Graft copolymerizations of modified cellulose,grafting of acrylonitrile,and methyl methacrylate on carboxy methyl cellulose

Graft copolymers of acrylonitrile (ACN), methyl methacrylate (MMA), and their mixtures on carboxy methyl cellulose (d.S 0.4–0.5) were prepared by the use of ceric ion initiator in aqueous medium. The graft copolymers were characterized by IR spectroscopy. The extent of graft copolymerization of ACN and MMA was measured in terms of graft level, molecular weight of grafted polymer chains, and the frequency of grafting as functions of ceric ion concentration. It was found that at comparable reaction conditions, the molecular weight of the grafted polymer chains and the frequency of grafting were not of the same order of magnitude. For the monomer mixtures, the copolymer compositions obtained from the total nitrogen contents of the copolymer samples showed that a disproportionately low amount of ACN monomeric units were incorporated into the graft copolymer, even at high ACN content of the feed. © 1996 John Wiley & Sons, Inc.     

Influence of starch granule swelling on graft copolymer composition. A comparison of monomers

Seven monomers, which varied widely in water solubility and ionic charge, were graft polymerized onto both unswollen starch and starch that had been swollen by heating in water to 60°C. Polymerizations were initiated with ferrous ammonium sulfate hexahydrate–hydrogen peroxide and, where applicable, with ceric ammonium nitrate. Graft copolymers were freed of ungrafted homopolymer by solvent extraction and were characterized by weight percentage of synthetic polymer incorporated in the graft copolymer, molecular weight of grafted branches, and grafting frequency. The influence of starch granule swelling on graft copolymer structure varied with the monomer used and could not be predicted on the basis of water solubility of monomer or its resulting polymer. With acrylonitrile and acrylamide, swollen starch gave higher molecular weight and less frequent grafts than unswollen starch. However, methyl methacrylate, N,N-dimethylaminoethyl methacrylate · HNO₃, N-t-butylaminoethyl methacrylate. HNO₃, and 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride produced less frequent graft of higher molecular weight when starch was unswollen. With acrylic acid, graft molecular weight was independent of starch granule swelling, although grafting was less frequent when swollen starch was used.     

Grafting of poly(methyl methacrylate) in aqueous slurries of wood pulp

Methods for initiating the free radical graft polymerization of methyl methacrylate onto wood pulp were investigated. Processes considered were all carried out in water slurries of the cellulose, for simplicity and low cost. Of the methods studied only three provided high conversions of monomer to polymer and reasonably good grafting efficiencies. These are ceric ion initiation, a redox reaction with ferrous ion and hydrogen peroxide, and initiation by potassium permanganate/nitric acid mixtures. The ferrous ion/peroxide redox system appears to be the best procedure overall, since it is inexpensive and environmentally innocuous. The best grafting frequency obtained was about one graft per 800 anhydroglucose units in the cellulose. High molecular weight poly(methyl methacrylate) polymers were made, with the grafted species larger than the corresponding homopolymers.     

Graft copolymerization of methyl methacrylate on holocellulose

Graft copolymerization of methyl methacrylate initiated by ceric ion in aqueous medium on bleached holocellulose was studied at 29°C. It was found that an increase in the concentration of ceric ion and oxidation of the holocellulose with aqueous potassium dichromate solution resulted in increased levels of incorporation of poly(methyl methacrylate) graft copolymer, but were associated with reductions in the efficiency of grafting. Thiol groups were introduced on the holocellulose by treatment with dilute thioglycollic acid solutions at 29°C. The influence on the level of grafting and on the molecular weight of the grafted polymer by the incorporated thiol groups on the substrate was examined.     

Studies in the graft copolymerization of vinyl monomers on cellulosic materials

Graft copolymerization of acrylonitrile, methyl methacrylate, and vinyl acetate on bleached holocellulose initiated by ceric ions in aqueous medium was studied at 29°C. The extent of graft copolymer formation was poly(methyl methacrylate) > polyacrylonitrile > poly(vinyl acetate), indicating the influence of polarity of monomer on graft copolymerization. It was found that, although the molecular weights of the grafted polyacrylonitrile copolymer were lower than the values obtained for poly(methyl methacrylate), the latter was less frequently incorporated on the cellulosic backbone polymer than the polyacrylonitrile grafts. The marked reductions in graft level associated with thiolation of the cellulosic material suggest that hydrogen abstraction reactions from carbon atom carrying hydroxyl groups may not be important in graft copolymer formation.     

