Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation
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 s...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-05-01
|
| Series: | Polymers |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4360/12/5/1107 |
| _version_ | 1797568197121015808 |
|---|---|
| author | Ahmad Joumaa Florence Gayet Eduardo J. Garcia-Suarez Jonas Himmelstrup Anders Riisager Rinaldo Poli Eric Manoury |
| author_facet | Ahmad Joumaa Florence Gayet Eduardo J. Garcia-Suarez Jonas Himmelstrup Anders Riisager Rinaldo Poli Eric Manoury |
| author_sort | Ahmad Joumaa |
| collection | DOAJ |
| description | 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)<sub>2</sub>] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield <i>n</i>-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal. |
| first_indexed | 2024-03-10T19:53:01Z |
| format | Article |
| id | doaj.art-de678b70e6744ed6941b2d73d6bbb704 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T19:53:01Z |
| publishDate | 2020-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-de678b70e6744ed6941b2d73d6bbb7042023-11-20T00:14:06ZengMDPI AGPolymers2073-43602020-05-01125110710.3390/polym12051107Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene HydroformylationAhmad Joumaa0Florence Gayet1Eduardo J. Garcia-Suarez2Jonas Himmelstrup3Anders Riisager4Rinaldo Poli5Eric Manoury6CNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 route de Narbonne, BP 44099, F-31077 Toulouse CEDEX 4, FranceCNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 route de Narbonne, BP 44099, F-31077 Toulouse CEDEX 4, FranceCentre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kemitorvet, Building 207, 2800 Kgs. Lyngby, DenmarkCentre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kemitorvet, Building 207, 2800 Kgs. Lyngby, DenmarkCentre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, Kemitorvet, Building 207, 2800 Kgs. Lyngby, DenmarkCNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 route de Narbonne, BP 44099, F-31077 Toulouse CEDEX 4, FranceCNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 route de Narbonne, BP 44099, F-31077 Toulouse CEDEX 4, FranceA 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)<sub>2</sub>] precatalyst to yield Rh-nixantphos@CCM, function as catalytic nanoreactors under aqueous biphasic conditions for the hydroformylation of 1-octene to yield <i>n</i>-nonanal selectively, with no significant amounts of the branched product 2-methyl-octanal.https://www.mdpi.com/2073-4360/12/5/1107aqueous biphasic catalysishydroformylationpolymerization-induced self-assemblyRAFT polymerizationrhodiumnixantphos |
| spellingShingle | Ahmad Joumaa Florence Gayet Eduardo J. Garcia-Suarez Jonas Himmelstrup Anders Riisager Rinaldo Poli Eric Manoury Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation Polymers aqueous biphasic catalysis hydroformylation polymerization-induced self-assembly RAFT polymerization rhodium nixantphos |
| title | Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation |
| title_full | Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation |
| title_fullStr | Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation |
| title_full_unstemmed | Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation |
| title_short | Synthesis of Nixantphos Core-Functionalized Amphiphilic Nanoreactors and Application to Rhodium-Catalyzed Aqueous Biphasic 1-Octene Hydroformylation |
| title_sort | synthesis of nixantphos core functionalized amphiphilic nanoreactors and application to rhodium catalyzed aqueous biphasic 1 octene hydroformylation |
| topic | aqueous biphasic catalysis hydroformylation polymerization-induced self-assembly RAFT polymerization rhodium nixantphos |
| url | https://www.mdpi.com/2073-4360/12/5/1107 |
| work_keys_str_mv | AT ahmadjoumaa synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation AT florencegayet synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation AT eduardojgarciasuarez synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation AT jonashimmelstrup synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation AT andersriisager synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation AT rinaldopoli synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation AT ericmanoury synthesisofnixantphoscorefunctionalizedamphiphilicnanoreactorsandapplicationtorhodiumcatalyzedaqueousbiphasic1octenehydroformylation |