@article {2446,
	title = {Mill Trial of the New Bleaching Agent -THPS},
	journal = {Pulp \& Paper-Canada},
	volume = {110},
	number = {7},
	year = {2009},
	note = {ISI Document Delivery No.: 508TWTimes Cited: 0Cited Reference Count: 31Hu, T. Q. Williams, T. Schmidt, J. A. James, B. R. Cavasin, R. Lewing, D.},
	month = {Sep},
	pages = {37-42},
	type = {Article},
	abstract = {An eight-day mill. trial of adding tetrakis(hydroxymethyl)phosphonium sulfate (THPS) (at 1.0 kg THPS/t pulp) to hydrosulfite (Y) bleaching of spruce SGW pulp shows an average, additional brightness gain of 2.0-2.3 ISO points without any bleach plant or paper machine process upsets. This additional brightness gain, sustained during subsequent one-year commercial implementation of the "THPS + Y" bleaching technology, allows the mill to reach brightness target during the difficult summer period, and to reduce the consumption of expensive brightness-enhancing additives for LWC papers. Overall estimated cost saving to the mill is $250,000/year.},
	keywords = {bleach, bleaching, brightness, BRIGHTNESS STABILIZING AGENTS, CHEMISTRY, COMPOUNDS, COSTS, mechanical pulps, PHOSPHONIUM, SODIUM HYDROSULFITE, SULFATE, TERTIARY PHOSPHINES, TETRAKIS(HYDROXYMETHYL)PHOSPHONIUM},
	isbn = {0316-4004},
	url = {<Go to ISI>://000270960500008},
	author = {Hu, Thomas Q. and Williams, T. and Schmidt, J. A. and James, Brian R. and Cavasin, R. and Lewing, D.}
}
@article {2446,
	title = {Mill Trial of the New Bleaching Agent -THPS},
	journal = {Pulp \& Paper-Canada},
	volume = {110},
	number = {7},
	year = {2009},
	note = {ISI Document Delivery No.: 508TWTimes Cited: 0Cited Reference Count: 31Hu, T. Q. Williams, T. Schmidt, J. A. James, B. R. Cavasin, R. Lewing, D.},
	month = {Sep},
	pages = {37-42},
	type = {Article},
	abstract = {An eight-day mill. trial of adding tetrakis(hydroxymethyl)phosphonium sulfate (THPS) (at 1.0 kg THPS/t pulp) to hydrosulfite (Y) bleaching of spruce SGW pulp shows an average, additional brightness gain of 2.0-2.3 ISO points without any bleach plant or paper machine process upsets. This additional brightness gain, sustained during subsequent one-year commercial implementation of the "THPS + Y" bleaching technology, allows the mill to reach brightness target during the difficult summer period, and to reduce the consumption of expensive brightness-enhancing additives for LWC papers. Overall estimated cost saving to the mill is $250,000/year.},
	keywords = {bleach, bleaching, brightness, BRIGHTNESS STABILIZING AGENTS, CHEMISTRY, COMPOUNDS, COSTS, mechanical pulps, PHOSPHONIUM, SODIUM HYDROSULFITE, SULFATE, TERTIARY PHOSPHINES, TETRAKIS(HYDROXYMETHYL)PHOSPHONIUM},
	isbn = {0316-4004},
	url = {<Go to ISI>://000270960500008},
	author = {Hu, Thomas Q. and Williams, T. and Schmidt, J. A. and James, Brian R. and Cavasin, R. and Lewing, D.}
}
@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 = {<Go to ISI>://000270967300001},
	author = {James, Brian R.},
	editor = {Prunier, M. L.}
}
@article {2106,
	title = {The fate of phosphorus in the bleaching of spruce TMP with the new bleaching agent - THPS},
	journal = {Holzforschung},
	volume = {62},
	number = {4},
	year = {2008},
	note = {ISI Document Delivery No.: 320ZETimes Cited: 1Cited Reference Count: 30Hu, Thomas Q. Yu, Eric James, Brian R. Marcazzan, Paolo},
	pages = {389-396},
	type = {Article},
