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Preparation of Polymer Supported Phosphine Ligands by Metal Catalyzed Living Radical Copolymerization and Their Application to Hydroformylation Catalysis
Author(s) -
Cardozo Andrés F.,
Manoury Eric,
Julcour Carine,
Blanco JeanFrançois,
Delmas Henri,
Gayet Florence,
Poli Rinaldo
Publication year - 2013
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201200446
Subject(s) - hydroformylation , polymer chemistry , copolymer , chemistry , atom transfer radical polymerization , phosphine , selectivity , catalysis , styrene , dispersity , living polymerization , rhodium , radical polymerization , monomer , polymer , organic chemistry
A series of well‐defined polystyrene‐supported tertiary phosphine ligands were prepared by copper‐catalyzed atom transfer radical polymerization (ATRP), involving direct copolymerization of styrene and 4‐diphenylphosphinostyrene (or 4‐styryldiphenylphosphine, SDPP). Copolymerization of the two monomers at different molar ratios showed a decreasing level of control as the SDPP molar fraction ( f SDPP ) increased. A satisfactory level of control was achieved for f SDPP ≤0.25 such that there was a constant concentration of growing “living chains”, and linear M n growth with conversion and low dispersity. Copper‐free polymers with different chain lengths were prepared and tested as polymeric ligands in the rhodium‐catalyzed hydroformylation of 1‐octene. The polymeric ligands yielded higher linear/branched selectivity and lower activity relative to PPh 3 at the same P/Rh ratio. The selectivity increased slightly as a function of the polymer chain length.