Thomas Q. Hu

Chemical modification, properties, and usage of lignin

1. Starch-Lignin Films S. Baumberger. 2. Lignosulfonic Acid-Doped Polyaniline (Ligno-PaniTM) -- A Versatile Conducting Polymer B.C. Berry, T. Viswanathan. 3. Polyurethanes Containing Lignin Hyoe Hatakeyama. 4. Lignins as Macromonomers for Polyesters and Polyurethanes A. Gandini, et al. 5. Lignin and its Polyblends -- A Review D. Feldman. 6. Arboform TM -- A Thermoplastic, Processable Material From Lignin and Natural Fibers H. Nagele, et al. 7. Lignin-Based Carbon Fibers J.F. Kadla, et al. 8. The Use of Lignosulfonates as Water Reducing Agents in the Manunfature of Gypsum Wallboard R.A. Northey. 9. Modified Kraft Lignin and its Use for Soil Preservation Kyoko Katsumata, Gyosuke Meshitsuka. 10. Nitrogenous Fertilizers from Lignins -- A Review K. Fischer, R. Schiene. 11. Pulping Catalysts from Lignin -- The Diels -- Alder Step D.R. Dimmel, et al. 12. Acetylation of Lignin and Photostabilization of Lignin-Rich Mechanical Wood Pulp and Paper M. Paulsson, R. Simonson. 13. Catalytic Modification and Photostabilization of Lignin Functional Groups T.Q. Hu, B.R. James. 14. Characteristics, Industrial Sources, and Utilization of Lignins from Non-Wood Plants J.H. Lora. Index.

Characterization of Secondary and Primary (Hydroxymethyl)Phosphines and Their Oxidation Products: Synergism in Pulp-Bleaching

Abstract With the aim of learning about the synergistic effect of a combination of (HOCH2)3P and Na2S2O4 for the bleaching of mechanical pulps, reactions of (HOCH2)3P (and its associated precursor, (HOCH2)4P+Cl−) with Na2S2O4 were studied in aqueous media under Ar and in air. The secondary phosphine (HOCH2)2PH is the major product in a 1:1 reaction of (HOCH2)3P and Na2S2O4 under Ar, the formaldehyde being removed in the form of HOCH2SO3Na and HOCH2SO2Na; the latter is Rongalite, itself an industrial bleaching agent. Significant amounts of the primary phosphine HOCH2PH2 are also seen. When the reaction is performed in air, the oxide (HOCH2)2P(O)H is the main product. Reaction of (HOCH2)4P+Cl− with Na2S2O4 (even under Ar) leads to solely the oxidation products: (HOCH2)3PO, (HOCH2)3PS, and (HOCH2)2P(O)OH. 31P{1H} and 1H NMR spectral data for secondary and primary (hydroxymethyl)phosphines and their oxidation products are reported for the first time. The toxicity of the primary and secondary phosphines is likely to curtail their use in commercial bleaching processes. Supplemental materials are available for this article. Go to the publishers online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. GRAPHICAL ABSTRACT

A new approach towards the yellowing inhibition of mechanical pulps. Part I : Selective removal of α-hydroxyl and α-carbonyl groups in lignin model compounds

Summary The α-hydroxyl group in lignin model compounds 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-propanediol (1) and 1-(4-hydroxy-3-methoxyphenyl)ethanol (3), and the α-carbonyl group in 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)ethan-1-one (5) are removed by treatment of the model compounds with trifluoroacetic acid (CF3CO OH) and triethylsilane (Et3sih) in methylene chloride. The reaction is highly chemoselective and it tolerates the lignin γ-hydroxyl group, phenol and β-O-4-aryl ether linkage. The α-hydroxyl group in 1 has also been removed with triethylsilane in aqueous trifluoroacetic acid (CF3CO OH : H2o = 75 : 25). The combination of trifluoroacetic acid and sodium borohydride, or sodium triacetoxyborohydride, is also effective in removing the α-carbonyl group in 5 and the α-hydroxyl group in lignin model compound 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)ethanol (7) and in milled wood lignin. The selective removal of the lignin α-hydroxyl and α-carbonyl groups may potentially be used, in conjunction with the protection of the lignin phenol, to inhibit the light and/or heat-induced yellowing of mechanical pulps.

