乙酸氧钛对碳酸二甲酯与苯酚酯交换的催化作用

doi:10.7503/cjcu20140420

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (11): 2418.doi: 10.7503/cjcu20140420

乙酸氧钛对碳酸二甲酯与苯酚酯交换的催化作用

唐荣芝^1,², 王松林^1,², 张元卓^1,², 陈彤¹(), 王公应¹

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

收稿日期:2014-05-04 出版日期:2014-11-10 发布日期:2014-10-09
作者简介:联系人简介: 陈彤, 女, 博士, 研究员, 博士生导师, 主要从事催化化学与绿色化工研究. E-mail:chentongw@sina.com.cn
基金资助:
国家“八六三”计划项目(批准号: SS2013AA031703)和四川省青年科技创新研究团队项目(批准号: 2013TD0010)资助

Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol^†

TANG Rongzhi^1,², WANG Songlin^1,², ZHANG Yuanzhuo^1,², CHEN Tong^1,^*(), WANG Gongying¹

1. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2014-05-04 Online:2014-11-10 Published:2014-10-09
Contact: CHEN Tong E-mail:chentongw@sina.com.cn
Supported by:
† Supported by the National High Technology Research and Development Program, China(No.SS2013AA031703) and the Youth Technology Innovation Team Project of Sichuan Province, China(No.2013TD0010).

摘要/Abstract

摘要：

采用溶剂热法合成了乙酸氧钛, 其对碳酸二甲酯(DMC)与苯酚的酯交换合成碳酸二苯酯(DPC)的催化反应显示出了很好的催化效果. 乙酸氧钛用量0.10 g时, 苯酚转化率即达到47.8%, 酯交换选择性在99.9%以上, 仅检测到微量副产物苯甲醚. 傅里叶变换红外光谱(FTIR)和固体核磁共振(¹³C NMR)等表征结果显示, 乙酸氧钛在反应过程中首先与苯酚反应, 苯氧基取代乙酸根生成苯氧基钛合物. 实验结果表明, 苯氧基钛合物作为实际催化剂参与DMC和苯酚的酯交换反应, 并且重复使用效果良好.

关键词: 乙酸氧钛, 碳酸二苯酯, 苯酚, 酯交换, 多相催化剂, 苯氧基钛合物

Abstract:

Titanyl acetate was prepared through the solvothermal reaction between titanium(Ⅳ) n-butoxide, acetic anhydride and distilled water. Titanyl acetate was firstly used in the transesterification reaction of dimethyl carbonate and phenol to diphenyl carbonate and exhibited excellent performance. When titanyl acetate amount is 0.10 g, the phenol conversion reaches to 47.8% and transesterification selectivity is 99.9% with trace anisole. Based on the results of FTIR, solid state ¹³C NMR, titanyl acetate reacts firstly with phenol. The acetate group of titanyl acetate is replaced by phenoxy group and generates phenoxy titanium complex. It could be considered that phenoxy titanium complex is the real catalyst for the transesterification of dimethyl carbonate and phenol with good resuability.

Key words: Titanyl acetate, Diphenyl carbonate, Phenol, Transesterification, Heterogeneous catalyst, Phenoxytitanium complex

中图分类号:

TrendMD:

唐荣芝, 王松林, 张元卓, 陈彤, 王公应. 乙酸氧钛对碳酸二甲酯与苯酚酯交换的催化作用. 高等学校化学学报, 2014, 35(11): 2418.

TANG Rongzhi, WANG Songlin, ZHANG Yuanzhuo, CHEN Tong, WANG Gongying. Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol^†. Chem. J. Chinese Universities, 2014, 35(11): 2418.

图/表 14

Fig.1 Monodentate(A), Bidentate chelating(B) and Bidentate bridging(C) modes occurring in metal and carboxylates[21]

Fig.2 FTIR spectrum of titanyl acetate sample

Scheme 1 Structure of titanyl acetate(structure Ⅰ)

Fig.3 Solid state 13C NMR spectrum of titanyl acetate sample

Fig.4 TG(a), DTG(b) and DTA(c) curves of titanyl acetate sample

Table 1 Catalytic performance of titanyl acetate on the transesterification of DMC and phenol*

Mass of catalyst/g	Conversion of phenol (%)	Selectivity of transesterification (%)	Yield (%)
Mass of catalyst/g	Conversion of phenol (%)	Selectivity of transesterification (%)	MPC	DPC	AN
0.05	42.2	99.9	22.3	19.9	trace
0.10	47.8	99.9	25.6	22.2	trace
0.15	47.7	99.9	25.3	22.4	trace
0.20	48.4	99.9	24.7	23.7	trace
0.40	47.1	99.9	23.3	23.8	trace

Fig.5 Effect of calcined temperature on catalytic performance of titanyl acetate Reaction condition: 160 mmol phenol, 160 mmol DMC, 0.10 g catalyst, 9 h, 150—180 ℃.

Fig.6 XRD patterns of titanyl acetate calcined at different temperatures a. 200 ℃; b. 250 ℃; c. 300 ℃; d. 400 ℃.

Table 2 Reusability of catalyst*

Running time	Conversion of phenol (%)	Selectivity of transesterification (%)	Yield (%)
Running time	Conversion of phenol (%)	Selectivity of transesterification (%)	MPC	DPC	AN
1	47.8	99.9	25.6	22.2	trace
2	47.5	99.9	23.2	24.3	trace
3	45.0	99.9	22.7	22.3	trace

Fig.7 FTIR spectra of used catalyst a. 1st run; b. 2nd run; c. 3rd run.

Fig.8 Solid state 13C NMR spectrum of used catalyst

Scheme 2 Structure of used catalyst(structure Ⅱ)

Scheme 3 Reactions equations between titanyl acetate and phenol

Scheme 4 Reaction mechanism over phenoxy titanium complex on the transesterification of DMC and phenol

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乙酸氧钛对碳酸二甲酯与苯酚酯交换的催化作用

Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol^†

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乙酸氧钛对碳酸二甲酯与苯酚酯交换的催化作用

Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol†

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Catalytic Property of Titanyl Acetate in the Transesterification Reaction of Dimethyl Carbonate and Phenol^†