常压下聚合物负载钯催化剂催化卤化烯丙基羰基化反应

Reactive Polymers Pub Date : 1994-10-01 DOI:10.1016/0923-1137(94)90009-4

Hanrong Gao, Yun Xu, Shijian Liao, Daorong Yu

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引用次数: 7

摘要

在温和条件下(40℃，0.1 MPa)，钯催化剂负载在聚(n -乙烯基-2-吡咯烷酮)(PVP)、聚丙烯酰胺(PAA)、改性聚(2,6-二甲基-1,4-苯基氧化物)(PPO)和聚砜(PSF)等聚合物上，催化烯丙基卤化物羰基化生成丁烯酸。这些聚合物负载的钯催化剂对烯丙基卤化物的羰基化表现出非常高的活性和稳定性。在两相(naoh -苯水溶液)介质中，氯丙烯和溴丙烯羰基化反应中，PVP-Pd的周转率(TOF, mol CO/mol Pd min−1)分别高达21和40。反复使用后，甲基化后的PPO-Pd在烯丙基溴羰基化反应中的周转量(mol CO/mol Pd)可达30,000。考察了溶剂、相转移剂和官能团对催化剂活性的影响。

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Carbonylation of allyl halides catalyzed by polymer-supported palladium catalysts under atmospheric pressure

Palladium catalysts supported on polymers, such as poly(N-vinyl-2-pyrrolidone) (PVP), polyacrylamide (PAA), modified poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and polysulfone (PSF), were used to catalyze the carbonylation of allyl halides to form butenoic acid under mild conditions (40°C, 0.1 MPa). These polymer-supported palladium catalysts exhibit very high activity and stability towards the carbonylation of allyl halides. The turnover frequencies (TOF, mol CO/mol Pd min⁻¹) of PVP-Pd are up to 21 and 40 for the carbonylation of allylchloride and allylbromide, respectively, in two-phase (aqueous NaOH-benzene) medium.

After repeated use, the turnover (mol CO/mol Pd) of phosphinated PPO-Pd in the carbonylation of allylbromide can be up to 30,000. The effects of solvent, phase transfer agent and the functional support group on the activity of these catalysts were investigated.

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Reactive Polymers

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