Functional gel-type resin based palladium catalysts: The role of polymer properties in the hydrogenation of the C C bond of maleic and fumaric acids, the isomers of dicarboxylic acids

• Published in: Reactive & functional polymers Vol. 68; no. 6; pp. 1059 - 1071
• Main Authors: Drelinkiewicz, A., Knapik, A., Waksmundzka-Góra, A., Bukowska, A., Bukowski, W., Noworól, J.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.06.2008; Elsevier Science
• Subjects: Applied sciences; Catalysis; Catalysts; Crosslinking; Exact sciences and technology; Fumaric acid; Functional gel-type resin; Hydrogenation; Nanostructure; Organic polymers; Palladium; Physicochemistry of polymers; Properties and characterization; Special properties (catalyst, reagent or carrier); Swelling; Functional gel-type resin; Hydrogenation; Palladium; Particle size; Nanoparticle; Suspension copolymerization; Crosslinked copolymer; Maleic acid; Size effect; Acid copolymer; Catalyst support; Matrix effect; Hydroxyethyl methacrylate copolymer; Organic anhydride; Experimental study; Metal particle; Esterification; Heterogeneous catalysis; Chemical modification; Fumaric acid; Preparation; Succinic acid; Methacrylate copolymer; Radical copolymerization; Catalyst activity; Styrene copolymer
• ISSN: 1381-5148
• DOI: 10.1016/j.reactfunctpolym.2008.02.008

Functional gel-type resins (OFP) composed of 2-hydroxyethyl methacrylate (HEMA, 20 mol%), styrene (60–77 mol%) and diethylene glycol dimethacrylate, the crosslinking reagent (DEGDMA, 3–20 mol%) are used as supports for palladium catalysts (0.25–2 wt% Pd). The influence of polymer mass expansion on the activity of Pd/OFP catalysts in the hydrogenation of cis- and trans-isomers of unsaturated dicarboxylic acids, maleic (MA) and fumaric (FA), is examined. Starting polymer swells very well in THF and this solvent is used in the hydrogenation experiments. Swelling ability of polymer decreases after insertion of palladium ions due to the crosslinking effect. Reduction of Pd/OFP by NaBH 4 leads to further decrease in swelling ability of polymer caused by the changes in polymer structure observed in FTIR spectroscopy. In the reduced form of the catalysts the nano-particles of Pd (2–3 nm) are formed. Hydrogenation experiments performed in a wide range of operating conditions (Pd loading, catalysts concentration, crosslinking degree of polymer, the size of catalysts grains) show that the swelling of polymer mass during the hydrogenation is a crucial factor for activity of Pd/OFP catalysts. When the catalyst does not swell, the rates of hydrogenation for both isomers are practically the same. They differ only when the catalysts grains are in swollen state. Much higher rate of hydrogenation is observed for MA (the cis-isomer) than for FA (the trans-isomer). This is related to easier penetration of cis-isomer (MA) inside the bulk of the polymer mass which results in more effective utilization of substrates, MA and FA, when present in THF both enhance the expansion of polymer mass but especially cis-isomer, MA. Substrate effect is attributed to the interaction between functional groups present in the reduced catalysts and the hydrogenated reagents, maleic or fumaric acids.