Cellulose graft copolymers. II. Graft copolymerization of ethyl acrylate with γ-irradiated cellulose from acetone–water systems

Ethyl acrylate was graft-copolymerized from acetone–water systems with γ-irradiated, purified cotton cellulose. The scavenging of the free radicals in the irradiated cellulose by water, acetone, and water–acetone systems was determined by electron spin resonance spectroscopy. The ESR spectra of free radicals, scavenged by water and acetone, were recorded by the use of a time-averaging computer attached to the ESR spectrometer, in which the ESR spectrum of the irradiated cellulose, which had been immersed in water and/or acetone, was electronically subtracted from the ESR spectrum of the irradiated cellulose control. For both water and acetone, the ESR spectra of the scavenged free radicals were singlets. This indicated that free radical sites formed on carbon C₁ or C₄ on radiation-initiated depolymerization, which would generate singlet ESR spectra, were readily accessible to these solvents. The maximum scavenging of the radicals was observed when irradiated cellulose was immersed in acetone–water solution which had a composition of 25/75 vol-%. The scavenging of the free radicals in irradiated cellulose when immersed in acetone–water solutions was less than when immersed in methanol–water solutions. Also, the extent of graft copolymerization of ethyl acrylate from acetone solutions with irradiated cellulose was less than that of ethyl acrylate from methanol solutions. These differences were probably due to differences in the diffusion rates of acetone and methanol into the cellulosie structure. The Trommsdorff-type effect in the acetone solutions would be less than in the methanol solutions, since acetone is a better solvent for poly(ethyl acrylate) than methanol.     

Cellulose graft copolymers. I. Graft copolymerization of ethyl acrylate with γ-irradiated cellulose from methanol–water systems

Ethyl acrylate was graft-copolymerized with γ-irradiated, purified cotton cellulose from methanol–water systems. The accessibility of the free radicals in the irradiated cellulose to water, methanol, ethyl acrylate, and methanol–water solutions was determined by electron spin resonance spectroscopy. The maximum scavenging of the radicals was recorded with the irradiated cellulose was immersed in methanol–water solution which had a composition of 50/50 vol-%. When ethyl acrylate was added to methanol–water solution (50/50 vol-%), maximum grafting on the irradiated cellulose occurred at a concentration of ethyl acrylate of about 20 vol-%. As the concentration of ethyl acrylate was decreased, maximum grafting occurred in solutions containing less than 50 vol-% methanol. It was also noted that maximum grafting of ethyl acrylate in methanol–water solutions to irradiated cellulose occurred at boundry conditions, that is, conditions where the ternary mixture was still one phase, slightly different from compositions which caused the mixture to separate into two phases. From methanol solution, maximum grafting occurred at a concentration of ethyl acrylate of 80 vol-%. The extent of grafting from methanol was less that obtained from methanol–water solutions at lower concentrations of ethyl acrylate. The accelerative effects of water was considered to be due to the Trommsdorff effect.     

Cellulose graft copolymers. III. Effects of oxygen on graft copolymerization of ethyl acrylate with γ-irradiated cellulose

The effects of oxygen on graft copolymerization of ethyl acrylate from methanol–water systems with γ-irradiated fibrous cotton cellulose were investigated by electron spin resonance spectroscopy and by the formation of cellulose–poly(ethyl acrylate) copolymer. The concentrations of free radicals in cellulose irradiated dry in an atmosphere of nitrogen at 25°C decreased during postirradiation storage in nitrogen or oxygen. The concentration of free radicals in the irradiated cellulose, moisture regain of the irradiated cellulose, and formation of cellulose–poly(ethyl acrylate) copolymer decreased with increase in temperature and time of postirradiation storage and to a greater extent when stored in oxygen rather than in nitrogen. From the decrease in moisture regain of irradiated cellulose during postirradiation storage, it was concluded that increased intermolecular bonding occurred in irradiated cellulose during storage in both nitrogen and oxygen atmospheres. When irradiated celluloses which had been stored in either oxygen or nitrogen were copolymerized with ethyl acrylate at 60°C, less formation of copolymer was observed than when the copolymerization reactions were conducted at 25°C. It was concluded that there was no evidence for the formation or decomposition of cellulose peroxides during these reactions and that formation of graft copolymer depended primarily on the concentration of free radicals in the irradiated cellulose at the time of copolymerization.     

Ionic graft copolymerization. II. Graft copolymerization of β-propiolactone onto acrylonitrile–sodium acrylate copolymer

Polyacrylonitrile–β-propiolactone (βPL) graft copolymer was synthesized by means of ionic polymerization, in which polymerization of βPL was initiated by polyacrylonitrile containing a small amount of some reactive groups such as ? COOK, ? COONa, ? COOLi, and ? COOH. Lower electronegativity of the countercation favored higher total conversion and higher grafting percentage. The grafting percentage increased with the reaction time and concentration of reactive groups in the trunk polymer, but grafting efficiency varied very little under these conditions. In the bulk polymerization at 60°C., grafting efficiency was about 60%, but in the solution polymerization in toluene or dioxane, grafting efficiency was higher than in bulk or nitrobenzene.     

Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with γ-olefins were carried out in bulk by γ-ray irradiation at 25°C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r₁ (FAN) and r₂ (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system.     

Ionic graft copolymerization. III. Graft copolymerization of β-propiolactone onto polyacrylonitrile containing diketene units

Polyacrylonitrile (PAN)–β-propiolactone (βPL) graft copolymer was synthesized by means of the ionic polymerization of βPL in the presence of polyacrylonitrile containing diketene units by using basic catalysts. A graft copolymer was produced by the copolymerization of βPL with the lactone ring in the trunk polymer. In this graft copolymerization method, the grafting efficiency was low. However, grafting efficiency increased with the mole ratio of polymeric lactone to βPL; also higher molecular weight of PβPL favored higher grafting efficiency. The reactivity ratio of polymeric lactone to βPL was estimated to be in the range of 0.1–0.3.     

Kinetics and thermal analysis of copolymerization of m-isopropenyl–α,α′-dimethylbenzyl isocyanate with styrene

The copolymerizations of m-isopropenyl–α,α′-dimethylbenzyl isocyanate (m-TMI) with styrene (STY) was investigated. The weight conversion of the copolymerization reaction increased as the duration of copolymerization increased. The reaction temperature was maintained between 60 and 75°C. Molecular weights of the copolymers decreased with increasing molar fraction of m-TMI in the feed. This study obtained reactivity ratios, Alfrey–Price parameters, Mark–Houwink constant, characteristic ratio, thermal degradation activation energy, difference of reactive propagation activation energy, and intrinsic viscosity for the copolymers. The copolymers were characterized by using elemental analysis (EA), gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. The copolymer chains in solution were observed to have a high degree of stiffness and a lack of rotational freedom. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2763–2770, 1999     

Plasticization of cellulose diacetate by graft copolymerization of ε‐caprolactone and lactic acid

Graft copolymerization of ε‐caprolactone (CL) and lactic acid (LA) onto cellulose diacetate (CDA) at the residual hydroxyl positions was conducted to obtain thermoplastic CDA. The effects of the reaction temperature and time and the CL/LA molar ratio in the feed on the progress of the graft copolymerization were investigated. The molecular weight of CDA was increased by this graft copolymerization. The oxycaproyl and lactyl molar substitutions (MS_CL and MS_LA, respectively) in grafted CDA (g‐CDA) were determined through ¹H‐NMR spectral analysis. These MS values were controllable by changing the reaction conditions adequately. The flow temperature and melt viscosity of g‐CDA decreased with an increase in the total substitution of MS_CL and MS_LA, and transparent polymer sheets could be obtained from the resulting g‐CDA by hot pressing at around 200°C without adding any plasticizer. The mechanical properties of the molded g‐CDA samples varied widely, depending on the different combinations of the MS_CL and MS_LA values; the g‐CDA sheets became elastic when the MS_CL was larger than the MS_LA, and their tensile strengths were enhanced as the MS_LA was increased. It was thus found that CDA was successfully plasticized by this graft copolymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2621–2628, 2002     

Electron spin resonance studies of γ-irradiated cellulose. I. Free radicals in decrystallized cellulose

The types of free radicals formed in decrystallized cellulose prepared from cellulose I and II after γ-irradiation in nitrogen atmosphere at room temperature were studied by ESR spectroscopy. X-Ray diffraction revealed that decrystallized cellulose I and II have the same microstructure. The ESR spectra obtained with the γ-irradiated decrystallized samples are simple. By contacting the irradiated sample with moisture in nitrogen atmosphere, the ESR spectrum changed to a narrow singlet, which gradually decreased in intensity until the spectrum completely disappeared. It was found that the types of free radicals generated in the decrystallized cellulose by γ-irradiation consist of the overlap of singlet and doublet. The singlet spectrum is mainly attributed to alkoxyl radical formed by the rupture of glycosidic linkage at the C 1 or C 4 position, and the doublet spectrum is ascribed to radical formed by hydrogen abstraction from the C 1 position in cellulose molecule.     

