The xanthate method of grafting. IV. Grafting of acrylonitrile onto high-yield pulp

A series of pulps with different lignin content was prepared from a softwood sodium bisulfite high-yield pulp. Sodium chlorite at pH 4 served as the delignification agent. The resulting pulps were subjected to grafting with acrylonitrile using the cellulose xanthate–hydrogen peroxide redox system to initiate the copolymerization reaction. The resulting products were isolated and analyzed for homopolymer content by dimethylformamide extraction. The results indicate that the presence of larger amounts of lignin in pulp may have a favorable effect on grafting. The plots of total conversion as well as of polymer loading show a minimum centered around approximately 15% of lignin. This minimum is observed invariably at five different reaction times and it coincides with the maximum concentration of reductive groups in the pulps as well as with the maximum cation exchange capacity. The parameter of grafting efficiency has a tendency to increase with rising lignin content, reflecting the lower relative yields of homopolymer obtained with high-lignin pulps. This observation is discussed in relation to possible chain transfer reactions by lignin.     

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.     

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.     

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.     

The xanthate method of grafting. XII. Effect of operating conditions on the grafting of vinyl monomers onto wood pulp

The present paper examines the influence of various reaction parameters (e.g., pH, type, and concentration of peroxide, reaction time, oxygen as well as reaction medium) on the graft copolymerization of methacrylic acid, butyl methacrylate, epoxypropyl acrylate, and epoxypropyl methacrylate onto chemithermomechanical pulps, initiated by the xanthate method. The optimum concentration of H₂O₂ changes with the monomer used. Among the peroxides investigated, H₂O₂ offered the best performance. Oxygen and organic solvents, e.g., acetone and vegetable oil, inhabited grafting reaction. In addition, epoxy monomers showed better results compared to other monomers; this may be due to the participation of epoxy groups in the polymerization reaction     

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.     

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     

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.     

Graft copolymerization of nylon 6 with methyl methacrylate using dimethylaniline/Cu2+ ion system

The ability of dimethylaniline (DMA)/Cu²⁺ ion initiator to induce grafting of methyl methacrylate (MMA) onto nylon 6 was investigated under a variety of conditions. It was found that the graft yield is dependent on the concentration of the Cu²⁺ ion, of DMA, and of MMA. While the graft yield increases as the monomer concentration increases, there are optimal concentrations of DMA and Cu²⁺ ion. Below or above these concentrations, lower grafting occurred. The type of cupric salt also affects grafting to varying degrees. While the presence of CuSO₄ and Cu(NO₃)₂ accelerates grafting, the presence of CuCl₂ offsets the reaction. Increasing the reaction temperature and reaction time favorably influences grafting. Addition of acetic acid enhances grafting, whereas formic acid decreases grafting. Preswelling of nylon with formic acid leaves the susceptibility of nylon toward grafting practically unaltered. Studies of the copolymerization reaction was not confined to the graft yield but was extended to homopolymer formation and total conversion.     

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.     

Surface Modification of Acrylonitrile Copolymer Membranes by Grafting Acrylamide. II. Initiation by Fe2+/H2O2

Surface modification of membranes of an acrylonitrile copolymer (PAN) containing 5.5% methyl methacrylate and 4.0% sodium methylpropylenesulfonate by grafting acrylamide (AAm) with ferrous ammonium sulfate/H₂O₂ as an initiator in aqueous medium was studied. The grafted copolymer was verified by infrared spectra, X-ray photoelectron spectroscopy, and a scanning electron microscope (SEM). From the SEM photos, we know that the AAm homopolymer branches were grafted onto the surface of the membrane and the morphology of the PAN membrane did not change. The results showed that the extent of grafting was varied with some parameters, such as the pH value of the medium, reaction time and temperature, and concentration of AAm and H₂O₂. The results of the water-absorption percent of the membrane showed that the wettability of the modified PAN membrane was improved. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1907–1915, 1998     

Graft polymerization of methyl methacrylate on poly(ethylene terephthalate) fibers using H2O2 as initiator

The presence of poly(ethylene terephthalate) (PET) fibers during polymerization of methyl methacrylate (MMA) using H₂O₂ as initiator resulted in a substantial, constant increase in the weight of the fibers after repeated extraction with acetone. Fractional precipitation curves of the extracted PET—MMA polymerization product and a physical mixture of PET and PMMA were different, indicating that the interaction of MMA with PET involved grafting. The magnitude of the latter enhanced considerably by increasing H₂O₂ concentration up to 30 mequiv/L, then decreased by further increasing H₂O₂ concentration. There was also an optimal temperature (80°C) for grafting; below or above this temperature, lower grafting was obtained. Similarly, carrying out the polymerization reaction at different pH values revealed that pH7 constituted the optimal. On the other hand, grafting increased upon increase of the methyl methacrylate concentration within the range studied (8–20%). Incorporation of Cu²⁺ or Fe³⁺ ions in the polymerization medium caused a decrement in grafting, irrespective of the metallic ion concentrations. Using methylene chloride as a swelling agent for the fibers failed to enhance the susceptibility of the latter toward grafting. On the contrary, tetrachloroethane was quite promising in this regard. The homopolymer formed during grafting was also reported.     

