Optimized condition for grafting reaction of poly(butyl acrylate) onto oil palm empty fruit bunch fibre

Preparation of poly(butyl acrylate)‐grafted oil palm empty fruit bunch fibre (OPEFB) has been successfully carried out using H₂O₂/Fe²⁺ as a redox initiator in aqueous solution. The effects of reaction temperature and period, as well as the amount of monomer, initiator and nitric acid, on the percentage of grafting were investigated. The percentage of grafting increases with amount of monomer and can be controlled by setting the appropriate reaction conditions. The maximum percentage of grafting (about 265%) was obtained when the reaction was carried out without acid under optimum conditions (reaction period: 2 h, reaction temperature: 55 °C, amount of H₂O₂: 5.88 mmol) with 42.2 mmol of monomer. Mechanisms of grafting of butyl acrylate onto OPEFB were proposed. Characterization of the grafted OPEFB was done by Fourier‐transform infrared spectroscopy and scanning electron microscopy. The thermal properties were studied by thermogravimetric analysis. Copyright © 2003 Society of Chemical Industry     

Graft Copolymerization of Methyl Acrylate onto Oil Palm Empty Fruit Bunch (OPEFB) Fiber

Graft copolymerization of methyl acrylate (MA) onto OPEFB fiber has been successfully carried out using hydrogen peroxide and ferrous ammonium sulfate as initiators in an aqueous medium. The effects of reaction temperature, reaction period, and amount of monomer and initiators on the percentage of grafting were investigated. The results show that the percentage of grafting depends on reaction period and temperature as well as concentration of monomers and initiators. With 33.36 mmol of MA, the optimum percentage of grafting was obtained when the reaction was carried out using 6.00 mmol of H₂O₂ and 0.191 mmol of Fe²⁺ for 210 min at 75°C. The presence of the functional group in the grafted polymers was characterized by FTIR spectroscopy. Scanning electron microscopy was used to study the surface morphology. Thermogravimetric analysis indicated that the grafted OPEFB is thermally stable than the OPEFB     

Optimized conditions for the grafting reaction of poly(methyl methacrylate) onto oil‐palm empty fruit bunch fibers

This article describes the graft copolymerization of poly(methyl methacrylate) (PMMA) onto oil‐palm empty fruit bunches (OPEFBs) with a fiber length of less than 75 μm. The graft copolymerization was carried out under a nitrogen atmosphere by a free‐radical initiation technique in an aqueous medium. Hydrogen peroxide and ferrous ions were used as a redox initiator/cocatalyst system. The PMMA homopolymer that formed during the reaction was removed from the grafted copolymers by Soxhlet extraction. Determining the effects of the reaction period, reaction temperature, and monomer concentration on the grafting percentage was the main objective, and they were investigated systematically. The optimum reaction period, reaction temperature, monomer concentration, and initiator concentration were 60 min, 50°C, 47.15 × 10^?3 mol, and 3.92 × 10^?3 mol, respectively. The maximum percentage of grafting achieved under these optimum conditions was 173%. The presence of PMMA functional groups on OPEFB and the enormous reduction of the hydroxyl‐group absorption band in PMMA‐g‐OPEFB spectra provided evidence of the successful grafting reaction. The improvement of the thermal stability of PMMA‐g‐OPEFB also showed the optimal achievement of the grafting reaction of PMMA onto OPEFB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Optimized conditions for the grafting reaction of poly(methyl acrylate) onto rubberwood fiber

Graft copolymerization of poly(methyl acrylate) (PMA) onto rubberwood fiber (RWF) was carried out by free radical initiation. Hydrogen peroxide and ferrous ions were used as an initiator system. Effects of various parameters (reaction temperature and reaction time, as well as hydrogen peroxide, ferrous ammonium sulfate and monomer concentrations) on the grafting percentage were investigated. A high percentage of grafting was achieved when optimum reaction conditions were used. The optimum temperature of the reaction was determined to be about 55 °C and the reaction time was 120 min. The optimum concentration of H₂O₂ was 0.03 M and the amounts of Fe²⁺ and MA were 0.4 mmol and 0.05 mol, respectively. The PMA homopolymer was removed from the graft copolymer by Soxhlet extraction using acetone. The presence of PMA on the fiber was confirmed by FT-IR spectroscopy and gravimetry. The surface morphology of the poly(methyl acrylate)-graft-(rubberwood fiber) was studied by means of scanning electron microscopy. Copyright © 2004 Society of Chemical Industry     