Electron spin resonance studies of γ-irradiated cellulose. II. Free radicals in accessible regions to water in cellulose I and cellulose II

The types of free radicals produced in the water-accessible regions of cellulose I and cellulose II fibers by γ-irradiation in nitrogen atmosphere at room temperature were studied by ESR spectroscopy. The ESR spectra of the irradiated cellulose I and II change by contacting the fibers with water, and after immersion in water the spectral shape depends on the orientation of the fiber axes to the magnetic field. These spectra are probably related to the free radicals generated in the highly ordered regions inaccessible to water in irradiated cellulosic fibers. The ESR spectrum of free radicals generated in decrystallized cellulose after irradiation consists of a singlet and a doublet. When the ESR spectra of free radicals formed in the highly ordered regions of cellulose I and II and the singlet and the doublet are combined in adequate ratio, the constructed spectra are similar to those of the radicals scavenged by water in the irradiated cellulose I and II fibers. From these facts, the spectra due to the free radicals in the water-accessible regions in irradiated cellulose I and II are considered to consist of the singlet and the doublet formed by free radicals in the typical amorphous regions and the spectra of other types of radicals generated in the semicrystalline regions.     

Graft copolymers of cellulose and vinylic ketones. I. Preparation of poly(methyl vinyl ketone)–cotton cellulose copolymers

The graft copolymerization reaction of methyl vinyl ketone from several solvents with fibrous cotton cellulose, preirradiated to a dosage of 5.2 × 10¹⁹ eV/g with γ-radiation from ⁶⁰Co, was investigated. Solvents included water, methanol, N,N-dimethyl formamide, and several combinations of these solvents. From water a maximum yield of copolymer product was obtained after 2 hr at 25°C. The addition of methanol to aqueous solutions of methyl vinyl ketone, in all concentrations, inhibited the graft copolymerization reaction. The addition of a small amount of N,N-dimethylformamide to aqueous solutions of the monomer increased the rate of the copolymerization reaction; however, the addition of large amounts of N,N-dimethylformamide to these solutions also inhibited the reaction. From solutions of methanol or N,N-dimethylformamide and monomer, little or no copolymerization of monomer with irradiated cellulose occurred. The copolymer products exhibited a strong infrared absorption band at 5.85 μ which is characteristic of the ? C?O group of the grafted poly(methyl vinyl ketone). Fibrous copolymer yarns exhibited increased yarn number and decreased breaking strength and average stiffness, as compared with unmodified cotton yarns.     

Luminescence from γ- and β-irradiated HDPE and LLDPE

The luminescence of polyethylene (high density polyethylene (HDPE) and linear low density polyethylene (LLDPE)) induced by ionising irradiation has been studied. The effects of filling materials, irradiation dose and dose rate on the luminescence have been investigated. For freshly irradiated samples, both unfilled and filled, the luminescence was concluded to consist predominantly of thermoluminescence (TL). Upon subsequent ageing, the contribution of TL was found to decrease due to its decay with time after irradiation. Light emission was found to increase in the later stages of ageing, for irradiated and also for un-irradiated samples. This light was interpreted as chemiluminescence (CL), emitted as a result of polymer oxidation. The maximum of the CL was higher for irradiated than for unirradiated polyethylene, indicating that the ionising radiation gave rise to an increased amount of oxidation products. Thus, CL has been shown to be a feasible technique in studies of radiation-induced oxidation. © of SCI.     

Graft copolymerization onto Tamarind Kernel Powder: Ceric(IV)‐initiated graft copolymerization of acrylonitrile

Tamarind Kernel Powder (TKP) is derived from the seeds of Tamarindus indica Linn., a common and most important tree of India. It is extensively used in cotton sizing, as a wet‐end additive in the paper industry, as a thickening, stabilizing, and gelling agent in the food industry. However, because of its fast biodegradability there is a need to prepare graft copolymers of TKP. The graft copolymerization of acrylonitrile (AN) onto TKP with ceric ammonium nitrate as a redox initiator in an aqueous medium has been studied. The reaction conditions were optimized to afford maximum percent grafting and percentage grafting efficiency of AN onto TKP, which was found to be 86% and 64%, respectively. Fourier Transform Infrared Spectrum of the grafted products showed an additional sharp absorption band at 2244 cm^?1 due to ? C?N stretching, thereby confirming the grafting of AN onto TKP. Scanning electron microscopy studies indicated change in contour of the polysaccharide on grafting and the thick polymeric coating of AN on the surface alongwith grafting of AN such that all the gap between polysaccharide particles have been closed. Thermal studies using thermogravimetric and differential gravimetric analyses confirmed that TKP‐g‐AN has overall high thermal stability than pure TKP. Reaction mechanism of grafting of acrylnitrile onto TKP is also proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization with depropagation: Prediction of kinetics and properties of α‐methylstyrene–methyl methacrylate copolymers. II. Bulk copolymerization

In order to calculate some kinetic parameters, such as the reactivity ratios, of the system α‐methylstyrene–methyl methacrylate, the bulk copolymerization of these two monomers with azobis isobutironitrile (AIBN) as a radical initiator was studied. Experiments were performed at the various temperatures of 50, 60, and 80°C with 0.5 mol % of initiator (AIBN). The kinetics, molecular weights, microstructure, and glass transition temperature (T_g) of the copolymers were followed. A software, previously developed (part I), taking into account the equilibrium of the homopolymerization of α‐methylstyrene, was used to simulate the experimental data. The model was in good agreement with all the experimental data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1611–1625, 1999     

