Graftability of beaten pulps and acetylated pulps

Ce(IV)-induced polymerization of acrylonitrile with acetylated bagasse and wood pulps, having different acetyl contents, has been investigated. The graft yield is dependent on the acetyl content as well as the origin of the pulp. Increasing the acetyl content of pulps caused a significant decrease in the polymer loading. However, the rate of polymerization of acetylated wood pulp is much higher than that of acetylated bagasse pulp. The ceric consumption during grafting decreases as the acetyl content of the pulp increases. The effect of beating of the pulps, to various degrees of freeness, on their reactivity toward grafting process has also been studied. Generally, the state of cellulose, as defined by its degree of beating, and the origin of the pulp strongly influenced the graft yield. In creasing the beating degree of bagasse pulp resulted in a decrease in graft yield, while beating of wood pulp, to a definite degree, inhibits the polymerization reaction. The consumption of Ce(IV) by the beaten pulps during oxidation is somewhat greater than that consumed by the unbeaten pulps, whereas the consumption during grafting of acrylonitrile onto beaten pulps depends on the initial concentration of ceric solution. Also, the effect of grafting of acrylonitrile onto acetylated wood and bagasse pulps on their strength properties as well as the effect of grafting onto beaten pulps on their properties has been investigated. Grafting of acrylonitrile onto acetylated bagasse pulp decreased its strength properties, but improved its beatability comparatively to those of original pulp (0 acetyl content). On the other hand, grafting of acrylonitrile onto acetylated wood pulp resulted in a great improvement in its strength properties compared to those of grafted unacetylated pulp. Grafted unbeaten pulps gave thinner and weaker paper than the original pulp (without grafting). Beating of bagasse pulp before grafting gave pulp which possessed a higher strength properties, at low °SR, than those of pulp beaten after grafting. Raising the °SR by rebeating the pulp after reaction up to the original value had an adverse effect on the strength. Beating of bagasse pulp before grafting did not accelerate the reaction rate, but it saved some power consumption, since the time required for beating of grafted pulp to a given °SR was lower than that of ungrafted pulp.     

Effect of Some Physical Treatments On the Reactivity of Cotton Stalk Pulp Toward Grafting

The effect of different physical treatments-for example, grinding, beating, and swelling with ethylene diamine-on the reactivity of bleached cotton stalk pulp toward grafting with methylmethacrylate monomer using ceric ion redox system is studied. the effect of monomer concentration and liquor ratio of grafting system on the graftability is also demonstrated. the graftability of treated samples is improved by using a liquor ratio of 50:1 instead of 40:1 for the untreated sample. Optimum graft yield for the beaten samples is obtained at 37°SR. Increasing the °SR of the beaten samples decreases the graft yield till it reaches a value lower than that of the untreated sample at 61°SR. Swelling of cotton stalk pulp with ethylene diamine has a high effect on the reactivity toward grafting. the physically treated pulps are characterized by infrared spectra to clarify the effect of these treatments on the crystallinity index (Cr I) of cotton stalk pulp.     

Activating pulp toward acetylation by chemical or mechanical means

Activation of pulps during acetylation, by prior mechanical or chemical treatment, has been investigated. The effect of degree of beating on the acetylation rate of wood and bagasse pulps has been studied. It is found that the acetylation rate of pulps increases when the degree of beating of pulps is increased to a definite degree, after which it slows down. The maximum reactivity of bagasse pulp is obtained at 50°SR, while that of wood pulp is observed at 30°SR. The effect of grafting of acrylonitrile onto bagasse and wood pulps on their reactivity during acetylation has been also studied. The results indicate that grafting of acrylonitrile onto pulps has a favorable effect on their acetylation rate. This is dependent on the degree of grafting as well as the origin of pulp fibers. The most suitable method of activation during acetylation reaction is dependent on the origin of the pulp. The reactivity of bagasse pulp during acetylation is influenced more by beating of pulp, prior to the reaction, than by the grafting of acrylonitrile onto pulp. On the other hand, the acetylation reaction of wood pulp is activated by grafting rather than by beating. Also the effect of the activation process, mechanical or chemical, on the strength properties of the paper sheets produced from acetylated pulps has been investigated. Chemical activation of wood pulp prior to acetylation resulted in pulp with slightly higher strength properties than that activated by mechanical means. But, in the case of bagasse pulp, mechanical activation resulted in a pulp with strength superior to that produced by chemical activation.     