Graft copolymerization of methyl methacrylate onto oil palm empty fruit bunch fiber using H2O2/Fe2+ as an initiator

Graft copolymerization of methyl methacrylate (MMA) onto oil palm empty fruit bunch fiber (OPEFB) was successfully carried out in aqueous medium using hydrogen peroxide as an initiator. Results from the investigation of the optimum conditions for grafting are presented. Maximum percentage of grafting was achieved when the amount of initiator, cocatalyst, and nitric acid were 5.877 × 10^?3 mol, 2.63 × 10^?4 mol, and 3.24 × 10^?3 mol, respectively. The optimum reaction temperature was 50°C and the reaction period was 120 min. The highest percentage of grafting and grafting efficiency were 220 and 47%, respectively, under optimum conditions. The grafted copolymer was characterized by FTIR spectroscopy and scanning electron microscopy. The presence of a band at 1730 cm^?1 provides strong evidence of grafting. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2233–2238, 2003     

Graft copolymerization onto starch. I. Complexes of Mn3+ as initiators

Advantages in using the pyrophosphate complex of trivalent managanese over the sulfate complex as initiator for graft copolymerization onto starch are discussed. The first successful attempts to graft copolymerize acrylonitrile, methyl methacrylate, and acrylamide to starch and starch derivatives are described using managanic pyrophosphate as initiator. Selective solvent extraction of the reaction products and very low conversions of monomer to homopolymer in absence of starch substrates provide evidence for high grafting efficiencies obtained with acrylonitrile and methyl methacrylate. With acrylamide as monomer, however, low grafting efficiencies and considerable amounts of homopolymer are obtained under the experimental conditions investigated. Reaction mechanisms responsible for initiation of graft copolymerization are discussed. These are (a) glycol cleavage in the anhydroglucose units by Mn³⁺ ions leading to formation of a radical, and (b) enolization and further oxidation of oxidized starch by Mn³⁺ ions also leading to radical species. Mechanisms are also proposed for homopolymerization through Mn³⁺ oxidation of enols which probably are formed by “vinylogous” addition of water molecules to acrylamide and methyl methacrylate.     

Studies on the grafting of methyl methacrylate onto polyacrylonitrile

Grafting of methyl methacrylate onto polyacrylonitrile was carried out using benzoyl peroxide as initiator and dimethylformamide as solvent. The occurrence of grafting was confirmed by IR spectroscopy and SEM analysis. Effects of various parameters such as reaction time, reaction temperature, initiator concentration, and monomer concentration on rate of polymerization, percentage grafting, and grafting efficiency were studied. The graft copolymers were found to have the similar thermal and structural properties like virgin polyacrylonitrile. Decreasing extent of swelling was observed for the polymers of higher percentage graft in polar solvents. © 1993 John Wiley & Sons, Inc.     

Grafting onto wool,XVII. Graft copolymerization of methyl acrylate and ethyl acrylate by use of VO(acac)2 as initiator. Comparison of monomer reactivities

Graft copolymerization of acceptor monomers methyl acrylate and ethyl acrylate onto Himachali wool fiber has been studied in aqueous medium by using vanadium oxyacetyl acetonate as initiator at 40, 50, 60, and 70°C. Graft copolymerization was carried out for various reaction periods and nitric acid was found to catalyse the reaction. Percentage of grafting and percent efficiency have been determined as functions of concentration of nitric acid, concentration of initiator, concentration of monomer, time, and temperature. Under optimum conditions, methyl acrylate and ethyl acrylate afforded maximum grafting to the extent of 28.4 and 18.5%, respectively. Relative reactivities of methyl acrylate and ethyl acrylate towards grafting have been compared with those of methyl methacrylate, acrylic acid and vinyl acetate reported earlier from this laboratory. Different vinyl monomers showed the following reactivity order: MMA > MA > EA > AAc > VAc. Several grafting experiments were carried out in the presence of various additives which included tert-butylhydroperoxide (TBHP), dimethylsulfoxide, pyridine, and dimethylformamide. Only TBHP was found to enhance grafting to a considerable extent, other additives decrease percent grafting of both methyl acrylate and ethyl acrylate.     

Synthesis and characterisation of PP-g-butyl acrylate copolymers

Butyl acrylate was grafted onto isotactic polypropylene using benzoyl peroxide as an initiator and toluene as a solvent. Effects of various parameters such as monomer and initiator concentration, reaction time and temperature on rates of polymerization, percentage grafting and grafting efficiency were studied. The extent of grafting achieved was 2.85%. The graft copolymers were characterized by IR, thermal, viscometric and contact-angle studies. Improved thermal stability and decreased intrinsic viscosity and critical surface tension were observed for graft copolymers.     

