenol, transesterification

中图分类号:

O623
O643

张元卓, 王松林, 肖忠良, 陈彤, 王公应. 硅羟基对二氧化硅固载有机锡酯交换催化性能的影响[J]. 化工学报, 2017, 68(5): 1892-1898.

ZHANG Yuanzhuo, WANG Songlin, XIAO Zhongliang, CHEN Tong, WANG Gongying. Effect of silanol content in silica support on catalytic performance of silica-anchored organotin catalyst for transesterification[J]. CIESC Journal, 2017, 68(5): 1892-1898.

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硅羟基对二氧化硅固载有机锡酯交换催化性能的影响

Effect of silanol content in silica support on catalytic performance of silica-anchored organotin catalyst for transesterification

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