Triphenylphosphane-Functionalised Amphiphilic Copolymers: Tailor-Made Support Materials for the Efficient and Selective Aqueous Two-Phase Hydroformylation of 1-Octene

Amphiphilic copolymers (random P1 and block P2) based on 2‐oxazolines were synthesised with triphenylphosphane ligands covalently linked to the polymers by means of a metal‐free synthesis route. The resulting macroligands were used in the aqueous two‐phase hydroformylation of 1‐octene. The influence of the polymer architecture (random and block copolymers) on activity and selectivity of the hydroformylation reaction was investigated and compared with that of nonfunctionalised copolymers (random P3 and block P4) and RhI/triphenylphosphane trisulfonate as a water‐soluble catalyst. The highest activities were observed for the random copolymer P1 (p=50 bar, T=100 °C, c=8×10−4 mol L−1) with a turnover frequency (TOF) of 3700 h−1, whereas the corresponding block copolymer P2 reached TOF numbers of 1630 h−1. Additionally, both macroligands indicated efficient suppression of isomerisation and led to almost constant n/iso selectivities of about 3 after complete substrate conversion. Copolymers P3 and P4 showed, under identical reaction conditions, strong isomerisation after 40–60 % conversion (n/iso≈0.7) and maximum activities of 1560 h−1 (P3) and 1330 h−1 (P4) at a concentration of 5×10−3 mol L−1. Tailor‐made polymer supports—beyond simple catalyst immobilisation: Amphiphilic polymer supports with random and block copolymer structures, functionalised with triphenylphosphane ligands, show excellent activity and selectivity in the aqueous two‐phase hydroformylation of 1‐octene (see scheme).