Ionic Xanthate Method of Grafting. II

In the ionic xanthate method of grafting, the increase of sodium hydroxide concentration and liquor ratio increased the grafting parameters up to a limit. The limit varied from one monomer to another. The positive values of the standard degree of concentration of sodium hydroxide indicate that the graft polymerization reaction has happened. The extent of decrease in the grafting parameters with the increase of the liquor ratio may be due to an increase of termination reactions as a result of the increasing number of HOH molecules, with resulting chain transfer reactions to solvent. Grafting parameters also increased with an increase of the concentration of monomers up to a limit. The reactivity of these monomers is in the order: methyl methacrylate > ethyl acrylate > allyl chloride > acrylonitrile > methyl acrylate > allyl alcohol, being dependent on both the radical stabilization and the strength of the electron acceptance of the monomers. The activation energy of the overall polymerization reaction (i.e., grafting and homopolymer) decreased with the increase of the crude grafting yield, and the reverse relation was achieved with the true grafting yield (i.e., grafting reaction only). This difference may contribute to the difference in the conformation of the polymer chains in graft polymerization on the active sites of the cellulose chains.     

Ionic Xanthate Method of Grafting. II

In the ionic xanthate method of grafting, the increase of sodium hydroxide concentration and liquor ratio increased the grafting parameters up to a limit. The limit varied from one monomer to another. The positive values of the standard degree of concentration of sodium hydroxide indicate that the graft polymerization reaction has happened. The extent of decrease in the grafting parameters with the increase of the liquor ratio may be due to the increase of the termination reactions as a result of increasing the number of HOH molecules and the consequent chain transfer reactions to solvent. Grafting parameters also increased with the increase of the concentration of monomers up to a limit. The reactivity of these monomers is in the order: methyl methacrylate > ethyl acrylate > allyl chloride > acrylonitrile > methyl acrylate > allyl alcohol, being dependent on both the radical stabilization and the strength of the electron acceptance of the monomers. The activation energy of the overall polymerization reaction (i.e., grafting and homopolymer) decreased with the increase of the crude grafting yield, and the reverse relation was achieved with the true grafting yield (i.e., grafting reaction only). This difference may be attributed to the difference in the conformation of the polymer chains to graft polymerize on the active sites of the cellulose chains.     

Structural changes of regenerated cellulose dissolved in FeTNa,NaOH/thiourea,and NMMO systems

Regenerated cellulose was prepared from microcrystalline cellulose (MCC) via dissolution in three well‐known nonderivatizing systems: ferric chloride/sodium tartarate/sodium hydroxide (FeTNa), sodium hydroxide/thiourea (NaOH/thiourea), and N‐methylmorpholine‐N‐oxide (NMMO) systems. The effect of regeneration using the different systems on the supramolecular structure of the regenerated celluloses was studied using X‐ray diffraction and Fourier transform infrared (FTIR). The effect of regeneration on supermolecular structure, morphology, and thermal stability of regenerated celluloses were studied using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The effect of regeneration systems used on the chemical reactivity of cellulose toward carboxymethylation, acetylation, and cyanoethylation reactions was briefly studied. The results showed dependence of all the aforementioned properties on the dissolution reagent used in spite of that all studied reagents cause the same change in cellulose crystalline structure (from cellulose I to cellulose II). The degree of polymerization, crystallinity, and thermal stability of the regenerated cellulose (RC) samples were in the following order: NaOH/thiourea RC > FeTNa RC > NMMO RC. SEM micrograph showed unique surface for the NMMO RC sample. The reactivity of the different regenerated cellulose samples toward carboxymethylation, cyanoethylation, and acetylation depended mainly on the reaction system and conditions used rather than on crystallinity of regenerated cellulose. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

机械活化甘蔗渣与丙烯[BF]酸(钠)的接枝共聚反应

采用搅拌球磨对甘蔗渣进行机械活化,以不同活化时间的甘蔗渣为原料,过硫酸铵和亚硫酸钠为引发剂,在水溶液中与部分中和的丙烯酸进行接枝共聚反应。以接枝率和接枝效率为评价指标,考察了活化时间、丙烯酸与甘蔗渣的用量比、反应时间和反应温度等因素对接枝反应的影响。并采用SEM、FT-IR对甘蔗渣和产物进行表征。结果表明：机械活化明显强化了甘蔗渣与丙烯酸的接枝共聚反应,接枝率和接枝效率随着活化时间的延长而增大,主要是由于机械活化破坏了甘蔗渣中木质素对纤维素的包裹作用,降低纤维素的结晶度,提高了其反应活性。以活化1.5 h的甘蔗渣为原料进行接枝共聚反应,在反应时间为3 h、丙烯酸（体积,ml）与甘蔗渣（质量,g）的用量比为6、反应温度为60℃的条件下,制得接枝率和接枝效率分别为165.29%和82.70%的接枝共聚产物。     