	abstract = {Tetrakis(hydroxymethyl)phosphonium sulfate (THPS) is a newly discovered, phosphorus-based bleaching agent that has been successfully tested in a pulp mill trial. The fate of phosphorus (P) and the chemistry in the course of THPS bleaching of a spruce TMP have been studied. The amount of P introduced into the THPS-bleached pulp depends on THPS dose and the bleaching conditions and it correlates well with the brightness gain. The P introduced into THPS-bleached pulp is covalently bonded to the pulp. The THPS-bleached and tetraethylphosphonium chloride-treated pulps have been additionally treated with calcium chloride before P analysis, and the results of these experiments support the covalent bonding hypothesis. Bleaching with 0.1 and 3.0\% THPS (\% based on oven-dried pulp) at 60 and 110 degrees C leads to pulps with 0.13 and 2.17 mg P g(-1) pulp, respectively, which corresponds to 0.08 and 1.4\% THPS. More precisely, P is covalently bonded to lignin chromophores, such as lignin coniferaldehydes. This was found by P-content analysis, UV-visible spectroscopy, and P-31 {H-1} NMR studies of a crude milled wood lignin (crude MWL) and a partially purified MWL isolated from a THPS-bleached pulp.},
	keywords = {bleaching, brightness, BRIGHTNESS STABILIZING AGENTS, CHEMISTRY, CHROMOPHORES, conk, feraldehyde, lignins, mechanical pulps, phosphonium compounds : phosphorus, tetrakis(hydroxymethyl) phosphonium sulfate, thermomechanical pulps},
	isbn = {0018-3830},
	url = {<Go to ISI>://000257273000003},
	author = {Hu, Thomas Q. and Yu, E. and James, Brian R. and Marcazzan, P.}
}
@article {2106,
	title = {The fate of phosphorus in the bleaching of spruce TMP with the new bleaching agent - THPS},
	journal = {Holzforschung},
	volume = {62},
	number = {4},
	year = {2008},
	note = {ISI Document Delivery No.: 320ZETimes Cited: 1Cited Reference Count: 30Hu, Thomas Q. Yu, Eric James, Brian R. Marcazzan, Paolo},
	pages = {389-396},
	type = {Article},
	abstract = {Tetrakis(hydroxymethyl)phosphonium sulfate (THPS) is a newly discovered, phosphorus-based bleaching agent that has been successfully tested in a pulp mill trial. The fate of phosphorus (P) and the chemistry in the course of THPS bleaching of a spruce TMP have been studied. The amount of P introduced into the THPS-bleached pulp depends on THPS dose and the bleaching conditions and it correlates well with the brightness gain. The P introduced into THPS-bleached pulp is covalently bonded to the pulp. The THPS-bleached and tetraethylphosphonium chloride-treated pulps have been additionally treated with calcium chloride before P analysis, and the results of these experiments support the covalent bonding hypothesis. Bleaching with 0.1 and 3.0\% THPS (\% based on oven-dried pulp) at 60 and 110 degrees C leads to pulps with 0.13 and 2.17 mg P g(-1) pulp, respectively, which corresponds to 0.08 and 1.4\% THPS. More precisely, P is covalently bonded to lignin chromophores, such as lignin coniferaldehydes. This was found by P-content analysis, UV-visible spectroscopy, and P-31 {H-1} NMR studies of a crude milled wood lignin (crude MWL) and a partially purified MWL isolated from a THPS-bleached pulp.},
	keywords = {bleaching, brightness, BRIGHTNESS STABILIZING AGENTS, CHEMISTRY, CHROMOPHORES, conk, feraldehyde, lignins, mechanical pulps, phosphonium compounds : phosphorus, tetrakis(hydroxymethyl) phosphonium sulfate, thermomechanical pulps},
	isbn = {0018-3830},
	url = {<Go to ISI>://000257273000003},
	author = {Hu, Thomas Q. and Yu, E. and James, Brian R. and Marcazzan, P.}
}
@article {1500,
	title = {alpha-monodeuterated benzyl alcohols and phosphobetaines from reactions of aromatic aldehydes with a water/D2O-soluble phosphine},
