@inbook {2453, title = {New Chemistry, Including Pulp Bleaching Processes, of the Golden-Aged, Water-Soluble Compound, Tris(hydroxymethyl)phosphine}, booktitle = {Catalysis of Organic Reactions}, series = {Chemical Industries}, volume = {123}, year = {2009}, note = {ISI Document Delivery No.: BLT07Times Cited: 0Cited Reference Count: 85James, Brian R.Proceedings Paper22nd Conference on Catalysis of Organic ReactionsMAR 30-APR 03, 2008Richmond, VAOrgan React Catalysis Soc, Avantium, BASF Catalysis LLC, Eli Lilly, Evonik Degussa Corp, WR Grace, Davison Catalysts, Parr Instrument, Air Prod, Amgen, Eastman, Umicore, Bristol Myers Squibb, DuPont, Headwaters, HEI, Lummus Technol, OMG, Seton Hall Univ, Sud Chem6000 BROKEN SOUND PARKWAY NW, STE 300, BOCA RATON, FL 33487-2742 USA}, pages = {1-14}, publisher = {Crc Press-Taylor \& Francis Group}, organization = {Crc Press-Taylor \& Francis Group}, address = {Boca Raton}, abstract = {Collaborative studies with the Pulp and Paper Institute of Canada (Paprican) have led serendipitously to development of a pulp bleaching process using tris(hydroxymethyl)phosphine, P(CH2OH)(3) (abbreviated THP), and this on-going work is reviewed. Work on hydrogenation of aromatic residues in lignin, using transition metal catalysts under homogeneous, aqueous-phase conditions, led to the discovery that commercially available THP, in the absence of any metal, bleached selected pulps. Use of THP or a related diphosphine 2 is competitive with the currently used bleaching agents, hydrosulfite (S2O42-) and alkaline peroxide. (Hydroxymethyl)phosphines react as strong nucleophiles and/or reductants toward unsaturated chromophore moieties of lignin, decreasing the degree of conjugation, and hence leading to bleaching. The resulting phosphorus-containing moieties in the lignin also give a more permanent brightening of the pulp. The organo-phosphorus chemistry realized is relevant to other processes catalyzed homogeneously by transition metal-phosphine systems. In situ metal-THP species can catalyze hydrogenation of C=C and/or C=O bonds in lignin chromophores, and investigations on such systems have unearthed new THP-promoted transition metal chemistry.}, keywords = {BIPHASIC CONDITIONS, BRIGHTNESS STABILIZING AGENTS, CATALYTIC-HYDROGENATION, CLUSTER CATALYSIS, HOMOGENEOUS CATALYST, LIGNIN MODEL COMPOUNDS, mechanical, PHOSPHORUS-COMPOUNDS, pulps, ruthenium complexes, TERTIARY PHOSPHINES}, isbn = {978-1-4200-7076-7}, url = {://000270967300001}, author = {James, Brian R.}, editor = {Prunier, M. L.} }