Some aspects of graft polymerization of vinyl monomers onto cellulose by use of tetravalent cerium. VI

The state of cellulose as defined by its crystallinity, grinding, and average degree of polymerization (D.P.) highly influences the grafting yield. Grinding of cellulose with a Wiley mill results in decreased grafting, while grinding with a ball mill or treatment with ethylenediamine, both of which lead to decrystallization of cellulose, nearly inhibits the grafting reaction from taking place. On the other hand, decreased D.P. leads to increased grafting yield. The governing factor being attributed to the specific surface of the cellulose. Increased specific surface, as decreased D.P., brings about an increase in the active sites formed on the cellulose and hence an increase in the grafting yield. However, this occurs up to a limit beyond which further increase in the specific surface, respectively, the formed active sites, as grinding with a Wiley mill and decrystallization, brings about termination reactions through disproportionation and coupling of the exceedingly increased free radicals, and hence grafting is decreased or nearly inhibited. Drying of cellulose at 105°C resulted in decreased grafting yield. This was attributed to condensation of the cellulose structure. It has been also found that the grafting yield is influenced by the type and origin of cellulose whose reactivities differ for different monomers.     

Morphological and grafting modification of natural cellulose fibers

Crystal structure and mechanical properties of cellulose fibers were studied to investigate the effect of chemical treatment on the fiber. Pretreatment by acetone extraction, mercerization with 3–20% wt/v sodium hydroxide (NaOH), and acrylonitrile (AN) grafting initiated by azo‐bis‐isobutylonitrile were performed. From Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction quantitative measurements, the pretreated fibers showed an induced slight decrease of crystallinity index. The structural transformation of the fibers from cellulose I to cellulose II was observed at high NaOH concentration of 10–20% wt/v. The amount of grafting, 1.56, 2.94, 6.04, 8.34, or 10.46%, was dependent upon the initiator concentration and the volume of monomer in the reactor. The AN grafted fibers had no transformation of crystalline structure as observed after mercerization. Only a variation of X‐ray crystallinity index with grafting amount was observed. Moisture regain of pretreated and modified fibers depended on the structure of the fiber and the amount of grafting. The mechanical properties performed by a single fiber test method were strongly influenced by the cellulose structure, lateral index of crystallinity, and fraction of grafting. Scanning electron microscopy was used for analysis of surface morphologies of treated fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2456–2465, 2004     

Flow birefringence and viscosity of cellulose solutions in semi-dilute regime

An attempt was made to study the flow birefringence and the viscosity of the systems of cellulose in aqueous sodium hydroxide and cadoxen solutions. For this purpose alkali-soluble cellulose samples with crystal form I (simply denoted as cellulose I sample), prepared from conifer wood pulp by the steam-explosion method, and alkali-soluble cellulose samples with crystal form of cellulose II (cellulose II sample), regenerated from cuprammonium cellulose solution under specific conditions, were used. The extinction angle χ of aqueous alkali solutions of the cellulose I sample is significantly less shear rate (γ) dependent as compared with that of the cellulose II sample. In the latter system the χ versus γ relations for a given cellulose sample shifted to the higher γ side with decrease in the average molecular weight. The viscosity of the cellulose II sample in aqueous sodium hydroxide solutions is approximately twice that of the cellulose I sample in the same solvent if compared at the same molecular weight, same concentration, and same temperature. The latter solution showed a non-Newtonian property at relatively smaller γ than the former solution did. Spin-lattice relaxation time T₁ (by ¹³C-NMR) of cellulose in cadoxen solution was smaller in cellulose I, suggesting the existence of intra- and intermolecular hydrogen bondings at the C₆ position of cellulose molecules in cellulose I solution. A dynamic light scattering study on cellulose in cadoxen showed that in a 5 wt % solution of cellulose I cellulose particles are dispersed with time into smaller particles and the larger particles could be excluded by ultracentrifuge and in cellulose II solutions the cellulose particles had almost the same size during storage. The above findings indicate that in 5 wt% cellulose I solutions in aqueous alkali or in cadoxen, cellulose I is not dissolved molecularly, but a supra-molecular structure of the solid is at least partly reserved in the above solutions.     

