UV‐radiation–induced preirradiation grafting of methyl methacrylate onto lignocellulose fiber in an aqueous medium and characterization

The preirradiation method of grafting has been established by ultraviolet radiation. Methyl methacrylate (MMA) was grafted onto jute fiber in an aqueous medium. The variation of graft weight with UV‐radiation time, monomer concentration, and reaction time was investigated. The conversion of monomer into homopolymer and graft copolymer was evaluated. The graft weight passes through a maximum value (～ 122%) with UV‐radiation time. The optimum value of the monomer concentration was evaluated for maximum degree of grafting. Graft copolymerization of MMA onto lignocellulose fiber significantly increases the elongation at break (～ 65%) compared to that of the “as‐received” sample. However, a linear decrease on breaking load was observed with the increase of graft weight. The estimation of degree of grafting was achieved using an IR technique by correlating band intensities with the degree of grafting. Considering the water‐absorption property, the grafted sample showed a maximum up to 61% decrease in hydrophilicity compared to that of the as‐received sample. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1667–1675, 2004     

Gamma radiation-induced graft copolymerization of divinylbenzene onto cellulose fabric

The extent of DVB grafting onto cellulose fabric increases with total gamma radiation dose up to 10–15 kGy while it decreases with the radiation dose rate. A quantitative analysis of DVB grafting has been attempted by means of IR spectroscopy using the baseline method. Characteristic bands were selected in the spectra of copolymers, namely, the cellulose band at 1160 cm^?1 and DVB band at 798 cm^?1. The former band decreased and the latter increased with the degree of copolymerization, and the values were in accordance with the calibration straight line. An attempt to graft DVB onto cotton fabric previously grafted with styrene showed greater extent of copolymerization than with pure fabric.     

Effect of Radiation Pretreatment on Photo-grafting of Acrylamide on Cellulose

To study the photo-grafting performance of acrylamide (AM) onto cellulose and the mechanical behavior of grafted cellulose, Whatman 41 filter paper was grafted with 30% AM in methanol by UV radiation using in situ technique. The amount of grafting (Gf) and tensile properties like tensile strength (TS) and elongation at break (Eb) were studied. In order to improve the tensile properties, cellulose was pretreated under UV and gamma radiations at different radiation intensities and subjected to grafting with 30% AM under in situ UV radiation. Cellulose was also pretreated by alkali (5% NaOH) along with UV and gamma radiations with different intensities and grafted with AM under UV radiation. Among the treatments, the alkali + UV irradiated 30% AM grafted sample showed the best mechanical performance (TS = 200%, Eb = 250%).     

Gamma ray-induced graft copolymerization of acrylamide and acrylic acid to nylon 6 fabric

Kinetics of radiation-induced grafting of acrylamide (Aam) and acrylic acid (Aa) to nylon 6 fabric were investigated employing a mutual radiation technique. Copper sulfate was used as the radical scavenger to reduce homopolymer formation. Formic acid was used for swelling, and its effect on grafting was studied. Maximum amount of grafting was doubled when formic acid was used for swelling nylon prior to, but not during, irradiation. The rate of grafting was not significantly affected if it was carried out in an atmosphere of air instead of nitrogen. The effect of monomer concentration, dose rate, and total dose on grafting has been studied. Rate of grafting was significantly higher when lower dose rates and monomer concentrations were used. Saturation grafting was proportional to monomer concentration up to 2.1M. Initial rate of grafting was proportional to monomer concentration. The rate of grafting of Aam was proportional to the dose rate to the power 0.25–1.0. A synergestic effect was noticed during grafting with mixtures of Aam and Aa (80:20; 20:80). Grafted fabrics showed considerable increase in moisture regain. Dyeability and tensile properties of the grafted fabrics were not significantly affected by grafting. Aa-grafted fabrics did not melt up to 320°C, whereas untreated nylon melts at 215°C.     

Radiation-induced graft copolymerization of mixtures of styrene and acrylamide onto cellulose acetate. VI. Permeability of sodium chloride and sodium sulfate

Acrylamide, styrene, and mixtures of acrylamide and styrene were grafted onto cellulose acetate film. The permeabilities of sodium chloride and sodium sulfate through the ungrafted and grafted cellulose acetate films were studied. Permeability increases with the increase in the extent of grafting of acrylamide; whereas it decreases with the increase in the extent of grafting of styrene onto cellulose acetate. The same trend in permeability was observed when cellulose acetate was grafted with the binary monomer mixture. Permeability is also found to depend on the nature of the solute dissolved in water. The results were discussed in terms of free volume concept of the water-swollen films.     

