期刊
POLYMER
卷 72, 期 -, 页码 327-335出版社
ELSEVIER SCI LTD
DOI: 10.1016/j.polymer.2015.02.024
关键词
Catalytic nanoreactor; Biphasic hydroformylation catalysis; Core-cross-linked micelle (CCM)
资金
- Agence Nationale de la Recherche (ANR) [ANR-11-BS07-025-01]
- Centre National de la Recherche Scientifique (CNRS)
- Institut Universitaire de France (IUF)
Core-cross-linked micelles (CCM) functionalized at the core with covalently linked bis(p-methoxyphenyl) phenylphosphine (BMOPPP) ligands have been synthesized by a three-step one-pot radical polymerization in emulsion, using the polymerization-induced self-assembly (PISA) strategy and reversible addition-fragmentation chain transfer (RAFT) as the controlling method. The CCM are obtained by chain extending in water poly(methacrylic acid-co-poly(ethylene oxide) methyl ether methacrylate) (P(MAA-co-PEOMA), degree of polymerization of 30, MAA/PEOMA units molar ratio of 50:50) synthesized in a first step by RAFT with a 95:5 M mixture of styrene and 4-[bis(p-methoxyphenyl)phosphino]styrene (BMOPPS) units. The resulting micelles exhibiting a core composed of P(S-co-BMOPPS) segments with a degree of polymerization of 300 are then crosslinked in a third step with a mixture of di(ethylene glycol) dimethacrylate (DEGDMA) and styrene. The resulting BMOPPP@CCM exhibit a narrow size distribution (PDI = 0.16) with an average diameter of 81 nm in water and swell in THF or by addition of toluene to the latex. The addition of [Rh(acac) (CO)(2)] to the toluene-swollen latex results in metal coordination to the phosphine ligands. P-31{H-1} NMR spectroscopy shows that the Rh centers undergo rapid intraparticle phosphine ligand exchange. Application of these nanoreactors to the aqueous biphasic hydroformylation of 1-octene shows excellent activity and moderate catalyst leaching. (C) 2015 Elsevier Ltd. All rights reserved.
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