The mechanism of cellulose alkalization in the isopropyl alcohol–water–sodium hydroxide–cellulose system

The mechanism of cellulose alkalization in isopropyl alcohol (IPA)–water–sodium hydroxide system was studied from the viewpoint of the selective distribution of sodium hydroxide between cellulose and the medium, and of the lattice transition of cellulose. A mixture of IPA, water, and sodium hydroxide spontaneously separates into two layers, i.e., the upper layer solution (ULS) consists of IPA, water, and a small amount of sodium hydroxide and the lower one (LLS) consists of sodium hydroxide, water, and a very small quantity of IPA. The role of the ULS and the LLS was distinctive. The ULS has a function to distribute sodium hydroxide with water in cellulose uniformly according to the distribution equilibrium between ULS and cellulose, and the ULS recovers sodium hydroxide with water from the LLS as the distribution equilibrium shifts in the alkalization of cellulose. The concentration of sodium hydroxide in the LLS and that of IPA in the ULS exerts an influence on the lattice structure of alkali cellulose. During the transformation from cellulose I to alkali cellulose, decrystallization does not occur. Some portion of alkali cellulose reverted to cellulose I by regeneration.     

预处理结合纤维素酶处理对醋酯纤维降解的研究

采用纤维素酶降解经氢氧化钠预处理过的醋酯纤维,考察了pH值、温度、酶用量、处理时间以及助剂对酶解效果的影响,并初步探索了超声波对氢氧化钠预处理效果的影响。结果表明,氢氧化钠预处理后,使用纤维素酶降解醋酯纤维的工艺条件为:pH值4.5,温度55℃,酶用量3 mL/L,反应时间4 h;使用超声波辅助氢氧化钠预处理后,醋酯纤维的取代度较单一碱处理略有降低,酶解活性提高;在纤维素酶催化水解反应中,加入非离子表面活性剂可以提高醋酯纤维的酶解效果。     

Redox-initiated vinyl graft copolymerisation onto wool with thiourea as the reductant. II. Fe3+-thiourea co-catalyst induced graft copolymerisation of methyl methacrylate on wool and modified wool fibres.

The capability of Fe³⁺-thiourea redox system to induce graft polymerisation of methyl methacrylate onto wool fibres was investigated under various conditions. Variables studied include sequence of addition of reagents, acidity of the reaction medium, temperature, monomer concentration and nature of the substrate. In addition, alkali solubility of wool before and after grafting was examined. Allowing the ferric ion to be absorbed first on wool before addition of the thiourea and monomer leads not only to higher grafting but to greater grafting efficiency and total conversion than when all the reagents were present together. The graft yield increases significantly by increasing reaction time in the initial stages of the reaction but it does slow down on prolonging the duration of grafting. The effect of increasing monomer concentration is to bring about a significant enhancement in the graft yield. The same holds true for acidity of the reaction medium and temperature. The graft yields are considerably influenced by chemical modification prior to grafting. For instance, wool reduced via treatment with thioglycolic acid is more amenable to grafting than untreated wool. The opposite holds true for esterified and dinitrophenylated wools. The alkali solubility of wool decreases significantly by increasing the graft yield; a graft yield of ca. 95% makes wool practically unimpaired with aqueous sodium hydroxide.     