Preparation,characterization, and properties of unbleached,bleached, and grafted pulps from JRC‐321 variety jute fiber

Graft copolymerization onto jute pulps opened the door to new concepts in pulp and paper research. Jute pulp from the JRC‐321 variety white jute fiber was prepared by the alkaline sulfite pulping process. The pulp obtained was bleached by the chlorination, extraction, and hypochlorite sequence technique to remove excess lignin for making bright and good quality paper. Special attention was focused on the graft copolymerization of acrylamide monomer onto the unbleached and bleached pulps by the use of a complex initiating system: Cu(II)/glycine/KHSO₅ in aqueous solution. It was found that percentage grafting was high in the case of bleached pulp. The grafted pulps so obtained were characterized by FTIR and their thermal behavior was characterized by TGA. Their mechanical properties such as tensile strength, percentage elongation, and tenacity were measured and compared. The physical properties such as rot‐resistance and water‐retention capacity of the grafted and the ungrafted pulps were determined. The effect of the percentage grafting variation on the above mentioned properties was examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1963–1969, 2002     

打浆前后酶处理对草浆性能的影响

用木聚糖酶处理漂白草浆能改善浆料性能。采用产自黑曲霉的木聚糖酶处理打浆前和打浆后的浆料 ,发现浆料的滤水性、白度和强度均得到提高。酶处理最适合的条件是 :酶用量 3～ 5IU/g ,处理温度 45℃ ,处理时间 60min ,浆浓 5 %。轻微打浆后再进行酶处理比打浆前酶处理的效果好     

Graft copolymerization of acrylonitrile onto bagasse and wood pulps

Graft copolymerization of acrylonitrile onto bagasse and wood pulps has been studied using ceric ammonium nitrate as initiator. The effect of order of reactants addition on grafting was examined: three methods were studied. Addition of the pulp to a mixture of initiator and monomer (method A) resulted in more efficient grafting than the other two methods. The reaction produced more grafting at 50°C than at 30°C or at 40°C. The results showed that the monomer and initiator concentrations are the major factors influencing the grafting rate of acrylonitrile. Increasing the acrylonitrile or initiator concentration was accompanied by a substantial increase in graft yields. Increasing the initiator concentration is more effective on polymerization rate than the increase in monomer concentration. The extent of grafting of this monomer can best be controlled by reaction time. Water swelling of pulps significantly affected the grafting rate of acrylonitrile as well as the ceric consumption during grafting. The reactivity of bagasse pulp towards grafting of acrylonitrile is higher than that of wood pulp due to a more open structure of cellulose in bagasse pulp as well as the presence of some lignin which accelerates grafting. Ceric consumption during grafting depends on the nature of the pulp as well as the monomer and initiator concentrations, time, temperature, and the method of grafting. More Ce(IV) is consumed during grafting than during oxidation of the pulps under identical reaction conditions, due to homopolymer formation which accompanied grafting. The ceric consumption by bagasse during grafting or oxidation is somewhat greater than that consumed by wood pulp under similar reaction conditions.     

Graft copolymers of wood pulp and 1-phenylethene. I. Generality of synthesis and proof of copolymerization

A method of grafting lignin-containing materials is now known that allows 1-phenylethylene (styrene, [100-42-5]) graft copolymers of a lignin source to be quantitatively made. The grafting reaction is a solution polymerization often run in aprotic, polar, organic solvents. Grafting changes solubility and surface properties of the lignin-containing material. The lignin-containing materials grafted are unbleached wood pulps produced by chemical, thermal, and mechanical pulping. Grafting wood pulp produces a wood-reinforced, thermoplastic composite. © 1993 John Wiley & Sons, Inc.     

