TY - JOUR
T1 - Synthesis of nixantphos core-functionalized amphiphilic nanoreactors and application to rhodium-catalyzed aqueous biphasic 1-octene hydroformylation
AU - Joumaa, Ahmad
AU - Gayet, Florence
AU - Garcia-Suarez, Eduardo J.
AU - Himmelstrup, Jonas
AU - Riisager, Anders
AU - Poli, Rinaldo
AU - Manoury, Eric
N1 - Publisher Copyright:
© 2020 by the authors.
PY - 2020/5/1
Y1 - 2020/5/1
N2 - A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 °C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO)2] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.
AB - A latex of amphiphilic star polymer particles, functionalized in the hydrophobic core with nixantphos and containing P(MAA-co-PEOMA) linear chains in the hydrophilic shell (nixantphos-functionalized core-crosslinked micelles, or nixantphos@CCM), has been prepared in a one-pot three-step convergent synthesis using reversible addition-fragmentation chain transfer (RAFT) polymerization in water. The synthesis involves polymerization-induced self-assembly (PISA) in the second step and chain crosslinking with di(ethylene glycol) dimethacrylate (DEGDMA) in the final step. The core consists of a functionalized polystyrene, obtained by incorporation of a new nixantphos-functionalized styrene monomer (nixantphos-styrene), which is limited to 1 mol%. The nixantphos-styrene monomer was synthesized in one step by nucleophilic substitution of the chloride of 4-chloromethylstyrene by deprotonated nixantphos in DMF at 60 °C, without interference of either phosphine attack or self-induced styrene polymerization. The polymer particles, after loading with the [Rh(acac)(CO)2] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield n-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.
KW - Aqueous biphasic catalysis
KW - Hydroformylation
KW - Nixantphos
KW - Polymerization-induced self-assembly
KW - RAFT polymerization
KW - Rhodium
KW - Water-confined polymeric nanoreactors
UR - https://www.scopus.com/pages/publications/85086725434
U2 - 10.3390/POLYM12051107
DO - 10.3390/POLYM12051107
M3 - Article
AN - SCOPUS:85086725434
SN - 2073-4360
VL - 12
JO - Polymers
JF - Polymers
IS - 5
M1 - 1107
ER -