Graft copolymerization of starch with methyl acrylate: An examination of reaction variables

Starch-g-poly(methyl acrylate) (S-g-PMA) copolymers containing 55–60% PMA were prepared from cornstarch, high amylose cornstarch, and waxy cornstarch with ceric ammonium nitrate initiation. Graft copolymers were characterized with respect to % PMA homopolymer, % conversion of monomer to polymer, grafted PMA content, grafting frequency, and the molecular weight and molecular weight distributions of PMA grafts. Variables investigated in the graft copolymerization reaction were nitric acid concentration, ceric ion-to-starch ratio, reaction time, gelatinization of the starch, and reactant concentration in water. At high reactant concentrations, high conversions of methyl acrylate to grafted PMA could be obtained in less than 0.5 h at 25°C. © 1993 John Wiley & Sons, Inc.     

Location of some typical vinyl polymers within radiation-grafted cotton fibers: An electron microscopical survey

Electron microscopical observations of radiation-induced rayon–styrene graft copolymers were published by Kaeppner and Huang in 1965. The present paper reports electron microscopical investigations on the relationship of the structure of vinyl–cotton graft polymers to the original morphology of the cotton fiber and into the distribution of the grafted vinyl polymer in the cotton fiber structure. The grafted vinyl monomers investigated in this study were acrylonitrile, styrene, methyl methacrylate, and vinyl acetate. Two radiation-induced procedures were used: simultaneous irradiation grafting and post-irradiation grafting. Ceric ion grafting of acrylonitrile to cotton was included for purposes of comparison. Distribution of the vinyl polymer within the cotton fiber is illustrated by a series of electron micrographs, selected as typical of the particular grafted species under consideration. Results indicate that the diffusion rate of monomer into the cellulose fiber plays an important role in the final distribution of polyacrylonitrile grafts within the fiber. Uniform distribution of polyacrylonitrile in the fiber was achieved by simultaneous irradiation grafting of acrylonitrile on a highly substituted cyanoethylated cotton. In samples of low degree of cyanoethylation the distribution of graft polymer was non-uniform. In grafting initiated by ceric ion the acrylonitrile graft polymer was evenly distributed. Polystyrene–cotton copolymers from grafts, made by simultaneous irradiation of cotton in methanol solutions of the styrene monomer, were uniform throughout the fiber but showed opening of structure associated with the amount of graft formed. Grafting of methyl methacrylate occurred only in the peripheral regions of the fiber; by contrast, grafting of vinyl acetate was uniform throughout the fiber wall. Important factors governing the successful irradiation grafting in cotton fibers are choice of solvent, ratio of monomer to cellulose, nature of prior chemical modification of the cellulose, and total irradiation dosage.     

Composition of methyl methacrylate-grafted cellulose

Graft copolymerization of methyl methacrylate on cellulose samples was carried out using various initiator systems, and extraction treatment was performed on the copolymers with 50% to 300% grafting by weight. Adding of ceric ion to a suspension of cellulose and methyl methacrylate in water resulted in more efficient grafting than other methods. That is, amount of extracted cellulose from graft copolymers obtained by the conventional ceric ion method was approximately 20%, whereas those obtained either by the hydrogen peroxide method or by the adsorbed ceric ion method amounted to 70% to 80%. However, the amount of extracted homopolymer was approximately proportional to that of extracted cellulose. The composition of refined samples ranged 20% to 30% of cellulose content and 70% to 80% of poly(methyl methacrylate) content throughout all samples, and it was recognized that the proportion of poly(methyl methacrylate) tended to increase slightly with higher per cent grafting. When the structure of refined graft copolymer was derived from these values, it was recognized that the extent of the grafted chain was at most 1 mole per 1 mole of cellulose molecule in the conventional ceric ion method and amounted to only 1/10 mole in the hydrogen peroxide and adsorbed ceric ion methods.     

Grafting of acrylonitrile and methyl methacrylate from their binary mixtures on cellulose using ceric ions

Ceric ion‐initiated grafting on cellulose from a binary mixture of acrylonitrile and methyl methacrylate was carried out in heterogeneous and acidic conditions at 30 ± 0.1°C in a nitrogen atmosphere. To avoid the complexation of water molecules with Ce(IV) ions, the concentration of the nitric acid was taken to be more than the concentration of ceric ions. The effect of the feed concentration, reaction time, and ceric ions concentration on grafting were investigated at a fixed composition. To investigate the effect of monomer–monomer interactions on grafting, the graft copolymerization was also studied, using different feed compositions (f_AN) ranging from 0.25 to 0.80. In this range of feed composition, the synergistic effect of methyl methacrylate molecules has shown an important effect on acrylonitrile monomer and facilitate the incorporation of the acrylonitrile monomer into the grafted chains. The reactivity ratios of acrylonitrile and methyl methacrylate were calculated using the Mayo and Lewis method and were found to be 0.74 and 1.03, respectively. The average sequence lengths of the monomers (m̄M) were found to be dependent on the feed compositions and found to be arranged in alternate fashion in the grafted chains. The probability of the addition of a monomer (P_1,1) to the growing radicals on cellulose ended with its own type of monomer was found to be dependent on the feed composition. The composition of the grafted copolymers, homocopolymers, was determined by IR and elemental analysis for nitrogen. None of the grafted chain on cellulose was found to be made of a single type of monomer. The ceric ion consumption during grafting was found to be independent of the molarity of the feed but shown an appreciable change in the initial few hours of grafting. The variation in the values of the grafting parameters as a function of the reaction conditions is suitably explained. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 767–778, 2001     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Effect of lignin in graft copolymerization of methyl methacrylate on cellulose by ceric ion