	journal = {Inorganic Chemistry},
	volume = {45},
	number = {25},
	year = {2006},
	note = {ISI Document Delivery No.: 111UETimes Cited: 11Cited Reference Count: 49Moiseev, Dmitry V. James, Brian R. Hu, Thomas Q.},
	month = {Dec},
	pages = {10338-10346},
	type = {Article},
	abstract = {With the aim of learning more about the bleaching action of pulps by (hydroxymethyl) phosphines, we reacted several benzaldehydes, containing MeO, Me, OH, or halogen substituents, with tris(3-hydroxypropyl) phosphine, [HO(CH2)(3)](3)P, in aqueous solution at 90 degrees C under argon. Effective reduction of the aldehydes to the corresponding benzyl alcohols with concomitant oxidation of the phosphine to the phosphine oxide takes place, the reaction proceeding via an initially formed phosphonium species. When the reactions are carried out in D2O, the benzyl alcohol product from 3,4-dimethoxybenzaldehyde contains one deuterium atom at the benzyl-carbon atom, consistent with the last step of the mechanism involving a carbanion intermediate. With syringaldehyde (3,5-dimethoxy-4-hydroxy-benzaldehyde), the reduction product (syringyl alcohol) is more reactive toward the phosphine than is the starting aldehyde, and a zwitterionic, phosphobetaine product is formed. In D2O, the zwitterion benzyl protons and protons of the hydroxypropyl-CH2 adjacent to the P atom undergo H/D exchange via presumed phosphorus ylide intermediates. Under the same aqueous reaction conditions, tris(3-hydroxypropyl) phosphine, [HO(CH2)(3)](3)P (THPP), does not undergo redox reactions with aliphatic aldehydes but simply promotes a base-catalyzed self-condensation (aldol) reaction. THPP reduction of an aromatic ketone is sluggish, presumably because the carbonyl C-atom is less electrophilic than that present in an aromatic aldehyde.},
	keywords = {ALIPHATIC ALDEHYDES, BRIGHTNESS STABILIZING AGENTS, CONDENSATION REACTIONS, CRYSTAL-STRUCTURE, HYDROGENATION, LIGNIN MODEL COMPOUNDS, mechanical pulps, METHIDE, NUCLEOPHILIC-ADDITION, P-QUINONE, PHOSPHONIUM SALTS},
	isbn = {0020-1669},
	url = {<Go to ISI>://000242479700055},
	author = {Moiseev, D. V. and James, Brian R. and Hu, Thomas Q.}
}
@article {1500,
	title = {alpha-monodeuterated benzyl alcohols and phosphobetaines from reactions of aromatic aldehydes with a water / D2O-soluble phosphine},
	journal = {Inorganic Chemistry},
	volume = {45},
	number = {25},
	year = {2006},
	note = {ISI Document Delivery No.: 111UETimes Cited: 11Cited Reference Count: 49Moiseev, Dmitry V. James, Brian R. Hu, Thomas Q.},
	month = {Dec},
	pages = {10338-10346},
	type = {Article},
	abstract = {<p>With the aim of learning more about the bleaching action of pulps by (hydroxymethyl) phosphines, we reacted several benzaldehydes, containing MeO, Me, OH, or halogen substituents, with tris(3-hydroxypropyl) phosphine, [HO(CH2)(3)](3)P, in aqueous solution at 90 degrees C under argon. Effective reduction of the aldehydes to the corresponding benzyl alcohols with concomitant oxidation of the phosphine to the phosphine oxide takes place, the reaction proceeding via an initially formed phosphonium species. When the reactions are carried out in D2O, the benzyl alcohol product from 3,4-dimethoxybenzaldehyde contains one deuterium atom at the benzyl-carbon atom, consistent with the last step of the mechanism involving a carbanion intermediate. With syringaldehyde (3,5-dimethoxy-4-hydroxy-benzaldehyde), the reduction product (syringyl alcohol) is more reactive toward the phosphine than is the starting aldehyde, and a zwitterionic, phosphobetaine