| 曹平,杨先贵,唐聪明,王公应.TiO(acac)2催化碳酸二甲酯和苯基乙酸酯合成碳酸二苯酯[J].分子催化,2010,(6):0 |
| TiO(acac)2催化碳酸二甲酯和苯基乙酸酯合成碳酸二苯酯 |
| TiO(acac)2 used as a catalyst for transesterification of dimethyl carbonate and phenyl acetate to diphenyl carbonate |
| 投稿时间：2010-09-21 修订日期：2010-10-15 |
| DOI： |
| 中文关键词: 乙酰丙酮氧钛 碳酸二甲酯 乙酸苯酯 酯交换 碳酸二苯酯 机理 |
| 英文关键词:bis(acetyl acetonate) titanium oxide dimethyl carbonate phenyl acetate transesterification diphenyl carbonate mechanism |
| 基金项目:国家十一五科技支撑计划;江苏省常州市科技局工业科技攻关计划 |
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| 中文摘要: |
| 碳酸二苯酯（DPC）是非光气法生产聚碳酸酯（PCs）的重要原料，具有多种酯交换法合成路线，如碳酸二甲酯（DMC）与苯酚酯交换法、DMC与苯基乙酸酯（PA）酯交换法、草酸二甲酯（DMO）与苯酚酯交换法等。本文对比测定了几种金属乙酰丙酮配合物和有机钛化合物对碳酸二甲酯(DMC)与苯基乙酸酯(PA)酯交换合成DPC反应的催化性能，结果表明，乙酰丙酮氧钛[TiO(acac)2]是一种良好的酯交换催化剂，具有优良的催化性能。在反应条件θ=180℃, n(PA)=0.8mol, n(DMC)/n(PA)=1/2, n(TiO(acac)2)/n(PA)=0.006, t=4 h下，DMC转化率可达74.9%，甲基苯基碳酸酯(MPC) 和DPC的选择性分别可达56.9%和38.9%。探索并提出了TiO(acac)2催化 DMC与PA酯交换合成DPC反应的机理。 |
| 英文摘要: |
| Diphenyl carbonate (DPC) is considered as a substitution for phosgene to synthesize polycarbonates (PCs), and some methods are used for the synthesis of DPC, such as the transesterification of dimethyl carbonate (DMC) with phenyl acetate (PA), dimethyl carbonate (DMC) with phenol, and dimethyl oxalate(DMO) with phenol. In this prescript, the catalytic performance of some metal acetylacetonates and titanium compounds for transesterification of DMC with PA to DPC was measured and it was found that bis(acetyl acetonate) titanium oxide (TiO(acac)2) was a novel and efficient catalyst and it is testified that Ti was the catalytic center of the catalyst. When the reaction was carried out at 180 篊, with a molar ratio of PA to DMC of 2:1, a reaction time 4 h, a catalyst amount 0.6% (molar ratio to PA), the conversion of DMC was 74.9%, and the selectivity of DPC and MPC was 38.9% and 56.9%, respectively. Furthermore, a plausible mechanism for the transesterification of DMC and PA to MPC and DPC catalyzed by TiO(acac)2 was proposed by changing the feeding order of the materials and catalyst. |
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