聚丙烯无纺布预辐射固相接枝丙烯酸的研究

以聚丙烯(PP)无纺布为基材,以丙烯酸为单体,进行预辐射固相接枝聚合,考察了外部环境、辐射剂量、温度、反应时间、单体用量、介质、阻聚剂、交联剂对接枝率的影响。结果表明,通过预辐射固相接枝聚合方法,可将丙烯酸单体接枝在PP无纺布上,辐射剂量增大可提高接枝率;反应时间对接枝率的影响在低、高温阶段有所不同。最佳反应条件为:氮气环境,辐射剂量大于50 kGy,反应温度65℃,反应时间3 h,单体浓度30%,反应介质为水,阻聚剂0.8 g,交联剂用量为5 mL。     

Preparation and characterization of henequen cellulose grafted with methyl methacrylate and its application in composites

The grafting polymerization of methyl methacrylate (MMA) and cellulose from henequen (Agave fourcroydes) is investigated as a function of the initiator concentration (cerium-and-ammonium nitrate) and the monomer/cellulose ratio. The formation of cellulose-g-PMMA is confirmed by IR spectroscopy, DSC, and TGA. Both the initiator concentration and the MMA/cellulose ratio have a strong influence over the grafting parameters and over the molecular weight of the grafted PMMA. A higher initiator concentration and a lower monomer/cellulose ratio result in a lower molecular weight of the grafted polymer. Increasing the amount and the molecular weight of the grafted PMMA increases the compatibility of the fibers with SAN and PVC, as demonstrated by a mechanical test and scanning electron microscopy. SAN and PVC composites made with grafted cellulose exhibit higher flexural and tensile moduli, respectively, than those produced with the ungrafted fibers. Both moduli increase as the amount of reinforcement increases. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 339–346, 1997     

Grafting of acrylamide to nylon-6 by the electron beam preirradiation technique: 3. Degree of crystallinity at high grafting yields

X-ray diffraction measurements of nylon-6 grafted with acrylamide indicate that the crystallites of the nylon-6 are only marginally affected by very extensive radiation grafting. Considerable stresses are built up in the samples during their grafting. Fusion endotherms of the grafted samples are masked to a large extent by the stress-release exotherms. Consequently, values of ΔH_f derived from d.s.c. measurements of the unannealed samples are not reliable. Stresses built up during grafting may be at least partially released by treating them with 65% formic acid at room temperature. This annealing procedure is preferable to thermal annealing because of the decomposition of polyacrylamide at elevated temperatures. Perfection and size of the nylon-6 crystallites also increases significantly as result of such treatment.     

Preparation of hydrophilic membranes by grafting acrylic acid onto pre-irradiated teflon-FEP films

Grafting of acrylic acid onto pre-irradiated poly(tetrafluoroethylene-hexafluoropropylene) (Teflon-FEP) films was investigated, and the reaction parameters dose, dose rate, monomer concentration and grafting temperature were examined. The results show that the degree of grafting depends on the dose (5-60 kGy), the weight of grafted specimen increased up to 37%. The degree of grafting was found to be independent of the dose rate. The overall activation energies were calculated to be 28.8 and 81.6 kJ mol^-1 for treatments at above and below 50°C, respectively. The swelling of grafted films was measured in water, aqueous potassium hydroxide and methanol. The degree of swelling was found to increase with the length of grafted chains.     

PP-g-(AA-AM)的制备与结构性能表征

利用电子束预辐照粉末聚丙烯,水溶液中引发丙烯酸(AA)和丙烯酰胺(AM)接枝共聚合,制备了PP-g-(AA-AM)接枝共聚物。研究预辐照剂量、反应时间、单体比例与浓度对接枝率的影响,用FTIR和接触角测量仪分析其结构和表面性能。结果表明:辐照剂量为5kGy,反应时间为3h,AM/AA单体比例为(60/40～0/100),AM单体浓度为(3～5mol·L-1),AA(2～3mol·L-1)时,接枝率较高;FTIR结果证明,AA和AM均已接枝到聚丙烯中,并随接枝率增加相应峰面积增大,对水接触角(WCA)减小,亲水性明显改善。     

Graft copolymerization of acrylamide–methylacrylate comonomers onto cellulose using ceric ammonium nitrate

