Xueqin Zhang

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.

Dual-component system dimethyl sulfoxide/LiCl as a solvent and catalyst for homogeneous ring-opening grafted polymerization of ε-caprolactone onto xylan.

The preparation of xylan-graft-poly(ε-caprolactone) (xylan-g-PCL) copolymers was investigated by homogeneous ring-opening polymerization (ROP) in a dual-component system containing Lewis base LiCl and strong polar aprotic solvent dimethyl sulfoxide (DMSO). DMSO/LiCl acted as solvent, base, and catalyst for the ROP reaction. The effects of the parameters, including the reaction temperature, molar ratio of ε-caprolactone (ε-CL) to anhydroxylose units (AXU) in xylan, and reaction time, on the degree of substitution (DS) and weight percent of PCL side chain (WPCL) were investigated. The results showed that xylan-g-PCL copolymers with low DS in the range of 0.03-0.39 were obtained under the given conditions. The Fourier transform infrared spectroscopy (FTIR), (1)H nuclear magnetic resonance (NMR), (13)C NMR, (1)H-(1)H correlation spectroscopy (COSY), and (1)H-(13)C correlation two-dimensional (2D) NMR [heteronuclear single-quantum coherence (HSQC)] characterization provided more evidence of the attachment of side chains onto xylan. Only one ε-CL was confirmed to be attached onto xylan with each side chain. Integration of resonances assigned to the substituted C2 and C3 in the HSQC spectrum also indicated 69.23 and 30.77% of PCL side chains attached to AXU at C3 and C2 positions, respectively. Although the attachment of PCL onto xylan led to the decreased thermal stability of xylan, the loss of unrecovered xylan fractions with low molecular weight because of the high solubility of xylan in DMSO/LiCl resulted in the increased thermal stability of the samples. This kind of xylan derivative has potential application in environmentally friendly and biodegradable materials considering the good biodegradability of xylan and PCL.

Per-O-acetylation of cellulose in dimethyl sulfoxide with catalyzed transesterification.

Cellulose acetylation was investigated in dimethyl sulfoxide (DMSO) with isopropenyl acetate (IPA) as acetylating reagent and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) as catalyst at 70-130 °C for 3-12 h. The degree of substitution (DS) of acetylated cellulose was comparatively determined by titration and ¹H NMR and confirmed by FT-IR analysis. The results indicated that per-O-acetylation was achieved at >90 °C for a relatively long duration. The three well-resolved peaks of carbonyl carbons in ¹³C NMR spectra also provided evidence of per-O-acetylation. The solubility of cellulose acetates in common organic solvents was examined, and the result showed that chloroform can be an alternative choice as a solvent for fully acetylated cellulose formed in this study besides DMSO. The intrinsic viscosity of acetylated cellulose solution implied almost no degradation of cellulose during acetylation in DMSO except at higher temperature (130 °C) for a long time.

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.

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.

Organic Catalysis for Ring-Opening Graft Polymerization of p-Dioxanone with Xylan in Ionic liquid

Recently, organic catalysis has become a powerful alternative to the use of more traditional metal-based catalysts. In this study, 4-dimethylaminopyridine (DMAP), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) were applied to mediate the ring-opening graft polymerization (ROGP) of p-dioxanone (PDO) with xylan-based hemicelluloses in ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). Excellent control of the molar ratio of the catalyst to anhydroxylose units (AXU) in xylan was found for a good tuning of the weight percent gain (WPG) of xylan-graft-poly(p-dioxanone) (xylan-g-PPDO) copolymers. As a result, the maximum WPG of xylan-g-PPDO copolymers was 431.07% (DMAP/AXU of 2/1), 316.72% (DBU/AXU of 0.2/1), and 323.15% (TBD/AXU of 0.2/1), respectively. The structure of xylan-g-PPDO copolymers was characterized with FT-IR and NMR. The thermal properties of copolymers were investigated using thermogravimetric analysis (TGA/DTG) and differential scanning calorimetry (DSC), and a significant difference was observed regarding the transition temperature (Tg), melting temperature (Tm), and crystallization temperature (Tc).

Acetylation of Microcrystalline Cellulose by Transesterification in AmimCl/DMSO Cosolvent System.

