Aiping Zhang

Homogeneous Modification of Cellulose in Ionic Liquid with Succinic Anhydride Using N-Bromosuccinimide as a Catalyst

The homogeneous chemical modification of cellulose with succinic anhydride was investigated in a solvent system containing 1-butyl-3-methylimidazolium chloride ionic liquid and dimethylsulfoxide using N-bromosuccinimide (NBS) as a catalyst. The results showed that the degree of substitution of the succinylated cellulosic samples, in the range of 0.24-2.31, noticeably increased as compared with the products without any catalysts, indicating that NBS was a novel efficient catalyst for cellulose succinoylation in ionic liquids. Fourier transform infrared and solid-state cross-polarization/magic angle spinning (13)C NMR spectroscopies also provided evidence of succinoylation reaction. The results indicated that the reaction of hydroxyl groups at C-6, C-2, and C-3 positions in cellulose occurred. The thermal stability of the succinylated cellulose was found to decrease upon chemical modification.

Isolation of cellulolytic enzyme lignin from wood preswollen/dissolved in dimethyl sulfoxide/N-methylimidazole.

Attempts were made to enhance polysaccharide digestibility by crude cellulases in the isolation of cellulolytic enzyme lignin (CEL) by dissolution of ball-milled wood in a dimethyl sulfoxide (DMSO)/N-methylimidazole solvent system as a pretreatment step. Wood regenerated from the DMSO/N-methylimidazole solution was hydrolyzed with crude cellulases for 48 h, removing 73.7 and 66.9% of the original carbohydrate for basswood and loblolly pine, respectively; only 61.7 and 49.2% were hydrolyzed by the crude cellulases without pretreatment. The yields of CEL isolated from regenerated ball-milled wood samples were therefore higher than those directly from ball-milled wood material, presumably via decreasing crystallinity of cellulose. For basswood, the yields of lignin were 45.8 and 36.5% (based on Klason lignin); for loblolly pine, the yields were 35.3 and 30.5%. The isolated lignins were structurally examined using two-dimensional heteronuclear single-quantum coherence ((1)H-(13)C HSQC) NMR methods, which showed that the main structural characteristics of the lignin fractions obtained using these two methods are similar except for slightly higher amounts of carbohydrates in the solvent dissolution product.

Enhanced enzymatic hydrolysis of sugarcane bagasse with ferric chloride pretreatment and surfactant

A FeCl3 pretreatment methodology was developed to convert raw sugarcane bagasse to highly digestible pretreated solid and selectively extract up to ∼100% of the hemicellulose from lignocellulosic biomass. FeCl3 pretreated solids yielded a quite high fermentable sugar yield compared to the native material. In addition, characterization of raw material and pretreated solid by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric (TG) analysis was carried out to better understand how hemicellulose removal affected subsequent enzymatic hydrolysis. Furthermore, the addition of surfactants during enzymatic hydrolysis achieved higher glucose yields. 82.3% of glucose could be obtained with addition of BSA, combined with that generated during pretreatment process, the total glucose yield reached 42.2g/100g raw material, representing 93.8% of glucose in the raw sugarcane bagasse. The FeCl3 process offered the potential to co-produce xylose-derived and glucose-derived chemicals in the bio-refinery.

Isolation and characterization of lignins from Eucalyptus tereticornis (12ABL).

A three-step sequential extraction-precipitation method was used to isolate lignin from Eucalyptus tereticornis. The ball-milled eucalyptus was extracted with 96% dioxane, 50% dioxane, and 80% dioxane containing 1% NaOH at boiling temperature, consecutively resulting in solubilization of lignin and hemicelluloses. By precipitating such solutions into 70% aqueous ethanol, the hemicelluloses were removed substantially although there were still some carbohydrates left over, especially for lignin fraction extracted by 50% dioxane. Lignins dissolved in the 70% ethanol solutions were recovered via concentration and precipitation into acidified water. About 37% of the original lignin was released following such procedure whereas only 13.5% can be isolated by traditional milled wood lignin (MWL) method. The obtained lignin fractions were analyzed by high performance anion exchange chromatography (HPAEC) following acid hydrolysis for sugar composition of the contaminating carbohydrates and characterized by quantitative (31)P NMR as well as two-dimensional heteronuclear single-quantum coherence ((13)C-(1)H) NMR. The results showed that 96% aqueous dioxane extraction of ball-milled wood under conditions used in this study resulted in lignin preparation with very similar structures and sugar composition as traditional MWL. Therefore extracting ball-milled wood with 96% aqueous dioxane produced lignin in 33.6% yield, which makes it very attractive as an alternative to the traditional MWL method. However further extraction with 50% aqueous dioxane or 80% aqueous dioxane containing 1% NaOH gave just a little more lignins with different carbohydrate compositions from those in MWL. The eucalyptus lignins obtained were syringyl and guaiacyl type units. Lignin fraction obtained from 96% dioxane extraction was found to have more phenolic hydroxyl and less aliphatic hydroxyl than the other two preparations.

Ring-Opening Graft Polymerization of Propylene Carbonate onto Xylan in an Ionic Liquid

The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young’s modulus of the films decreased, while the elongation at break increased.

