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An insight into the catalytic hydrogenation mechanism of modified dendrimer-loaded rhodium ionic catalyst for unsaturated copolymer

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Abstract

A catalytic mechanism of ionic rhodium catalyst stabilized by macrcycles-modified dendrimer (G2-M(Rh3+)) for the hydrogenation of unsaturated copolymer was proposed. It was found that the co-catalyst of triphenylphosphine (PPh3) possessed significant influence on the catalytic hydrogenation activity of G2-M(Rh3+). An active specie of [Rh(PPh3)3]+ could be generated from a ligand exchange between G2-M(Rh3+) and PPh3 during the hydrogenation process, which could outstandingly improve the selective hydrogenation activity for unsaturated co-polymers. Totally different from other catalyst for hydrogenation, the active [Rh(PPh3)3]+ was reduced to Rh0 nanoparticles which could be further recaptured by the non-coordinated macrocycles in G2-M after hydrogenation. The Rh0 recapture could significantly reduce Rh residues in the hydrogenated co-polymers. This research can give an insight into the interaction of dendrimer-loaded Rh and the co-catalyst of PPh3 during hydrogenation processs.

The Rh0, genarated from the reduction of [Rh(PPh3)3]+, can be recaptured by the non-coordinated macrocycles in G2-M after the hydrogenation. Thus, the Rh residues of HNBR and HSBR catalyzed by G2-M(Rh3+) decreased 81.1 wt% and 82.1 wt% compared with those of Rh(PPh3)3Cl. The Rh0 nanoparticle possesses weak interaction with PPh3 to generate active catalytic species for the hydrogenation in NBR and SBR, which reduced the catalytic activity of the recycled catalyst.

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Funding

This work was supported financially by the National Natural Science Foundation of China (Project No. 51273071).

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Authors and Affiliations

  1. Department of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China

    Wei Zhou

  2. Department of Materials Science and Engineering, South China University of Technology, Guangzhou, 510640, China

    Wei Zhou & Xiaohong Peng

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  1. Wei Zhou
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Zhou, W., Peng, X. An insight into the catalytic hydrogenation mechanism of modified dendrimer-loaded rhodium ionic catalyst for unsaturated copolymer. Colloid Polym Sci 297, 1001–1009 (2019). https://doi.org/10.1007/s00396-019-04533-2

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