The effect of lignin contained in cellulosic materials in graft copolymerization of methyl methacrylate on such materials using ceric ion as initiator was studied. It was found that the percent grafting and the average molecular weight of grafts became lower in samples having a larger lignin content but the number of grafts formed increased proportionally up to lignin content of about 2.5%. Ceric ion reacted at a faster rate with lignin than with cellulose in wood pulp, and the results indicating that the active sites formed on lignin by oxidation with ceric ion accelerate the formation of grafts and increase the number of grafts were obtained. But on the other hand, the active sites participated in the termination reaction of the growing graft polymer radicals to cause lowering of the average molecular weight of grafts.     

Graft copolymers of starch and poly(ethyl acrylate) dilution effects

Graft copolymerization of ethyl acrylate onto starch initiated by ceric ion in an aqueous medium was studied at 29°C. It was found that the grafting frequencies and molecular weights of grafted poly(ethyl acrylate) changed from 2 graft polymer molecules per 10⁴ anhydroglucose units (AGU) and 3.03 · 10⁵ to 34 and 6.80 · 10⁵, respectively, when the starch content was varied from 1.0 wt.-% to 0.2 wt.-%. The influence of dilution of ceric ion on the extent and rate of graft polymerization of ethyl acrylate onto starch was also examined.     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Grafting of cellulose–thiocarbamate with vinyl monomers: Antimicrobial activity

Grafting of vinyl monomers onto cellulose-thiocarbamate was carried out using ceric ammonium sulfate (CAS) as an initiator. The graft yield was found to depend on the amount of thiocarbamate groups, initiator, and monomer concentrations as well as temperature. The graft yield increased with increasing (CAS) concentration. The reactivity of vinyl monomers studied followed the order ethyl acrylate>acrylonitrile. A comparison between the graft yields obtained with the modified cullulose indicated that cellulose thiocarbamates having less than 1.1% nitrogen showed lower graft yields than the unmodified cellulose. Above this, cellulose thiocarbamate was much more amenable to grafting than the unmodified cellulose. The grafted cellulose thiocarbamates exhibited high antifungal activity and had no effect on gram-negative, gram-positive bacteria and yeast. The maximum zone of inhibition was obtained after grafting with 2 h which resulted in 43 and 50% add-on polymer in the cases of acrylonitrile and ethyl acrylate, respectively. Grafted cellulose thiocarbamates with acrylonitrile had higher potency for antifungal activity than that grafted with ethyl acrylate.     

Radiation-initiated graft copolymerization of binary monomer mixtures containing acrylonitrile with cotton cellulose

By the use of the cobalt 60 postirradiation grafting technique, purified cotton cellulose fibers were graft-copolymerized with binary mixtures of acrylonitrile and other monomers, including styrene, 1,3-butylene dimethacrylate, vinylpyrrolidone, vinylidene chloride, and methyl, butyl, lauryl, glycidyl, and allyl methacrylates. The irradiated cotton fibers were immersed in solutions of the monomers at 25°C to initiate graft copolymerization. Solvents were water, methanol, dimethyl sulfoxide, and methyl ethyl ketone, alone or in several combinations. The extent of graft copolymerization and the composition of the grafted copolymer depended on the composition of the binary mixtures of monomers and on the solvent or mixtures of solvents used. For example, addition of styrene, 1,3-butylene dimethacrylate, or vinylpyrrolidone to acrylonitrile increased the extent of graft copolymerization to a maximum value; addition of vinylidene chloride or allyl methacrylate to acrylonitrile did not greatly affect the extent of graft copolymerization; and addition of methyl or glycidyl methacrylate to acrylonitrile increased the extent of graft copolymerization without passing through a maximum value. The proportion of acrylonitrile in the grafted copolymer was generally less than that in the binary mixtures. As the reaction time was increased, the extent of graft copolymerization increased to a maximum value; however, the composition of the grafted copolymer did not change significantly. Generally, the addition of water to the solutions increased the extent of graft copolymerization. The mechanisms of these graft copolymerization reactions are discussed.     

