Preparation of Methylcellulose from Annual Plants

Identifier:  TDX:318

Handle: https://hdl.handle.net/20.500.11797/TDX318

Authors:  Ye, Daiyong

Abstract:
Preparation and characterization of methylcelluloses from some annual plants<br/>were investigated.<br/><br/>Miscanthus, cardoon, and eucalyptus pulps were produced by Impregnation Rapid Steam Pulping (IRSP) process and bleached by Total Chloride Free (TCF) sequences using hydrogen peroxide and sodium hydroxide. With an increase of pulping severities, accessibilities and reactivities of bleached pulps increased while viscosities and kappa numbers decreased. A novel facile methylation was developed in order to prepare methylcelluloses from wood and annual plants. Each methylcellulose of TCF bleached pulps was synthesized in isopropanol slurry with iodomethane at 600C for 22 hours after the TCF bleached pulp was mercerized in 40% NaOH solution for 1 hour. The mercerization and methylation were repeated in order to obtain a higher degree of substitution (DS). Fourier Transform Infrared (FTIR) spectra showed OH groups of cellulose were partially substituted by methoxyl groups. Supramolecular substitution patterns of methylcelluloses were determined by 13C nuclear magnetic resonance (NMR) spectroscopy. Intrinsic viscosities of methylcelluloses were measured in distilled water, 4% NaOH solution, or dimethyl sulphoxide (DMSO). Rheological properties of methylcelluloses were measured in DMSO, 4% NaOH solution or distilled water, in which the synthesized methylcelluloses had similar properties as commercial methylcelluloses. Watersoluble and alkali-soluble contents of methylcelluloses were determined by solvent<br/>extraction.<br/><br/>We used iodomethane to synthesize methylcelluloses from Elemental Chloride Free (ECF) bleached abaca, hemp, flax, jute, and sisal pulps via heterogeneous and homogeneous methylations. The heterogeneous methylation was carried out in isopropanol with iodomethane at 600C for 22h after a ECF bleached pulp was mercerized in excessive 50% NaOH solution for one hour at ambient temperature. The homogeneous methylation was carried out in dimethyl sulfoxide with iodomethane at 300C for 48h using a methylcellulose of low degree of substitution. Fourier Transform Infrared (FTIR) spectra of the synthesized methylcelluloses showed the existence of methoxyl groups on methylcellulose molecules. The degrees of substitution of the synthesized methylcelluloses were measured by 13C Nuclear Magnetic Resonance (NMR) spectroscopy. The molecular weights of the waterVI soluble methylcelluloses were determined by Size Exclusion Chromatography (SEC). Intrinsic viscosities of the synthesized methylcelluloses were measured in 4% NaOH solution. Methylcelluloses with better properties, such as greater degrees of substitution, molecular weights, viscosities, and intrinsic viscosities, were prepared from the pulps with higher accessibilities and reactivities. The factors influencing the preparation of methylcelluloses from these pulps were discussed.<br/><br/>Pretreatments (water-soaking, pre-mercerization, mercerization under a pressure of 15 bars, and steam explosion) were used to improve the accessibilities and reactivities of celluloses of bleached flax, hemp, sisal, abaca, and jute pulps for the synthesis of methylcellulose. Glucose and xylose contents of these pulps were determined by High Performance Liquid Chromatograph (HPLC) after hydrolysis. Degrees of crystallinity of these pulps were determined by X-ray Diffraction (XRD) spectra. Figures of Scanning Electron Microscope (SEM) showed that their fibrils had different morphological structures. The iodine adsorption accessibilities of these pulps were low and accessible fractions ranged from 1.3% to 5.2%. Accessible fractions in amorphous cellulose were calculated in the 5% to 18% range. The accessibilities of these pulps were hemp pulp > flax pulp > sisal pulp > jute pulp > abaca pulp. Fourier Transform Infrared (FTIR) spectra showed that mean hydrogen bond strengths were weakened and relative crystallinity indexes were decreased by pretreatments. The accessibility and reactivity of the abaca pulp were improved by water soaking, mercerization under 15 bars pressure, steam explosion and preliminary mercerization, of which steam explosion and pre-mercerization were the<br/>best treatments. Species was the main factor for the accessibility and reactivity.<br/><br/>We studied the factors that influenced the molecular weights (Mw) of watersoluble<br/>methylcelluloses prepared from annual plants and juvenile eucalyptus. Miscanthus and cardoon stalks, and bleached pulps of abaca, jute, sisal, hemp, and flax were used as the annual plant materials. A higher concentration of NaOH solution during the impregnation led to a spring cardoon methylcellulose having a lower molecular weight. As the impregnation times increased, so did the molecular weights of the water-soluble methylcelluloses of spring cardoon. The impregnation conditions had less influence on the methylcelluloses of summer cardoon than on the methylcelluloses of spring cardoon. As the cooking times increased, so did the molecular weights of miscanthus methylcelluloses. A lower pulping severity increased the molecular weight of eucalyptus methylcellulose. The preliminary treatments (water soaking, pre-mercerization, mercerization under pressure and<br/>steam explosion) improved the molecular weights of water-soluble abaca methylcelluloses. The steam explosion method was the best of the preliminary treatments for the abaca pulp. Different species led to different molecular weights for methylcelluloses synthesized from ECF bleached pulps, and these were further improved by preliminary mercerization. The molecular weight of &#61537;-cellulose methylcellulose changed as the ratio of the methylation reagent was varied. In order to synthesize an optimum Mw of methylcellulose, the different raw materials can be chosen, the pulping parameters adjusted (including impregnation and cooking), the cellulose pretreated, and the methylcellulose conditions changed. The plant species is the decisive factor for the Mw of methylcellulose.<br/><br/>The pulping parameters, the methylation conditions, the species, the pretreatments, and the morphological structures of pulps influenced the degrees of substitution of the methylcelluloses prepared from the annual plants. A higher impregnation severity, a higher pulping temperature, and a longer pulping time caused a higher degree of substitution. An increase of methylation reagents led to an increase of degree of substitution. Methylcelluloses of different degrees of substitution were synthesized from the pulps of different species when a same methylation condition was used. The pretreatments increased the degrees of substitution of methylcelluloses.<br/><br/>This investigation contributes to find appropriate conditions for the production of methylcellulose from annual plants. The present investigation demonstrates these annual plants have the capacities to produce upgraded and high quality methylcelluloses for varied applications, such as additives of foods, construction, pharmaceutics, polymerization, paints, and detergents etc. The industry can utilize these annual fast-growth plants to produce methylcelluloses. Therefore, a lot of wood will be saved.<br/><br/>Keywords: abaca, accessibility, annual plants, cardoon, degree of substitution, eucalyptus, flax, hemp, IRSP pulping, jute, methylation, methylcellulose, miscanthus, molecular weight, sisal, steam explosion, TCF bleaching.