Photo-induced graft copolymerization of methyl methacrylate onto cellulose containing benzoyl xanthate chromophore

Summary Cellulose is conveniently functionalized to the corresponding S-benzoyl cellulose xanthate. Photolysis of S-benzoyl cellulose xanthate in presence of methyl methacrylate (MMA) initiated graft copolymerization which was confirmed by different analytical techniques.Document No. RRLT-PRU-25     

Photoinitiated graft copolymerization of hydroxyethyl methacrylate onto cotton cellulose

The photoinitiated graft copolymerization of hydroxyethyl methacrylate (HEMA) onto cotton cellulose was studied using uranyl nitrate (UN) and ceric ammonium nitrate (CAN) photoinitiators. Optimization of various parameters of the graft-copolymerization reaction viz., time, temperature, initiator, and monomer concentration, was carried out. The optimized conditions of grafting were employed to cotton samples swollen in zinc chloride as well as sodium hydroxide. Graft add-on was found to be dependent on the nature of substrate and the concentrations of monomer and photoinitiator. UN was found to be the better photoinitiator, giving higher grafting with HEMA. The grafted samples showed initially decrease and then marginal increase in the moisture regain with increase in graft add-on. The dye uptake of both direct and reactive dyes decreased with increase in graft add-on.     

Photo-induced graft copolymerization. III. Graft copolymerization of methyl methacrylate onto cellulose using peroxydiphosphate as photoinitiator

Photo-induced graft copolymerization of methyl methacrylate onto cellulose was investigated using peroxydiphosphate ion as the photoinitiator. The percentage graft yield increases with increasing both the monomer and initiator concentration. The reaction was carried out at three different temperatures, and the overall activation energy was computed. The kinetic data and other evidence indicate that the overall polymerization takes place by a radical mechanism. A suitable kinetic scheme has been suggested.     

The combined effect of stirring and oxygen on the graft copolymerization of methyl methacrylate onto cellulose

Methyl methacrylate was grafted onto bleached kraft pulp using ceric ammonium nitrate as initiator. The effect of stirring on the conversion to polymer and copolymer was strongly influenced by the presence of oxygen. In an oxygen-free system, the conversion was found to first increase rapidly with rising stirrer speed and then level off. No decrease in conversion was observed even at very high stirrer speeds (up to 1000 rpm). Inclusion of oxygen resulted in the appearance of a maximum on the conversion versus stirring speed curve, followed by a decrease in conversion at more intense agitation. The presence of oxygen also adversely affected the grafting efficiency.     

Ceric salt-initiated graft copolymerization of methyl methacrylate on preoxidized cellulose samples

The effects of preoxidation of cellulose samples on graft copolymerization in the presence of ceric salt (Ce⁴⁺) as an initiator were investigated. The use of Ce⁴⁺ as oxidizing agent inhibited the formation of grafts, and the number of grafts decreased as the concentration of Ce⁴⁺ in the pretreatment rose. In contrast, the samples oxidized with periodic acid (HIO)₄ or hydrogen peroxide (H₂O₂) tended to show improved initiation characteristics and gave a larger number of grafts than the unoxidized samples. The reactivity of oxidized samples toward Ce⁴⁺ was examined and the following results were obtained: The part of easy reactivity decreased in the Ce⁴⁺-oxidized samples but it increased in the HIO₄-oxidized samples; on the other hand, it did not vary greatly in the H₂O₂-oxidized samples. Cellulose is probably oxidized to different states by different oxidizing agents, and the reactivity of Ce⁴⁺ toward these oxidized samples, as one index, seems to be reflected in the graft copolymerization. It was consequently recognized that the graft copolymerization characteristics of cellulose samples could be improved significantly by proper selection of oxidiation conditions.     

A study on graft copolymerization of methyl methacrylate onto jute fiber

A kinetic study of the graft copolymerization of methyl methacrylate onto jute fiber using KMnO₄–malonic acid redox initiator system has been made. Effects of the concentrations of malonic acid, monomer, and KMnO₄ on graft yield have been studied. Besides, the effects of temperature, acid, and reaction medium, some inorganic salts on graft yield have been investigated. The most remarkable features of the investigation include the proposition of a mechanism, derivation of rate expression for the grafting process, and characterization of the grafted fiber by thermogravimetric analysis.     