Hot Alkali Refining of Cellulosic Pulps in the Presence of Sodium Sulfide

Cotton linter pulp and paper pulp were subjected to hot refining with potassium and sodium hydroxide in the presence of sodium sulfide at concentrations of 5% and 20%. The resulting changes in their chemical, physical, and submicroscopic properties as well as their mercerization depth were studied. The addition of sodium sulfide during hot sodium or potassium hydroxide refining of the pulps resulted in a small increase in α-cellulose content of the cotton linters. Remarkable increase was observed in the case of the paper pulp as well as in the resulting decrystallization, and it increased the heterogeneity of the macromolecular structure of both pulps. This led to an increase in the swelling ability of the fibers as revealed from the results of water retention value (WRV), liquor retention value (LRV), and sodium hydroxide retention value (NaOH RV). The addition of sodium sulfide to sodium or potassium hydroxide during hot refining of the cotton linters or to sodium hydroxide during refining of the paper pulp led to the reduction in the degree of polymerization and to improvement in the reactivity towards xanthation. This was in contrast to the results of the alkali refining of the paper pulp with a mixture of potassium hydroxide-sodium sulfide in which the degree of polymerization was increased and the reactivity towards xanthation was decreased. The mercerization depth of the hot refined pulps was also investigated using FUR 1650 spectrophotometer absorption method. The cotton linters refined with a mixture of 5% sodium hydroxide-sodium sulfide possessed a higher degree of chemical purity and a good open and accessible fine structure and at the same time were characterized with a higher degree of polymerization suitable for use as a starting refined pulp for the manufacture of paper documents.     

水悬浮体系中苯乙烯和马来酸酐接枝聚丙烯改性研究

采用过氧化苯甲酰（BPO）为引发剂,通过水相悬浮法制备苯乙烯（St）和马来酸酐（MAH）双单体接枝聚丙烯（PP-g-St/MAH）。考察St加入量对接枝反应的影响,通过熔体流动速率和水接触角测试分析接枝产物的性能,采用X射线衍射和红外光谱分析表征接枝产物的结构。结果表明,随St加入量的增加,MAH接枝率升高,在St/MAH为3/1时,MAH接枝率为3.10 %,接枝效率高达70.02 %。随着接枝率的增加,接枝产物的熔体流动速率减小,PP主链间相互缠绕作用增强,熔体强度增大,结晶度降低,亲水性改善。     

Creation of reactive centers on cotton. IV. Reaction of acrylamidomethylated cotton with some sulfur compounds

The addition of mercaptoethanol and hydrogen sulfide to the pendent double bonds of acrylamidomethylated cotton (AMC) has been investigated. The interaction of acrylonitrile with the modified celluloses so obtained (substrate I and II) and with AMC treated with ammonium hydroxide (substrate III) in the presence of Ce(IV) is studied. Substrate I shows higher initial grafting yields. than AMC; the opposite holds true for the maximum graft yields. The graft yields obtained with substrate II are lower than those of AMC. All modified cottons studied are less amenable to grafting compared with the unmodified cotton. The graft yields of AMC and substrate III are comparable due to the fact that both substrates are crosslinked. Probable reasons for the inferior reactivity of substrates I and II are also given.     

Hydroxyethyl Cellulose. I. Variables Affecting the Hydroxyethylation Reaction

A few studies have been made on the mechanism of hydroxyethylation of cellulose; however, contradictory results were obtained. The studies in this work reveal that the use of a low aqueous liquor ratio leads to high percentage of ethoxyl groups per glucose anhydride. There is a maximum depending on the time, sodium hydroxide concentration, ethylene oxide-to-cellulose ratio, and the use of diluent. The explanation of the effects of these variables on the hydroxyethylation reactions is summarized as follows: (a) The reaction is diffusion controlled. (b) The increase of the number of OH groups as a result of the increase of sodium hydroxide concentration and liquor ratio leads to an increase in the rate of the hydroxyethylation reaction, but only up to a limit. (c) The use of tertiary butanol as a diluent increases the ethoxyl percent. (d) The most suitable concentrations of sodium hydroxide, which lead to the highest ethoxyl percent, are 5% and 14.5%. The manner of adding ethylene oxide was also studied. The results indicate that the addition of ethylene oxide in one portion to contact with the alkali cellulose in the presence of tertiary butanol and with continuous heating leads to the highest ethoxyl percent. The activation energies of the reaction are higher when using 5% sodium hydroxide concentration than those when using 14.5%; i.e., the energy required for the collision of molecules to undergo reaction is lower in the latter than in the former. Therefore, the use of 14.5% sodium hydroxide concentration is preferable.     