The graft copolymerization of acrylamide–methylacrylate comonomers was carried out using ceric ammonium nitrate as initiator in the presence of nitric acid at 25 ± 1°C. The effects of feed molarity, feed composition, reaction time, and temperature on graft yield (%G) and other grafting parameters were investigated. The determination of rate of ceric (IV) ions disappearance as a function of feed molarity and reaction time was useful in the determination of the rate of ceric (IV) ions consumption during graft copolymerization. The graft yield (%G) in the presence of acrylamide increases because of the synergistic effect of acrylamide comonomer. The composition of the grafted chains (F_AAm) varies on varying the feed composition and reaction temperature but is almost constant during feed molarity variation. The Mayo and Lewis method was used to determine the reactivity ratios of acrylamide (r₁) and methylacrylate (r₂), which are 0.65 and 1.07, respectively. The product of reactivity ratio (r₁ r₂) is less then unity; hence, an alternate arrangement of comonomer blocks in the grafted copolymer chain is proposed. The rate of graft copolymerization of comonomers onto cellulose is second power to the concentration of comonomers and square root to the concentration of ceric ammonium nitrate. Suitable reaction steps for graft copolymerization of comonomers onto cellulose are proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2631–2642, 2002     

Graft copolymerization of acrylamide onto nylon 6 using quinquevalent vanadium ion

Nylon 6 has been graft copolymerized with acrylamide using a quinquevalent vanadium ion as an initiator in aqueous media under a variety of conditions. Effects of initiator concentration, monomer concentration, acid concentration, CuSO₄ concentration, temperature, and chain transfer solvents have been studied. The graft yield shows a maxima at 0.005 mole/liter of initiator concentration. Similarly, the graft yield maxima with respect to acid concentration is 0.45 mole/liter. The graft yield increases within the range of the monomer concentration studied. The graft yield is temperature dependent. In addition, the reactions involved in initiation of grafting are elucidated. The work was also extended to study the moisture regain of grafted samples.     

超细纤维素胶体和丙烯酰胺的接枝共聚

本文用纤维素材料经酸分解制备具有平衡聚合度（LODP）的微晶纤维素，再分散成超细纤维素胶体（准均相纤维素体系）。用扫描电镜（SEM）观察处理前后的纤维素颗粒尺寸，并比较它们和丙烯酰胺接枝共聚的反应速率、聚合转化率、接枝率、接技效率、聚丙烯酰胺支链的分子量及其分布的情况。     

Study of radiation-induced graft copolymerization of vinyl acetate onto ethylene-co-propylene rubber

The radiation-induced graft copolymerization of vinyl acetate (VAc) onto ethylene-copropylene rubber (EPR) has been studied in methanol with radiation of cobalt-60. The effects of irradiation dose, dose rate, concentration of monomer, Cu⁺⁺ concentration, and temperature on the degree of grafting were investigated. The dependence of the initial grafting rate on dose rate, monome, and Cu⁺⁺ concentration were found to be 1.0, 1.95, and 0.5 order, respectively. The apparent activation energy was calculated to be 49 kJ/mol. Mechanical properties of the grafted polymer were investigated as a function of the grafting percentage. The tensile strength increases and elongation of break decreases with the increase of the degree of grafting in the region of low grafting percentage (≅ 10%). © 1996 John Wiley & Sons, Inc.     

Dielectric Properties of Bagasse and its Constituents

Abstract

Dielectric properties of bagasse raw material and its constituents, cellulose and lignin was studied. The effect of γ-radiation of different doses (0–40 M rad) on the dielectric properties of these investigated samples was also studied. However, the study of the grafting process of these materials with acrylamide initiating with 7-radiation (dose 20 M rad) was also clarified. The dielectric properties of these grafted materials were also investigated.     

一种新型辐射接枝材料的制备及性能

采用直接辐射法将丙烯酸(AA)和丙烯酰胺(Am)的混合单体接枝于聚乙烯(PE)膜制备了一种新型的功能性材料。研究了单体浓度、辐照环境和剂量率对接枝反应的影响。结果表明,AA/Am(1:1)混合单体体系的接技率大大高于AA和Am单独体系的接枝率。利用光学显微镜观察到接枝链充满整个基材。接枝材料具有优良的亲水性、染色性、离子交换能力、导电性能、机械性能、耐热和耐化学性能。     

Low protein fouling polypropylene membrane prepared by photoinduced reversible addition‐fragmentation chain transfer polymerization

