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发布时间：2019-10-22

论文类型：期刊论文

发表时间：2003-05-01

发表刊物：JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL

收录刊物：EI、SCIE

卷号：198

期号：1-2

页面范围：23-27

ISSN号：1381-1169

关键字：thermoregulated phase transfer catalysis; hydroformylation; thermoregulated phosphine; high olefins

摘要：A novel water soluble phosphine,N,N-dipolyoxyethylene-substituted-2-(diphenylphosphino)phenylamine (PEO-DPPPA), was synthesized by a two-step ethoxylation of 2-(diphenylphosphino)phenylamine (2-Ph2P-C6H4NH2, DPPPA). In the first step, DPPPA was ethoxylated without catalyst to give an intermediate with an average polyethylene glycol (PEG) chain length (L = m + n) of 3. Thereafter, this intermediate was further ethoxylated by using KOH as a catalyst to obtain the products with needed values of L. The solubility of the products in water increases with increasing of L. When L is more than 35, the products are water-soluble and possess the property of inverse temperature-dependent solubility in water (cloud point, C-p) as nonionic surfactants. The PEO-DPPPA/Rh complex catalyst formed in situ by RhCl3.3H(2)O and PEO-DPPPA (L = 45) has been applied to the aqueous-organic biphasic hydroformylation of 1-decene. The conversion of olefin and the yield of aldehyde are 99.5 and 99.0%, respectively, under the conditions of 120 degreesC, 5.0 MPa (CO/H-2 = 1), P/Rh = 4 (molar ratio), 1-decene/Rh = 1000 (molar ratio) and 5 h. Recycling test shows that both the conversion of olefin and the yield of aldehyde are still higher than 94.0% even after the catalyst has been recycled 20 times. The high reactivity of PEO-DPPPA/Rh complex can be attributed to a process termed thermoregulated phase transfer catalysis. (C) 2002 Elsevier Science B.V. All rights reserved.