Radiation grafting of vinyl monomers onto wood pulp cellulose. Part I

The effect of dose, dose rate, monomer type, and monomer concentration on the water transport behavior in grafted cellulose pulp and hand sheets was studied. At low dose rates, grafting rates of styrene onto wood pulp were less with hand sheets than with the pulp itself. Grafting was also found to be decreased by increasing the dose rate. Grafting mixtures of styrene and acrylonitrile gave better yields than styrene alone. Excellent grafting yields were obtained by treating the pulp or hand sheets with water before adding vinyl monomers. In this way, solvents such as dioxane could be eliminated from the grafting mixture. The hand sheets, grafted with mixtures of acrylonitrile and styrene, had good mechanical properties although less than the corresponding ungrafted sheets. Grafting decreased the moisture regain in pulp and hand sheets. Gamma irradiation of wood pulp under ambient conditions without additives reduced the water sorption considerably.     

Bleaching of Rice Straw Paper Pulp and Possibilities for Replacement of Sodium Hydroxide by Ammonium Hydroxide During the Extraction Stage

Bleaching of rice straw soda pulp was investigated under various conditions. The rate of the chlorination and hypochlorite reactions were studied; the best properties were attained by shortening the chlorination time to about 20 min. The extraction efficiency of ammonium hydroxide on chlorinated soda pulp was also investigated. The effectiveness of extraction can be deduced from the reduction of the kappa number, cuprammonium viscosity and the brightness obtained after the hypochlorite step. Extraction can be carried out with ammonium hydroxide instead of sodium hydroxide used in the conventional method. The strengths of unbleached and fully bleached pulps were evaluated. The fully bleached ammonium hydroxide extracted pulps were beaten faster and were usually stronger than the corresponding pulps extracted with sodium hydroxide.     

The xanthate method of grafting. III. Effect of lignin content on the graftability of wood pulp

Several commercial wood pulps of different chemical origin and with various lignin content were copolymerized with acrylonitrile using the xanthate grafting process. A number of experiments were carried out to evaluate the effects exerted by the residual lignin and by other wood components on the grafting reaction. The results obtained show that graft copolymers can be prepared in good yields with pulps containing as much as 23% lignin. With the aim to investigate the effect of lignin in more detail, two series of pulps were prepared by delignification of a crude sulfite pulp and a crude Kraft pulp to different levels of lignin content. Sodium chlorite was used as a bleaching agent. Copolymerization results obtained with these pulps indicate some fundamental differences in behavior between sulfite and Kraft pulps. In both cases, the copolymerization is afflicted by a short inhibition period whose duration, however, does not depend on the lignin content in the pulp.     

苇浆回用性能的研究

本文研究了漂白硫酸盐苇浆在反复回用过程中物理化学性能的变化规律。试验表明，随着回用次数增加，聚戊糖含量、保水值、纸页紧度、抗张与耐破强度、耐折度逐渐降低，且对原浆打浆有较大的下降趋势；平均聚会度、相对结晶指数与散射系数具有增加的总趋势；纤维平均长度由于细小级分流失有所增加；零距裂断长变化较小。打过浆与未打浆苇浆在回用过程中抗张指数与紧度均成对数直线关系，其斜率分别为2．481和2.09。     

Evaluation of paper properties of thermomechanical pulp modified by ozonation and grafting with thermoplastic polymers

Paper properties of the thermochemical pulp modified by ozonation and grafting with styrene, acrylamide or their mixtures have been studied. Paper sheets, prepared by hot pressing from ozonated and grafted pulps showed improvement in: wet breaking length; dry breaking length; burst and dimensional stability.     

Fe~(2+)-H_2O_2-二氧化硫脲引发绒毛浆与MMA接枝共聚的研究

研究了Fe2+-H2O2-二氧化硫脲体系引发绒毛浆与甲基丙烯酸甲酯的接枝共聚。考察了该引发体系下反应温度、反应时间、过氧化氢用量、二氧化硫脲用量、单体浓度和液比对接枝率和接枝效率的影响。并用红外光谱对接枝纤维产物进行了鉴定。结果表明,二氧化硫脲的加入能有效地使接枝共聚得以顺利进行;适当地提高温度,增加单体浓度,控制合适的二氧化硫脲用量都能提高接枝率和接枝效率,并在较短的时间就能成功接枝;接枝效率几乎不受液比的影响,一般维持在90%以上,接枝过程产生的均聚物极少。     