Recently, IL/cosolvent systems have generated a lot of interest as cellulose-dissolving solvents and reaction media for various kinds of cellulose modification. In the present study, both 1-allyl-3-methylimidazolium chloride (AmimCl)/dimethyl sulfoxide (DMSO) and AmimCl/N,N-dimethylformamide (DMF) systems were employed to synthesize cellulose acetate by transesterification. Microcrystalline cellulose, 1,8-diazabicyclo[5.4.0]undec-7-ene and isopropenyl acetate were chosen as the raw material, catalyst and acetylation reagent, respectively. The results revealed that DMSO was a suitable cosolvent for the transesterification in the homogeneous solution. Moreover, DMSO had a positive effect on the reaction as the cosolvent under the given conditions and the degree of the substitution of cellulose acetate could be significantly enhanced through increasing the molar ratio of DMSO. The synthesized products were characterized by Fourier transform infrared (FT-IR) spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR), correlation spectroscopy (COSY), heteronuclear single quantum correlation (HSQC) spectroscopy, and X-ray diffraction (XRD) to confirm the chemical and physical structure of the cellulose acetate generated. The thermal properties were also evaluated using thermogravimetric analysis (TGA)/derivative thermogravimetry (DTG).

Reaction Behavior of Cellulose in the Homogeneous Esterification of Bagasse Modified with Phthalic Anhydride in Ionic Liquid 1-Allyl-3-methylimidazium Chloride

In order to elucidate the reaction behavior of cellulose component in bagasse, the homogeneous phthalation of bagasse was investigated comparatively with the isolated cellulose in 1-allyl-3-methylimidazium chloride (AmimCl) with phthalic anhydride (PA) at the dosage of 10–50 mmol/g. The phthalation degrees of bagasse and the isolated cellulose were in the range of 5.66% to 22.71% and 11.61% to 44.11%, respectively. A phthalation degree increase of cellulose was proportional to phthalic anhydride dosage due to its regular macromolecular structure and followed the equation . FT-IR and 2D HSQC NMR analyses confirmed the attachment of phthaloyl group. The phthalation reactivity of the three hydroxyls in the isolated cellulose followed the order of C-6 > C-2 > C-3, and the more selective phthalation to C-6 position was found in the cellulose component in bagasse. These results provide detailed understanding of the homogenous modification mechanism of lignocellulose.

Reaction Behaviors of Bagasse Modified with Phthalic Anhydride in 1‐Allyl‐3‐Methylimidazolium Chloride with Catalyst 4‐Dimethylaminopyridine

The modification of lignocellulose with cyclic anhydrides could confer stronger hydrophilic properties to lignocellulose, which could be used in many industrial fields. To elucidate the modification mechanism of lignocellulose, bagasse was phthalated comparatively with its three main components in 1-allyl-3-methylimidazolium chloride (AmimCl) using 4-dimethylaminopyridine as catalyst and phthalic anhydride as acylation reagent in the present study. From FT-IR and 2D HSQC analyses, the skeleton of bagasse and the fractions were not significantly changed during phthalation in AmimCl. 2D HSQC results suggested that the reactive hydroxyls in bagasse were partially phthalated, and the reactivity of the hydroxyls in anhydroglucose units followed the order C-6 > C-2 > C-3. Similarly, the reactivity order of hydroxyls in anhydroxylose units was C-2 > C-3. For lignin, the predominant diesterification occurred during the homogeneous modification, and both aliphatic and aromatic hydroxyls were phthalated. The reactivity order of phenolic hydroxyls was S-OH > G-OH > H-OH, which was distinct from that without catalyst. In addition, it was found that the thermal stability of phthalated bagasse was affected by the disruption of cellulose crystallinity and the degradation of components. The thermal stability of the phthalated bagasse decreased upon chemical modification and regeneration.

Esterification Mechanism of Bagasse Modified with Glutaric Anhydride in 1-Allyl-3-methylimidazolium Chloride

The esterification of bagasse with glutaric anhydride could increase surface adhesion compatibility and the surface of derived polymers has the potential of immobilizing peptides or proteins for biomedical application. Due to its complicated components, the esterification mechanism of bagasse esterified with glutaric anhydride in ionic liquids has not been studied. In this paper, the homogenous esterification of bagasse with glutaric anhydride was comparatively investigated with the isolated cellulose, hemicelluloses, and lignin in 1-allyl-3-methylimidazolium chloride (AmimCl) to reveal the reaction mechanism. Fourier transform infrared (FT-IR) indicated that the three components (cellulose, hemicelluloses, and lignin) were all involved in the esterification. The percentage of substitution (PS) of bagasse was gradually improved with the increased dosage of glutaric anhydride (10–40 mmol/g), which was primarily attributed to the increased esterification of cellulose and hemicelluloses. However, the PS fluctuation of lignin led to a decrease in the PS of bagasse at high glutaric anhydride dosage (50 mmol/g). The esterification reactivity of bagasse components followed the order of lignin > hemicelluloses > cellulose. The esterification mechanism was proposed as a nucleophilic substitution reaction. Nuclear magnetic resonance (NMR) analysis indicated that lignin aliphatic hydroxyls were prior to be esterified, and primary hydroxyls were more reactive than secondary hydroxyls in cellulose and hemicelluloses.