Graft polymerization of acrylonitrile and methyl acrylate onto hemicellulose

Graft polymerizations of acrylonitrile onto both a commercial larchwood hemicellulose and a purified (low lignin) wheat straw hemicellulose could be initiated by ceric ammonium nitrate. The resulting hemicellulose-g-polyacrylonitrile (PAN) copolymers were fractionated by extraction at room temperature with dimethylformamide and dimethylsulfoxide. Fractions were characterized by determining both the wt % PAN in each polymer fraction and the molecular weight of grafted PAN. Saponification of the PAN component of hemicellulose-g-PAN gave a water-dispersible graft copolymer with good thickening properties for water systems. An absorbent polymer, similar to the starch-based absorbents (Super Slurpers), was produced when saponified hemicellulose-g-PAN was isolated by methanol precipitation and then dried. Larchwood hemicellulose was also graft-polymerized with methyl acrylate using ceric ammonium nitrate initiation, and the hemicellulose-g-poly(methyl acrylate) was extrusion-processed into a tough, leathery plastic. Although ceric ammonium nitrate could be used as an initiator for graft polymerizations onto low-lignin hemicelluloses, it was inert with crude wheat straw hemicellulose containing 11% lignin. The ferrous sulfate–hydrogen peroxide redox system was used to initiate graft polymerizations onto this high-lignin material, and properties of the resulting hemicellulose-g-poly(methyl acrylate) and saponified hemicellulose-g-PAN graft copolymers were evaluated.     

Grafting vinyl monomers onto silk fibers III. Graft copolymerization of methyl methacrylate onto silk using tetravalent cerium as initiator

The use of tetravalent ceric ions to initiate graft-copolymerization of methyl methacrylate onto silk has been investigated. The rate of grafting has been determined by varying monomer, cerium (IV), temperature, and nature of silk. The graft yield increases with increasing monomer concentration up to 0.65 mol/l and with further increase of monomer, the graft yield decreases. The percentage of grafting increases with increasing ceric ion concentration up to 0.03 mol/l and thereafter it decreases. The rate of reaction is temperature dependent, with increasing temperature, the graft yield increases. The grafting is considerably influenced by chemical modification prior to grafting. The effect of different species of ceric ion and CuSO₄ on the rate of grafting has also been investigated.     

Graft copolymerization of wool using acrylate monomers. I. Optimum conditions of grafting and molecular weight of grafts

Wool fibres were grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate and methylmethacrylate to various percentages of grafting in nitrogen atmosphere using ceric ammonium nitrate in nitric acid as initiator. The effects of concentration of the initiator, acid, monomer, temperature and time on the grafting were investigated. A comparison of such results indicated the following reactivity order of monomers: methyl acrylate > ethyl acrylate > methylmethacrylate > n-butyl acrylate. The molecular weights of the grafts were investigated by isolating the grafts from the fibres.     

Graft copolymerization of vinyl monomers on modified cottons. III. Grafting of acrylonitrile and methyl methacrylate on cyanoethylated cotton by the ceric ion method

The interaction of acrylonitrile and methyl methacrylate with cyanoethylated cotton in the presence of ceric ion has been studied under a variety of conditions. Increasing the reaction time, the monomer concentration, and the temperature favorably influences the degree of grafting. The same holds true for initiator concentration up to a certain limit, after which a decrease in the graft yield was obtained. On the other hand, ceric consumption during grafting and oxidation increases by increasing the magnitudes of all these factors. However, the consumption during grafting is always higher than that during oxidation. The graft yields obtained with cyanoethylated cotton are greater than those of the control, being increased by increasing the degree of substitution (D.S.) of the cyanoethylated cotton, suggesting that the cyanoethyl groups afford additional sites of grafting. On the other hand, the ceric consumption during oxidation of cyano-ethylated cotton was much lower than that of the control, being increased also by increasing the D.S., indicating perhaps that ceric ion attacks the cyanoethylated cotton exclusively at the cyanoethyl groups. Based on these findings, a scheme for the mechanism of reaction of a vinyl monomer with cyanoethylated cotton was proposed.     

Copolymer of ketonic resin–polyacrylonitrile

The polymerization of acrylonitrile in the presence of Ce(IV) salts and ketonic resin such as methyl ethyl ketone/formaldehyde and cyclohexanone/formaldehyde resin was investigated. Block copolymer of ketonic resin–polyacrylonitrile was produced. The effect of Ce(IV) concentration, temperature, time, and monomer concentration on the yield and molecular weight was studied. Maximum yield was obtained at 50°C and ceric ammonium nitrate concentration of 0.033 mol/L.