Trivalent manganese chelate-initiated graft copolymerization of methyl methacrylate onto silk fibers

The graft copolymerization of methyl methacrylate onto silk fibers was investigated in aqueous solution using Mn³⁺ acetyl acetonate [Mn(acac)₃] as initiator. The rate of grafting was determined by varying monomer, acidity of medium, temperature, and reaction medium. The graft yield increases significantly with increase of [Mn(acac)₃] concentration up to 0.01M, and with further increase of [Mn(acac)₃] the graft yield decreases. The effect of the increase of monomer concentration brings about a significant enhancement in the graft yield, and with further increase the graft yield decreases. The rate of reaction is temperature dependent; with increasing temperature, the graft yield increases. Among the solvent composition studied, a water/solvent mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and, with further increase of solvent composition, the graft yield decreases. The effect of some inorganic salts, organic solvents, and complexing agents has been investigated.     

Radiation-Induced graft copolymerization,I. Graft copolymerization of methyl methacrylate onto nylon-6

The radiation-induced graft copolymerization of methyl methacrylate onto nylon fibers was investigated at room temperature. The homopolymer was separated by soxhlet extraction. The graft yield increases with increase of dose rate from 0.1768 to 0.7072 Mrad. The percentage of grafting increase with increasing monomer concentration. Addition of copper sulphate and a non-ionic surfactant, sodium lauryl sulphate, supresses the formation of homopolymer. The value of G_b, the number of branches per 100 eV of energy absorbed in the substrate polymer, and the value of α, the fraction of substrate polymer grafted, have been computed. A kinetic scheme has been suggested.     

高氯氯化聚乙烯对CR与MMA接枝共聚合的影响

以甲苯为溶剂,在９０℃条件下,研究了１０份氯含量为５７％的高氯氯化聚乙烯（ＨＣＰＥ）对１００份粘接型氯丁橡胶与７５份甲基丙烯酸甲酯（ＭＭＡ）接枝共聚合的影响。结果表明,该体系与无ＨＣＰＥ体系相比,ＭＭＡ转化率约提高４０％,产物接枝效率约高５０％,接枝度约高９０％。产物含有较高相对分子质量的级分,相对分子质量分布较宽,并且有较好的物理机械性能和较高粘接强度。     

Vanadium-cyclohexanone–initiated graft copolymerization of methyl methacrylate onto jute fibers

Graft copolymerization of methyl methacrylate (MMA) was carried out on jute fibers using a V⁵⁺ -cyclohexanone redox initiator system. The effect of the concentration of acid, monomer, and V⁵⁺ on graft yield have been studied. In order to obtain optimum conditions of grafting, the effects of temperature, acid, reaction medium, solvent, and some inorganic salts on graft yield have been investigated. The most remarkable features of the investigation include the proposition of a mechanism and derivation of rate expression for the grafting process. More than 100% grafting could be achieved with the present system.     

Factors affecting the photo-induced graft copolymerization of methyl methacrylate onto fibrous polymer

The effects of sample swelling, photosensitizer, and solvent on the photo-induced graft copolymerization of methyl methacrylate onto fibrous polymers such as Vinylon, nylon 6, and polyester were examined. Each separate factor, sample swelling, or solvent, or their combination, increased activity of polymerization. Only some sensitizer were effective. Studying the ESR spectra of photo-irradiated polymers also showed that either the sample swelling, the photosensitizer, or the organic solvent is very effective for the formation of polymer radicals under irradiation.     

羧甲基甲壳素接枝甲基丙烯酸甲酯的制备及成膜性

通过高速搅拌,未使用乳化剂,制备了羧甲基甲壳素和甲基丙烯酸甲酯的接枝共聚物,避免了产物中引入乳化剂杂质。利用红外光谱对接枝共聚物进行了表征。考察了不同接枝率的产物在12种常见溶剂中的溶解性,结果表明,不同接枝率的接枝共聚物都有良好的水溶性,可以形成无色透明的膜,扩大了其实际应用价值。     

Effects of redox initiator on graft copolymerization of methyl methacrylate onto natural rubber