Homogeneous ring opening graft polymerization of ɛ-caprolactone onto xylan in dual polar aprotic solvents.

Homogeneous ring-opening graft polymerization (ROGP) of ɛ-caprolactone (ɛ-CL) onto xylan was investigated in dual polar aprotic solvents, N,N-dimethylformamide/lithium chloride (DMF/LiCl), N,N-dimethylacetamide/LiCl (DMAc/LiCl), and 1-methyl-2-pyrrolidinone/LiCl (NMP/LiCl). The effects of reaction solvents, temperature, and the molar ratio of ɛ-CL to anhydroxylose units (AXU) on the degree of substitution (DS) of xylan-graft-poly(ɛ-caprolactone) (xylan-g-PCL) copolymers and the degree of polymerization (DP) of the attached PCL side chains were investigated. FT-IR and NMR analyses provided the evidence of the occurrence of ROGP reaction. The thermal stability of xylan increased upon ROGP reaction due to the increased length of PCL side chains. With the increased attachment of PCL side chains, the tensile strength and Youngs modulus of the films decreased, whereas the elongation at break increased. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) observations provided the evidences of the increased film properties due to the attachment of PCL side chains.

Homogeneous acylation of eucalyptus wood at room temperature in dimethyl sulfoxide/N-methylimidazole.

Succinoylation and benzoylation of ball-milled eucalyptus wood using succinic anhydride and benzoyl chloride as acylating reagent, respectively, were investigated at room temperature using dimethyl sulfoxide/N-methylimidazole (DMSO/NMI) as reaction medium without additional catalysts. The effects of the corresponding acylating reagent dosage (1-5:1 for succinoylation and 0.5-5:1 for benzoylation) and reaction time (0.35-5h for succinoylation and 0.5-3h for benzoylation) on the extent of acylation, measured by weight percent gain (WPG), were studied. WPG of succinoylation and benzoylation was in the range of 70.8-144.7% and 17.3-43.1%, respectively. The efficiency of acylation at room temperature significantly increased in DMSO/NMI compared with ionic liquid 1-butyl-3-methylimidazolium chloride because of the role of NMI as solvent, base and catalyst. Fourier transform infrared (FT-IR), and solid-state cross-polarization/magic-angle spinning (CP/MAS) (13)C nuclear magnetic resonance (NMR) spectroscopy studies provided evidence for the occurrence of succinoylation and benzoylation reactions and the attachment of functional groups via ester bonds.

Chemical Modification of Cellulose with Succinic Anhydride in Ionic Liquid with or without Catalysts

CF Liu1, AP Zhang2,3, WY Li1 and RC Sun1,4 1State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, 2Institute of New Energy and New Material, South China Agricultural University, 3Biomass Energy Key Laboratory of Guangdong Regular Higher Education Institutions, South China Agricultural University, 4Institute of Biomass Chemistry and Technology, Beijing Forestry University, China

Synthesis of Thermoplastic Xylan-Lactide Copolymer with Amidine-Mediated Organocatalyst in Ionic Liquid

Ring-opening graft polymerization (ROGP) of l-Lactide (l-LA) is a practical method of altering the physical and chemical properties of lignocellulose. Previous studies have mainly investigated cellulose and tin-based catalysts, particularly of tin(II) 2-ethylhexanoate (Sn(oct)2), at high temperatures and reported low graft efficiencies. In the present study, ROGP of l-LA was successfully achieved on xylan-type hemicelluloses in ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl) using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an effective organic catalyst. Mild reaction condition (50 °C) was used to limit transesterification, and thus enhance the graft efficiency. The hydroxyl groups on xylan acted as initiators in the polymerization, and DBU, enhanced the nucleophilicity of the initiator and the propagating chain. Xylan-graft-poly(l-Lactide) (xylan-g-PLA) copolymer with a degree of substitution (DS) of 0.58 and a degree of polymerization (DP) of 5.51 was obtained. In addition, the structures of the xylan-g-PLA copolymers were characterized by GPC, FT-IR and NMR, confirming the success of the ROGP reaction. Thermal analysis revealed that the copolymers exhibited a single glass-transition temperature (Tg), which decreased with increasing molar substitution (MS). Thus, modification resulted in the graft copolymers with thermoplastic behavior and tunable Tg.

Homogeneous esterification mechanism of bagasse modified with phthalic anhydride in ionic liquid. Part 2: Reactive behavior of hemicelluloses

The phthalation of bagasse was comparatively investigated with the isolated three main components in 1-allyl-3-methylidazium chloride (AmimCl) to reveal the reaction behavior of bagasse. In the present study, the reaction behavior of hemicelluloses during the homogeneous phthalation was extensively explored. The phthalation degree of hemicellulosic samples ranged from 16.37% to 52.14%. The reaction priority on the main and side chains of hemicelluloses were revealed by the changes of monosaccharide contents upon phthalation. The results indicated that side-chains of hemicelluloses were more easily phthalated than main-chains, and the phthalation of secondary hydroxyl groups on uronic acids was more difficult than that on neutral sugars. 13C NMR and HSQC analyses suggested the similar reactivity of the secondary hydroxyls at C-2 and C-3 positions in anhydroxylose units. These results provide more detailed understanding of the homogenous modification of lignocellulose.