Synthesis and Identification of Graft Copolymers of Wood Pulp and 4-Methyl-2-oxy-3-oxopent-4-ene

A set of graft copolymers of wood pulp and 4-methyl-2-oxy-3-oxopent-4-ene has been synthesized. The graft reaction is a free radical polymerization coinitiated by calcium chloride, hydrogen peroxide on wood pulp in dimethylsulfoxide at 30°C. The wood pulps used in this research are unbleached products produced by chemical, thermal and mechanical pulping. All of them contain 25 to 29 weight percent lignin. Separation of the grafted wood pulp from homopoly(1-methyl-1-(2-oxy-1-oxopropyl)ethylene) formed during the reaction was done by benzene extraction. The results show that after the reaction, virtually all the wood pulps have a weight increase and, for very high yield sodium bisulfite pulp, a weight increase of up to 92.7% of the original weight of pulp was obtained. The Fourier transform infrared spectra of the benzene unextr-actable fractions provide strong proof of grafting.

The grafted wood pulp is a surface-modified pulp. Grafting has changed the surface properties of the starting wood pulp from hydrophilic to hydrophobic. The importance of this change is that the grafted wood pulp has potential use as a reinforcing material without use of coupling agents in many hydrophobic polymer matrixes.

The reaction products contain homopoly(1-methyl-1-(2-oxy-1-oxopropyl)ethylene) and uniformly dispersed grafted wood pulp. Under ordinary thermal compression conditions, thermoplastic composite objects can be made directly from the reaction products which contain up to 56 weight percent wood pulp.     

Eucalyptus globulus kraft process modifications: Effect on pulping and bleaching performance and papermaking properties of bleached pulps

BACKGROUND: Increasing the yield of the wood pulping process allows the reduction of specific wood costs. Process modifications with a great impact on pulp yield are the profiling of chemical charges and addition of anthraquinone (AQ). The aim of the present work is to investigate the influence of effective alkali (EA) profiling and addition of anthraquinone on E. globulus kraft pulping performance. The impact of such process modifications on the ECF bleaching process and on the papermaking properties of the resulting bleached pulps is also evaluated. RESULTS: An EA profiling cook may lead to a pulp yield gain, which is more significant as the total EA charge used in the kraft cook increases. AQ addition to kraft pulping leads to a significant yield increase. The ClO₂ charge required to fully bleach the pulps is lower for EA profiling and higher for kraft + AQ unbleached pulps. Bleached AQ pulp presents a high beatability due to high pulp xylan retention. CONCLUSION: A low total EA charge is the key parameter for high polysaccharide retention on pulp. AQ addition constitutes a feasible strategy to increase pulp yield. Bleaching performance and papermaking properties of pulps produced with the three different methods may be affected by the kraft pulping modifications. Copyright © 2008 Society of Chemical Industry     

Graft Pulping in Organosolv Systems

It has been previously demonstrated that free radicals are produced in the delignification of wood. These free radicals can be utilized to initiate grafting of vinyl polymers to the wood pulp. This simultaneous delignification and graft copolymerization has been referred to as graft pulping. The grafting of a variety of vinyl monomers to aspen wood pulp in alcohol-based solvent pulping has been evaluated in this study. Variables evaluated included cooking conditions, catalysts and two-stage pulping. The analysis of the reaction is complicated due to effects of the vinyl monomers on the delignification process and losses of wood during the extraction sequences. Although only low levels of polymer loading were obtained when single monomers were added to the pulping solvent, much better results were obtained using a binary monomer system of acrylonitrile(AN) and styrene(ST). At a monomer addition level of 10% (1.75% AN, 8.25% ST) to the aqueous ethanol solvent, a 14.6% polymer loading was achieved with the majority of the graft as polystyrene (88%) . The use of a two-stage pulping sequence improved the polymer loading of polyacrylonitrile but not polystyrene. Lignin was the primary site of grafting.     

