Journal
POLYMERS
Volume 12, Issue 5, Pages -Publisher
MDPI
DOI: 10.3390/polym12051107
Keywords
aqueous biphasic catalysis; hydroformylation; polymerization-induced self-assembly; RAFT polymerization; rhodium; nixantphos; water-confined polymeric nanoreactors
Categories
Funding
- European Union [860322]
- Agence Nationale de la Recherche [ANR-11-BS07-025-01]
- Marie Curie Actions (MSCA) [860322] Funding Source: Marie Curie Actions (MSCA)
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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 degrees 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.
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