Modification of xylan in alkaline treated bleached hardwood kraft pulps as classified by attenuated total-internal-reflection (ATR) FTIR spectroscopy

The glucuronoxylan composition of a pulp affects the bonding between cellulosic fibres, and thus correlates with such network properties as tensile strength. Here, we demonstrate the promise of attenuated total-internal-reflection (ATR) FTIR spectroscopy as a rapid means for classifying the xylan contained in commercial bleached kraft pulps. This study draws upon samples composed of bleached eucalyptus kraft pulps and combinations of eucalyptus with other commercial bleached kraft pulps. We subject these pulp samples to systematic extraction by sodium hydroxide solutions with concentrations ranging from 0.5% to 6% to build a standard sample library with varying xylan content, quantified by acid hydrolysis, HPLC carbohydrate separation and titration. This pulp chemistry of mild alkaline extraction removes up to two-thirds of the xylan. In the NaOH concentration regime of 0.5-4%, the infrared spectral variance reflects the decrease in hemicellulose concentration as well as the cellulose crystallinity. A residual xylan component remains resistant to base solutions of higher concentrations. Principal component analysis of infrared spectra distinguishes this residual xylan as structurally variant. Both partial least squares multivariate analysis and univariate analysis confined to a feature at 964 cm(-1) in normalized second derivative IR spectra show a very good correlation with xylan content quantified by HPLC.

Removal of Phenolic Hydroxyl Groups in Lignin Model Compounds and Its Effect on Photostability

Summary The phenolic hydroxyl groups in the lignin model compounds, 2-methoxy-4-propylphenol and 4-hydroxy-3-methoxyacetophenone, were removed by first converting the hydroxyl groups to the trifluoromethanesulfonates (triflates) and then cleaving the triflate substituents via catalytic hydrogen transfer. The products, 1-methoxy-3-propylbenzene and 3-methoxyacetophenone, were characterized by 1H and 13C NMR, mass spectrometry and elemental analyses. The effect of the removal of the phenolic groups on the photostability of the model compounds was evaluated by impregnating the compounds into Whatman filter paper sheets, and subjecting them to an accelerated yellowing experiment in a UV chamber. The removal of the phenolic groups resulted in a significant yellowing inhibition, with a higher photostabilizing effect than methylation or acetylation of the hydroxyl, particularly for the model compound without an α-carbonyl group.

The fate of phosphorus in the bleaching of spruce TMP with the new bleaching agent – THPS

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°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 31P{1H} NMR studies of a crude milled wood lignin (crude MWL) and a partially purified MWL isolated from a THPS-bleached pulp.

Multivariate Analysis of Hemicelluloses in Bleached Kraft Pulp Using Infrared Spectroscopy.

The hemicellulose composition of a pulp significantly affects its chemical and physical properties and thus represents an important process control variable. However, complicated steps of sample preparation make standard methods for the carbohydrate analysis of pulp samples, such as high performance liquid chromatography (HPLC), expensive and time-consuming. In contrast, pulp analysis by attenuated total internal reflection Fourier transform infrared spectroscopy (ATR FT-IR) requires little sample preparation. Here we show that ATR FT-IR with discrete wavelet transform (DWT) and standard normal variate (SNV) spectral preprocessing offers a convenient means for the qualitative and quantitative analysis of hemicelluloses in bleached kraft pulp and alkaline treated kraft pulp. The pulp samples investigated include bleached softwood kraft pulps, bleached hardwood kraft pulps, and their mixtures, as obtained from Canadian industry mills or blended in a lab, and bleached kraft pulp samples treated with 0–6% NaOH solutions. In the principal component analysis (PCA) of these spectra, we find the potential both to differentiate all pulps on the basis of hemicellulose compositions and to distinguish bleached hardwood pulps by species. Partial least squares (PLS) multivariate analysis gives a 0.442 wt% root mean square errors of prediction (RMSEP) for the prediction of xylan content and 0.233 wt% RMSEP for the prediction of mannan content. These data all support the idea that ATR FT-IR has a great potential to rapidly and accurately predict the content of xylan and mannan for bleached kraft pulps (softwood, hardwood, and their mixtures) in industry. However, the prediction of xylan and mannan concentrations presented a difficulty for pulp samples with modified cellulose crystalline structure.