棉纤维蒸汽闪爆改性及其化学反应性能

研究采用高压热蒸汽闪爆技术,对棉纤维进行物理改性,并对闪爆前后棉纤维形态、溶解度、聚合度分析表征。通过改性前后棉纤维合成羧甲基纤维素研究发现,闪爆改性后其反应性能有大的提高。     

Decrement of cellulose recalcitrance by treatment with ionic liquid (1‐ethyl‐3‐methylimidazolium acetate) as a strategy to enhance enzymatic hydrolysis

BACKGROUND: The high crystallinity of cellulose underlies the recalcitrance that this polymer presents in enzymatic degradation. Thus, a pre‐treatment step is applied in most bioconversion processes. Treatments with ionic liquids are considered an emerging pre‐treatment technology, owing to their high efficiency in solvating cellulose, over molecular solvent systems. RESULTS: Crystalline cellulose with and without ionic liquid (1‐ethyl‐3‐methylimidazolium acetate) treatment, both commercially available, were used as substrates in enzymatic hydrolysis reactions using the earlier evaluated cellulolytic system of Fusarium oxysporum. The in situ removal of the hydrolysate during reactions enhanced the reaction rate as well as the overall glucose production. Ionic liquid treatment significantly decreased cellulose crystallinity and enhanced bioconversion yields and rates. The effects of cellulose structural changes during treatment on hydrolysis rate were investigated and the recalcitrance constants were determined. CONCLUSION: The study showed that ionic liquid‐treated cellulose became more homogeneous and more easily degradable than the untreated cellulose, a conclusion that was expressed mathematically by the difference in the recalcitrance constants for the two substrates. It was concluded that glucose production from ionic liquid‐treated cellulose could achieve very high conversion yields in consolidated bioprocesses or during simultaneous saccharification and fermentation. Copyright © 2012 Society of Chemical Industry     

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

A novel redox system, potassium ditelluratoargentate(III) (DTA)–cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA–cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two‐step single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X‐ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry     

Effects of substitution of triphenylmethyl groups into cellulose on the fine structure and thermal properties of the products

Mercerized cellulose in the form of 7/2 yarn was reactivated with 17.5% sodium hydroxide and then heated at 100°C. with 5 moles of trityl chloride, in pyridine, per anhydroglucose unit. The time of reaction was varied, giving ether derivatives of the cellulose containing 0.31–0.79 triphenylmethyl groups (DS) per anhydroglucose unit. Controls consisted of (1) the untreated cellulose yarn and (2) a portion subjected to all the reaction conditions except the reactant. The density of the product decreased hyperbolically with increasing substitution. The mixed x-ray pattern of the untreated control cellulose (35% cellulose I, 43% cellulose II) was largely converted by the activation treatment (10% cellulose I, 53% cellulose II). As reaction proceeded the crystal structure largely disappeared. The assumption is that substitution was confined almost exclusively to the primary hydroxyl position. The behavior of tensile stiffness, elastic recovery, and work recovery was explored at temperatures from about 25 to 225°C. Considerable improvement, which generally increased with increasing substitution, was observed in both elastic and work recovery at all temperatures studied.     

纤维素辐照改性及其应用

辐照技术利用电离辐射诱发物理化学反应(例如交联、聚合、接枝、降解等)对材料进行加工或改性,与常规加工方法相比,具有节能、无环境污染等特点。将辐照技术应用于纤维素改性过程近年已成为非动力核技术应用领域研究的热点之一。本工作对目前纤维素的辐照技术及其基本反应机理进行了概述,其中包括纤维素膜材料、纤维素水凝胶、纤维素微晶/纳米材料,并对纤维素辐照改性过程的辐照环境,包括溶剂、敏化剂、温度、辐照剂量、环境氛围、结晶度等进行了总结。     

Influence of alkali treatment on the fine structure and morphology of bamboo fibers

Bamboo fibers in the form of strips and dust were treated with NaOH solution of varying concentration (10, 15, and 20%). These treated and untreated samples were then subjected to FTIR and morphological studies. Again XRD study was carried out on those treated and untreated bamboo samples in both strip and dust form. It was found that during alkali treatment a lattice transformation from cellulose‐I to cellulose‐II took place. It is observed from IR index value that the conversion is maximum in between 15 and 20% of alkali treatment. Swelling in NaOH introduces considerable changes in crystallinity, orientation angle, etc. Degree of crystallinity and crystallinity index for bamboo strips increases with increasing treatment concentration of alkali and falls off after 15% alkali concentration. This is also supported by d‐spacing value. Orientation factor f_x was calculated from the FWHM and it was found that f_x value has been increased from 0.9879 to 0.9915 for 15% alkali treated and again lowered to 0.8522 for 50% alkali treated samples. Same observation of X‐ray study was obtained for dust samples but at an earlier concentration. Morphological study of bamboo dust with scanning electron microscope indicates fibrillation at higher alkali concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5050–5056, 2006