Effects of cumene hydroperoxide (CHPO)/tetraethylene pentamine (TEPA), tert‐butyl hydroperoxide (TBHPO)/TEPA, and potassium persulfate (K₂S₂O₈)/sodium thiosulfate (Na₂S₂O₃) redox initiator on methyl methacrylate (MMA) grafted natural rubber by emulsion polymerization were investigated. The optimum reaction condition for each redox initiator on the grafting of natural rubber was studied. The grafted poly(methyl methacrylate) (PMMA) stays on the surface of rubber particles. CHPO dissolves very well in the oil phase and TBHPO dissolves moderately in the oil phase, and K₂S₂O₈ /Na₂S₂O₃ initiation is water‐soluble. Each can interact with TEPA in the aqueous phase. CHPO was found to give a higher grafting efficiency. To promote a greater grafting efficiency and yield a lower homopolymer content of PMMA, vinyl neo‐decanoate (VneoD) was added. Percentages of grafting of MMA on natural rubber latex initiated by CHPO/TEPA, TBHPO/TEPA, and K₂S₂O₈/K₂S₂O₃ of 84.4, 74.5, and 61.1, respectively, were in good agreement with percentages of PMMA in the aqueous phase as 7.2, 12.0, and 17.9 by CHPO, TBHPO, and K₂S₂O₈. VneoD produces allylic radicals on polyisoprene chains, favoring the grafting reaction with other vinyl monomers. CHPO/TEPA is thus a better redox system for grafting of MMA monomer on natural rubber latex. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2587–2601, 2006     

Studies on graft copolymerization of methyl methacrylate onto poly(vinyl chloride)

The grafting of methyl methacrylate on suspension-grade poly(vinyl chloride) in the presence of lauroyl peroxide has been studied. The reaction was carried out in a water suspension of the starting PVC polymer swollen with the monomer. The influence of reaction temperature, T, starting monomer/polymer ratio, M/P, and initiator concentration, I, in the monomer on the grafting efficiency of both polymers present in the system was found to be well described by the following linear regression equations: and      

Grafting vinyl monomers onto cellulose. I. Graft copolymerization of methyl methacrylate onto cellulose using quinquevalent vanadium ion

Graft copolymerization of methyl methacrylate on cellulosic materials with the use of quinquevalent vanadium as an initiator was studied. Increase of V⁵⁺ion concentration up to 0.0025 mole/liter increases graft yield, and with further increase of the initiator the graft yield decreases. The graft yield increases with increase of monomer concentration. The increase of acid concentration is accompanied by decrease of graft yield. A measurable increase in graft yield was observed with increase in temperature from 65 to 75°C. The graft yield is medium and substrate dependent. A suitable kinetic scheme has been pictured and a rate equation has been derived.     

Graft copolymerization of methyl methacrylate onto cellulosic biofibers

In this article, we have used the potassium persulfate to initiate the graft copolymerization of methyl methacrylate onto cellulosic biofibers in aqueous medium. Different reaction parameters, such as reaction time, initiator molar ratio, monomer concentration, amount of solvent, and reaction temperature, were optimized to get the maximum percentage of grafting (50.93%). The graft copolymers thus formed were characterized by Fourier transform infrared, scanning electron microscopy, X‐ray diffraction, and thermogravimetric, differential thermal analysis, and derivative thermogravimetric techniques. A mechanism is proposed to explain the generation of radicals and the initiation of graft copolymerization reactions. On grafting, percentage crystallinity decreases with reduction in its stiffness and hardness. The effect of grafting percentage on the physicochemical properties of raw as well as grafted fibers has also been investigated. The graft copolymers have been found to be more moisture resistant and also showed better chemical and thermal resistance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Effect of solvents on gamma radiation induced graft copolymerization of methyl methacrylate onto polypropylene

Methyl methacrylate was grafted onto polypropylene films using gamma radiation. Effects of different parameters, such as radiation dose, inhibitor concentration, monomer concentration, and type of solvents on the graft yield were investigated. It was established that the graft yield depends on the proper choice of solvent mixtures, and its maximum value can be obtained by using decalin/methanol mixture in the ratio 2 : 3 wt %. Thermal characteristics using differential scanning calorimetry shows that grafting has practically no effect on the crystallinity of PP. © 1997 John Wiley & Sons, Inc.     

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.