Structure and properties of cellulose graft copolymers. I. Radiation-induced rayon–styrene graft copolymer

Rayon–styrene graft copolymers were prepared by the direct radiation method, with the use of the preswelling technique, by irradiation with γ-rays from ⁶⁰Co. The grafting was carried out in bulk styrene and in styrene–solvent mixtures, such as styrene–methanol and styrene–acetone, to study their effect on the graft copolymerization reaction and the structure of the resulting graft copolymer. The effects of carbon tetrachloride, a chain-transfer agent, was also investigated. Three different types of rayon yarn were used; Fortisan, a modifier-type high wet-modulus rayon, and a high-tenacity tire yarn, in order to study the effect of rayon microstructure on the grafting reaction. The molecular structure of the rayon–styrene graft copolymers was studied by hydrolyzing away the cellulose backbone and measuring the molecular weights of the grafted polystyrene branches. For grafting in bulk styrene, the molecular weights of the grafted polystyrene ranged from 400,000 to 1,000,000, while those of the polystyrene homopolymer formed in the outside solution were of the order of 30,000–50,000. The molecular weights of the grafted polystyrene branches tended to increase with per cent grafting in the graft copolymer. For grafting in styrene–methanol and styrene–acetone mixtures, the molecular weights of the polystyrene branches decreased with increasing solvent content. The addition of carbon tetrachloride to bulk styrene resulted in a sharp decrease in the molecular weights of the grafted branches. The grafting frequency or number of polystyrene branches per cellulose chain was calculated from the per cent grafting and the molecular weights of the polystyrene branches. The morphology of the rayon–styrene graft copolymers and some of their physical properties are discussed.     

Photochemistry of α,α′-Disubstituted Azoalkanes. I. Photosolvolytic Inversion and Substitution of α,α′-Dichloro- and α,α′-Dialkoyloxyazoalkanes

A series of α,α′-dichloro (α DClA), α,α′-dialkoyloxy- (αDAlA) and α,α′-dibenzoxy-azoalkanes (αDBeA) without α-aryl substituents was found to undergo meso ? dl photointerconversion upon direct irradiation through Pyrex in the presence of oxygen in a number of solvents. Furthermore, irradiation of α,α′-dipropionoxy-azoalkanes in benzene in the presence of excess acetic acid leads to substitution of the propionoxy groups by acetoxy groups in addition to meso ? dl photointerconversion. Similar irradiation in the presence of CH₃CO₂D does not lead to deuterium substitution of the β-hydrogens. The presence of benzenethiol radical scavenger does not affect the course of these photoreactions. Photosolvolysis schemes involving heterolysis (in the case of αDAlA and αDBeA) or an unstable intermediate (in the case of αDClA) are proposed.     

Effect of crystalline structure on the infrared spectra of γ-irradiated cotton cellulose

The effect of crystalline modifications on the infrared spectra of γ-irradiated cotton cellulose is presented. The crystalline modifications were brought about by treating cotton material with an aqueous solution of NaOH of various concentrations. The infrared spectra of the irradiated samples indicate an absorption band corresponding to the absorption of C?O groups. It was found that the intensity and frequency of this band depend on the crystalline structure. Thus, it appears at 1735 cm^?1 in the spectrum of cellulose I and at 1610 cm^?1 in the spectrum of cellulose II.     

Ionic graft copolymerization. V. Graft copolymerization of β-propiolactone onto the trunk polymers containing carboxylic acid,sulfonic acid,and other salts

β-Propiolactone (βPL) was graft-copolymerized onto styrene–divinylbenzene copolymers containing various carboxylates or sulfonates, composed of anions and cations having different electronegativities. In parallel, the mechanism of polymerizations of βPL by relatively neutral catalysts was studied in comparison with the behaviors of graft copolymerizations. In the graft copolymerization onto the trunk polymer containing various carboxylates, a lower electronegativity of countercation favors a higher anionic polymerization activity and the order of rate of polymerization coincides with that of anionic activities of catalysts. On the other hand, in the case of trunk polymer containing sulfonates, a higher electronegativity of countercation favors a cationic polymerization activity, and the order of rate of polymerization coincides with that of cationic activity of catalyst. The order of grafting efficiency at fixed total conversion coincides almost with that of anionic activity. The comparatively higher grafting efficiency in the grafting onto trunk polymer containing carboxylic acid might support an anionic graft copolymerization mechanism by carboxyl anion. The two following mechanisms were proposed for the initiation of the polymerization by the trunk polymer containing sodium sulfonate, in which acrylic acid is transformed from βPL.