product is formed. In D2O, the zwitterion benzyl protons and protons of the hydroxypropyl-CH2 adjacent to the P atom undergo H/D exchange via presumed phosphorus ylide intermediates. Under the same aqueous reaction conditions, tris(3-hydroxypropyl) phosphine, [HO(CH2)(3)](3)P (THPP), does not undergo redox reactions with aliphatic aldehydes but simply promotes a base-catalyzed self-condensation (aldol) reaction. THPP reduction of an aromatic ketone is sluggish, presumably because the carbonyl C-atom is less electrophilic than that present in an aromatic aldehyde.</p>},
	keywords = {ALIPHATIC ALDEHYDES, BRIGHTNESS STABILIZING AGENTS, CONDENSATION REACTIONS, CRYSTAL-STRUCTURE, HYDROGENATION, LIGNIN MODEL COMPOUNDS, mechanical pulps, METHIDE, NUCLEOPHILIC-ADDITION, P-QUINONE, PHOSPHONIUM SALTS},
	isbn = {0020-1669},
	url = {<Go to ISI>://000242479700055},
	author = {Moiseev, D. V. and James, Brian R. and Hu, Thomas Q.}
}
@article {1499,
	title = {New oligophosphines and (hydroxymethyl)phosphonium chlorides},
	journal = {Inorganic Chemistry},
	volume = {45},
	number = {7},
	year = {2006},
	note = {ISI Document Delivery No.: 028HCTimes Cited: 6Cited Reference Count: 46},
	month = {Apr},
	pages = {2917-2924},
	type = {Article},
	abstract = {{The new oligophosphines [H2P(CH2)(2)](2)PH, [H2P(CH2)(2)P(H)CH2](2), and {[(H2P(CH2)(2)](2)PCH2}(2) have been made by hydrophosphination of diethyl vinylphosphonate (2) with H2P(CH2)(2)PH2 (1), using different ratios of 2/1, followed by LiAlH4 reduction of the phosphonate intermediates; the three phosphonate precursors were obtained as oils of varying purity (similar to 90-95\%) in low (similar to 20\%) to almost quantitative yield. The tri-, tetra-, and hexaphosphines were then treated with formaldehyde in the presence of hydrochloric acid to generate the corresponding water-soluble (hydroxymethyl)phosphonium chlorides {(HOCH2)(3)P[(CH2)(2)P(CH2OH)(2)](n)(CH2)(2)P(CH2PH)(3)}Cl-m (n = 1},
	keywords = {ALDEHYDES, BRIGHTNESS STABILIZING AGENTS, COMPLEXES, CRYSTAL-STRUCTURE, DERIVATIVES, FORMALDEHYDE, LIGANDS, phosphines, SALTS, WATER},
	isbn = {0020-1669},
	url = {<Go to ISI>://000236476700018},
	author = {Moiseev, D. and James, Brian R. and Patrick, B. O. and Hu, Thomas Q.}
}
@article {1499,
	title = {New oligophosphines and (hydroxymethyl)phosphonium chlorides},
	journal = {Inorganic Chemistry},
	volume = {45},
	number = {7},
	year = {2006},
	note = {ISI Document Delivery No.: 028HCTimes Cited: 6Cited Reference Count: 46},
	month = {Apr},
	pages = {2917-2924},
	type = {Article},
	abstract = {{The new oligophosphines [H2P(CH2)(2)](2)PH, [H2P(CH2)(2)P(H)CH2](2), and {[(H2P(CH2)(2)](2)PCH2}(2) have been made by hydrophosphination of diethyl vinylphosphonate (2) with H2P(CH2)(2)PH2 (1), using different ratios of 2/1, followed by LiAlH4 reduction of the phosphonate intermediates; the three phosphonate precursors were obtained as oils of varying purity (similar to 90-95\%) in low (similar to 20\%) to almost quantitative yield. The tri-, tetra-, and hexaphosphines were then treated with formaldehyde in the presence of hydrochloric acid to generate the corresponding water-soluble (hydroxymethyl)phosphonium chlorides {(HOCH2)(3)P[(CH2)(2)P(CH2OH)(2)](n)(CH2)(2)P(CH2PH)(3)}Cl-m (n = 1},
	keywords = {ALDEHYDES, BRIGHTNESS STABILIZING AGENTS, COMPLEXES, CRYSTAL-STRUCTURE, DERIVATIVES, FORMALDEHYDE, LIGANDS, phosphines, SALTS, WATER},
	isbn = {0020-1669},
	url = {<Go to ISI>://000236476700018},
	author = {Moiseev, D. and James, Brian R. and Patrick, B. O. and Hu, Thomas Q.}
}