Infrared Absorption Spectra of Cellulose Pulps of Palm Tree

Palm leaves are used for the production of different cellulose pulps; their properties are investigated, the resulting pulps were bleached by a multistage process, the effects of the addition of solvent during the pulping process on the chemical structure of the pulps are discussed. The strength properties of the paper which is produced from unbleached and bleached pulps increased with increasing cellulose percentage and decreasing lignin content in the pulp. Infrared absorption spectra were recorded for different unbleached and bleached pulp in the frequency range 200–4000 cm^-1 by using the alkali halide disk technique; the factors which affect the experimental technique were calibrated through these studies. The structural units within pulping yield (holocellulose, hemicellulose, cellulose, lignin, and ash) were interpreted within the pulp network structure by the infrared absorption spectra, where different samples of unbleached, bleached soda, and kraft pulps were also elucidated by IR spectra, after preheating at different temperatures and with using different ratios of organic solvents. The addition of organic solvents decreased or increased the crystallinity indices, depending on the type of solvent and the pulping temperature. It was also found that, at the same pulping temperature (155°C) and with the same percent of organic solvents in the pulping liquor, the asymmetry indices also the mean hydrogen bonding strength (A _OH/A_CH) of the unbleached soda pulps (organosolv or nonorganosolv pulping) were less than that of unbleached kraft pulps, except for the pulps obtained by pulping with dioxan at 155°C. The mean hydrogen bond strength of the bleached pulps decreased or increased, depending on the type solvent used and the pulping temperature.     

A novel method for vinyl grafting onto cotton fabric using ceric-cellulose thiocarbonate redox system

Treatment of cotton fabric with carbon disulphide in presence of NaOH resulted in cellulose thiocarbonate. The latter formed a complex when treated with ceric ammonium nitrate (CAN). After being thoroughly washed, the Ce^IV cellulose thiocarbonate was capable of initiating vinyl graft polymerization onto cotton fabric without homopolymer formation. The graft yield obtained with methyl methacrylate was found to increase by increasing CAN from zero to 50 mmol/l at temperatures from 60 to 80°C. Grafting was greatly favoured at pH 2; alkaline pH offset grafting. Incorporation of up to 7% of methanol, ethanol, or isopropanol in the aqueous polymerization medium enhanced grafting significantly with the certainty that the highest graft yield was obtained with isopropanol; using higher alcohol percentages decreased grafting. The rate of grafting showed an initial fast rate followed by a slower rate; 60 minutes reaction time proved appropriate for grafting irrespective of the condition used. In addition to methyl methacrylate the ability of Ce^IV-cellulose thiocarbonate to induce grafting of acrylonitrile and acrylamide was also examined. The rate of grafting followed the order methyl methacrylate > acrylonitrile > acrylamide.     

Developments in Ozone-Based Bleaching of Pulps

ABSTRACT

This paper summarizes the review of developments in the area of ozone-based elemental chlorine free (ECF) and total chlorine free (TCF) bleaching of wood and non-wood pulps. Focused areas of review are reaction mechanism of ozone with carbohydrates and lignin, effect of process conditions maintained during ozone bleaching on pulp properties, effect of using different cellulose protectors, effect of alkaline extraction after ozone bleaching of pulps, effect of ozone bleaching on final bleached pulp properties, ECF and TCF bleaching sequences used along with ozone for of wood and non-wood pulps, and commercial scale utilization of ozone for pulp bleaching.     

Thermal behavior of ungrafted and grafted bagasse and wood pulps

The effect of grafting of methyl methacrylate (MMA) and acrylonitrile (AN) on the thermal behavior of the pulp of sugar cane loaded with CaCO₃ and the pulp of a broad-leaved tree has been studied by thermal methods. Different experimental conditions of grafting AN onto the eucalyptus pulp have been used, including both water and organic solvent systems as the medium of reaction. To optimize the grafting of MMA onto wood pulp, the effect of pulp swelling and the contact time of the monomer with the pulp have been examined. Ungrafted as well as grafted cellulose samples with different levels of grafting were characterized by differential scanning calorimetry (DSC) and the thermogravimetric analysis (TGA). The CaCO₃ filler makes the pulp of bagasse thermally more stable. The grafting of MMA onto the bagasse or the wood pulps improves their thermal stability. This is not the case for wood grafted with poly(AN). The thermal stability of the grafted and ungrafted samples varies after a few weight percent has been lost. The glass transition temperature (T_g) of the copolymers have been measured and they are in good agreement with the calculated data. © 1993 John Wiley & Sons, Inc.