Radiation grafting of vinyl monomers onto wood pulp cellulose. II

The effect of radiation dose rate and beating time on the mutual radiation grafting of styrene to unbleached and bleached kraft wood pulp was studied. Companion studies on the effect of beating time, peroxidation grafting, and order of monomer addition on the preirradiation graft copolymerization of acrylamide and diethylaminoethyl methacrylate were conducted on bleached wood pulp. The grafting rate of styrene increased with dose rate, but the kinetics suggests a significant diffusional resistance to the observed grafting rate. The per cent graft measured at fixed grafting conditions decreased markedly as pulp beating (effected prior to grafting) was increased. It is suggested that the decrease in grafting with beating is due to an increase in the accessibility and swelling of the beaten fibers. Dimethylaminoethyl methacrylate appeared to inhibit the grafting of acrylamide, and double grafting had to be used to graft both hydrophilic polymers to the pulp. The mechanical properties of high-yield pulp and groundwood were improved by the addition of the grafted pulps. The double grafts appeared to show promise as fibrous beaten additives for dry strength improvement. The styrenegrafted pulps were found not to respond at all to the beating process.     

Optimized Catalytic Bleaching Sequences for Eucalyptus Kraft Pulp

Contemporary multi-stage bleaching processes partially remove residual lignin and hexenuronic acid from cellulosic pulps. The reactions in the steps could be faster and consume smaller amounts of chemicals. Catalytic bleaching (H_cat), utilizing hypochlorite (H), triethylenediamine (DABCO) and its derivative N-carboxymethyl triethylenediamine (CM-DABCO), is a new discovery that has the potential to improve the chemical and energetic efficiency of bleaching processes in chemical pulp mills, e.g. through reducing the reaction time of the bleaching processes. The objective of this study was to clarify if new kraft pulp bleaching sequences with initial stage of chlorine dioxide (ClO₂; D) and an intermediate stage of H_cat could provide fully bleached pulps. The bleaching sequences of the studied eucalyptus pulps include D₀E_(OP)H_cat(Q)P and H_catZ/DP, which attained a final brightness of 88 and 89% ISO, respectively. H_catZ/DP showed to be the best sequence for the catalytic bleaching of eucalyptus kraft pulps. This study may open new doors to future bleaching of cellulose pulps with fewer towers and decreased use of chemicals.     

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.     

Graft polymerization of methyl methacrylate onto wool initiated by ferric acetylacetonate/dichloroacetic acid system

The graft polymerization of methyl methacrylate (MMA) initiated by ferric acetyl acetonate/dichloroacetic acid [Fe(acac)₃–Cl₂CHCOOH] system onto wool has been investigated in a mixture of water and dioxane. No grafting occurred in organic solvent; water was essential to the grafting. Both the total conversion and the percentage of grafting showed maxima when the mole ratio of Fe(acac)₃ and Cl₂CHCOOH was ¼. Increasing wool content increased the percentage of grafting, while homopolymer conversion was independent of wool content. The rate of grafting was not proportional to MMA concentration. The grafting mechanism was discussed from these results.     

The xanthate method of grafting. II. Effect of operating conditions on the grafting of acrylonitrile onto Wood pulp

Wood pulp was copolymerized with acrylonitrile as a monomer using the xanthate grafting method. This method takes advantage of the capability of cellulose xanthates to form a redox couple with a suitable oxidation agent. The present work uses the degree of xanthation γ ? 5 and hydrogen peroxide as an oxidant. Experiments carried out under different conditions have permitted to evaluate the influence of various reaction parameters on the graft copolymerization. Among the factors investigated, two appeared to be a paramount importance: the initial pH of the reaction mixture and the concentration of hydrogen peroxide. A change in one of these two parameters produced profound effects on the total conversion to polymer as well as on the copolymer:- homopolymer ratio. By a suitable combination of initial pH and peroxide concentration, it was possible to synthesize graft copolymers whose homopolymer content approaches zero.     

The xanthate method of grafting. VI. The copolymer–homopolymer ratio

Wood pulp was compolymerized with butyl acrylate as monomer. The xanthate redox method was employed to initiate the reaction. The effect of reaction time and temperature on the relative yield of grafted polymer and homopolymer was investigated. In the lower temperature region (15°–25°C), induction periods ranged from 10 to 30 min. No induction periods were observed at higher temperatures (40° and 60°C). The copolymer/homopolymer ratio was found to depend on both time and temperature. A considerable amount of homopolymer was formed in the initial stage of the reaction. Increased reaction temperature resulted in lower grafting efficiency. Similarly, both graft and homopolymer molecular weight decreased with rising reaction temperature.     

Photograft copolymerization of methyl methacrylate on silk fiber using titanium(III) chloride–potassium persulphate redox initiator in a limited aqueous system. I

Graft copolymerization of methyl methacrylate (MMA) onto mulberry silk fibers has been investigated in a limited aqueous system employing titanium(III) chloride–K₂S₂O₈ as the redox initiator under a photoactive condition with visible light. Polymerization in the presence of light at 32 ± 1°C has been found to be more pronounced than in the dark under identical conditions. The percentage of grafting, the percentage of total conversion, and the percentage of grafting efficiency have been studied by varying the reaction time, concentration of monomer, initiator concentration, solvent composition, and pH of the medium. A high percentage of grafting (∼ 93%), high grafting efficiency (∼ 97%), and the percentage of total conversion (∼ 25%) have been obtained with little homopolymer formation. Characterization of the grafted fibers has been investigated by Fourier transform infrared spectroscopy and scanning electron microscopy. Finally, the reaction mechanism has been discussed by considering hydrogen bonding. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2187–2193, 1999     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on the mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂/polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both percentage grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. Due to partial chain scission and deterioration of the ordered structure of PP during the graft polymerisation, the grafted PP exhibits worse thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂/PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have important influences on the toughening effect of the functionalised PP.