In this study, 2‐hydroxyethyl methacrylate and N‐isopropyl acrylamide was block grafted onto the polypropylene macroporous membrane surface by photo‐induced reversible addition‐fragmentation chain transfer (RAFT) radical polymerization with benzyl dithiobenzoate as the RAFT agent. The degree of grafting of poly(2‐hydroxyethyl methacrylate) on the membrane surface increased with UV irradiation time and decreased with the chain transfer agent concentration increasing. The poly(2‐hydroxyethyl methacrylate)‐ grafted membranes were used as macro chain transfer agent for the further block graft copolymerization of N‐isopropyl acrylamide in the presence of free radical initiator. The degree of grafting of poly(N‐isopropyl acrylamide) increased with reaction time. Furthermore, the poly(2‐hydroxyethyl methacrylate)‐ grafted membrane with a degree of grafting of 0.48% (wt) showed the highest relative pure water flux and the best antifouling characteristics of protein dispersion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure and properties of cellulose graft copolymers. II. Cellulose–styrene graft copolymers synthesized by the ceric ion method

Styrene was graft-copolymerized onto wood cellulose by the ceric ion method of Mino and Kaizerman. The grafting reaction was found to depend strongly on the concentration of ceric ion in the grafting system and maximum grafting occurred in a narrow range of concentration of initiator, 1.0 × 10^?3-1.8 × 10^?3 mol/l, at 58 ± 1°C. A pretreatment technique, developed to enhance the monomer diffusion into cellulose, was found to increase the grafting considerably. The structures of the cellulose-styrene graft copolymers were studied by hydrolyzing away the cellulose backbone to isolate the grafted polystyrene branches. The molecular weight and the molecular weight distributions of the grafted polystyrene were determined using gel permeation chromatography. The number-average molecular weight (M?_n) ranged from 23,000 to 453,000 and the polydispersity ratios (M?_w/M?_n) varied from 2.5 to 8.0. The grafting frequencies calculated from the per cent grafting and molecular weight data were of the order of 0.05–0.4 polystyrene branches per cellulose chain.     

Radiation initiated grafting on fluoro polymers II. Grafting of N-vinylpyrrolidone on copolymers of vinyl fluoride and vinylidene fluoride by accelerated electrons

The radiation initiated grafting of N-vinylpyrrolidone (NVP) onto copolymers of vinyl fluoride/vinylidene fluoride (VF/VF₂) with compositions of 75/25 mol-%, 50/50 mol-% and 20/80 mol-% VF/VF₂ has been investigated. The active species, initiating the grafting, have been created by accelerated electrons (160 keV) applying preirradiation technique in vacuo. The time conversion curves present a characteristic temperature dependence. Increasing grafting temperature rises the initial grafting rate. The final (saturation) grafting yield increases with temperature up to 333 K, and then declines. This behaviour was described by the influences of glass transition on the rate of termination in the semicrystalline trunk polymers. The grafting rate (at constant irradiation dose and grafting temperature) decreases with increasing VF₂ content in the copolymers. The reason is discussed by means of a semiquantitative mathematical analysis of the graft kinetics applying “non-steady-state”-conditions. The grafting rate does not depend on dose rate, but strongly depends on irradiation dose passing a maximum. This maximum has been interpreted by means of “Differential-Interference-Contrast”-microscopy. The enthalpies of melting ΔH_m of the semicrystalline copolymers decrease after grafting with increasing grafting yield. This change is due to the partial destroying of crystalline regions in the trunk copolymers caused by stresses arising from grafted polymer chains. The membrane resistance of films grafted through is <10 Ω cm². The membranes proved to be permeable for urea.     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Influence of synthesis conditions

SYNOPSIS: The graft copolymerization of acrylamide monomer into polyethylene films was carried out by the preirradiation method. The influence of synthesis conditions, such as monomer concentration, preirradiation dose, reaction temperature, Mohr's salt, and pregrafting storage was investigated. The order of dependence of the rate of grafting on preirradiation dose and monomer concentration was found to be 0.87 and 1.86, respectively. An activation energy of 22.9 kJ/mol for the grafting reaction was obtained. The storage of preirradiated polyethylene film at −4°C prior to the reaction showed a decrease in the degree of grafting up to 10 days, beyond which the degree of grafting remained constant. The addition of FeSO₄ in the grafting medium not only inhibits the homopolymerization of the monomer but also decreases the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1331–1337, 2000