Catalytic hydrogenation and gas permeation properties of metal‐containing poly(phenylene oxide) and polysulfone

Abstract

SYNOPSISMetal-containing polymers, PPO-DPP-Pd, PPO-CPA-Pd, PSF-DPP-Pd, PSF-CPA-Pd (DPP = diphenylphosphinyl, CPA = o-carboxy phenyl amino), PPO-M ( M = Pd, Cu, Co, Ni) , and PSF-Pd, were prepared by incorporating metal chloride with either modified or unmodified poly (2,6-dimethyl-l,4-~henylene oxide) (PPO) and polysulfone (PSF) . The Pd-containing polymers exhibit catalytic activity in the hydrogenation of cyclopentadiene under mild conditions (40"C, 0.1 MPa) both in alcohol solution and in the gas phase. The selectivity in the hydrogenation of diene to monoene in the gas phase can be controlled by adjusting the hydrogen partial pressure. The metal-containing polymers, PPO-M and PSFPd, can be cast easily into the membranes. The H2/N2 permselectivity for PPO-M is higher than that for unmodified PPO, whereas the permeability of H2 changes slightly. The H2 permeability and H2/Nz permselectivity for the PPO-Pd membrane are up to 67.5 barrers and 135, respectively. 0 1993 John Wiley & Sons, Inc. I NTRO D U C T 1 0 NMetal-containing polymeric materials have been studied extensively because of their potential applications as versatile materials.'-6 Much effort has been expended in studying these materials as catalysts, which are presumed to combine the virtues of both homogeneous and heterogeneous catalysts in various chemical reactions such as hydrogenation, carbonylation, oxidation, and polymeri~ation.~-'~ It has been indicated that in these materials metal complexes or metal ions, surrounded by giant polymer chains, show interesting physical properties and chemical reactivities that are different from those of the corresponding ordinary metal complexes or metal ions. On the other hand, many studies have also reported that the doping or coordination of metal ions or complexes, which may selectively and reversibly coordinate gases, into polymers is one approach to improve the permeability and permselectivity of the polymeric membranes."-23However, up to now, there has been no report dealing with metal-containing polymeric materials to be used in both catalytic reactions and gas separation. Recently, we prepared several metal-containing polymeric materials by incorporating transition metal chlorides into modified or unmodified poly ( 2,6-dimethyl-1,4-phenylene oxide) (PPO) and polysulfone (PSF) . The catalytic activities in the hydrogenation of cyclopentadiene and isoprene as well as the H2 and N2 permeabilities of these polymeric materials have been investigated. EXPERIMENTAL Preparation of Materials Preparation of PPO-DPP-Pd and PSF-DPP-PdThe brominated PPO substituted with bromine at aromatic carbon (PPO, Shanghai Institute of Syn-

Adlayers of palladium particles and their aggregates on porous polypropylene hollow fiber membranes as hydrogenization contractors/reactors

“…Follow-up studies on the development of polymeric catalytic membranes were performed in the two following directions: (i) dense catalytic membranes [9][10][11][12][13][14][15][16][17][18] and (ii) porous catalytic membranes for both gas phase hydrogenation [19][20][21][22][23][24] and liquid phase hydrogenation [25][26][27][28][29][30][31][32][33][34][35].…”

Esterification of Lactic Acid and Ethanol with/without Pervaporation

“…Several studies have been conducted on membrane reactors applied to gas-phase reactions such as catalytic dehydrogenation, hydrogenation, and decomposition reactions. [1][2][3][4][5][6][7][8] However, much less work has been done on liquid-phase reactions because of a lack of suitable membranes with good permselectivity and solvent resistance.…”

Structural Characterization of Catalytically Active Metal Nanoclusters in Poly(amide imide) Films with High Metal Loading

“…21 A few examples of catalysis using protected catalyst particles in polymer films have been reported. 22,23 Rarely were such films utilized in the membrane mode for catalysis. 24 Other methods to form clusters in polymer films take advantage of the ability to bind cluster precursors to ionic polymers like Nafion 25,26 followed by reduction to metal clusters or use organometallics as precursors.…”

“…These films have been proposed as membranes 20 and tested in the membrane mode for catalytic activity . A few examples of catalysis using protected catalyst particles in polymer films have been reported. , Rarely were such films utilized in the membrane mode for catalysis …”