溶剂热法制备AS接枝马来酸酐的研究

以马来酸酐(MAH)为单体、苯乙烯(St)为共单体、过氧化二异丙苯(DCP)为引发剂,采用溶剂热法分别制备了苯乙烯-丙烯腈共聚物(AS)接枝物AS-g-MAH以及AS-g-(MAH-St).利用红外光谱对接枝物进行了结构表征,证明MAH已经成功接枝在AS链上.并用反式滴定法测定了接枝率,讨论了引发剂用量、马来酸酐用量、反应温度、反应时间、反应物浓度和共单体用量对接枝率的影响.结果表明:随着引发剂用量的增加和反应时间的延长,接枝率先增大,然后趋于平稳;随着马来酸酐用量、反应温度和反应物浓度的增加,接枝率先增大后下降;共单体苯乙烯的加入对接枝率的提高有很大的促进作用.     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatoargentate(III)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) using potassium diperiodatoargentate(III) [Ag(III)]–PVA redox system as initiator was studied in an alkaline medium. Some structural features and properties of the graft copolymer were confirmed by Fourier‐transfer infrared spectroscopy, scanning electron microscope, X‐ray diffraction and thermogravimetric analysis. The grafting parameters were determined as a function of concentrations of monomer, initiator, macromolecular backbone (X?_n = 1750, M? = 80 000 g mol^?1), reaction temperature and reaction time. A mechanism based on two single‐electron transfer steps is proposed to explain the formation of radicals and the initiation profile. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate and n‐butyl acrylate, were also used to produce graft copolymerizations. It has been confirmed that grafting occurred to some degree. Thermogravimetric analysis was performed in a study of the moisture resistance of the graft copolymer. Copyright © 2004 Society of Chemical Industry     

Grafting of vinyl monomers onto nylon-6. 1. Graft copolymerization of acrylamide onto nylon-6 using trivalent manganese as initiator

The use of trivalent manganese to initiate graft-copolymerization of acrylamide onto nylon-6 has been investigated. The rate of grafting has been determined by varying monomer, manganese(III), temperature and solvent mixtures. The graft yield increases with increasing monomer concentration up to 0.8 M and with further increase of monomer concentration the graft yield decreases. The percentage of grafting increases with managanese (III) ion concentration up to 5.25 × 10^?3 M and thereafter it decreases. The rate of reaction depends on temperature. Among the solvent composition studied, a water/solvent mixture containing 25% of the solvent seems to constitute the most favourable medium for grafting and with further increase of solvent composition, the graft yield decreases.     

A new simple procedure to calculate monomer reactivity ratios by using on-line 1H NMR kinetic experiments: Copolymerization system with greater difference between the monomer reactivity ratios

Free radical copolymerization reaction of vinyl acetate (VA) and methyl acrylate (MA) in solution of benzene-d₆ using benzoyl peroxide (BPO) as the initiator was studied with on-line ¹H NMR kinetic experiments at 60 °C. It was observed that composition drifts in the comonomer mixture with reaction progress is significant. Hence, the monomer reactivity ratios of VA/MA system could be calculated by the data collected only from one sample via on-line following the comonomer mixture and copolymer compositions at different reaction time intervals up to medium overall monomer conversions. The results were in good agreement with the literature data reported for this system. The good fitting between theoretical and experimental changes in the comonomer mixture compositions as a function of reaction progress was observed, indicating the accuracy of the monomer reactivity ratios calculated by the new procedure presented here.     

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

The feasibility of a cellulose thiocarbonate–azobisisobutyronitrile (AIBN) initiation system to induce graft copolymerization of methyl methacrylate (MMA) and other acrylic monomers onto cotton fabric was investigated. Other acrylic monomers were acrylic acid, acrylonitrile, and methyl acrylate. The initiation system under investigation was highly activated in the presence of a metal‐ion reductant or a metal‐ion oxidant in the polymerization medium. A number of variables in the grafting reaction were studied, including AIBN concentration, pH of the polymerization medium, nature of substrate, monomer concentration, duration and temperature of polymerization, and composition of the solvent/water polymerization medium. The solvents used were methanol, isopropanol, 1,4‐dioxane, cyclohexane, benzene, dimethyl formamide, and dimethyl sulfoxide. There were optimal concentrations of AIBN (5 mmol/L), MMA (8%), Fe²⁺ (0.1 mmol/L), Mn²⁺ (8 mmol/L), and Fe³⁺ (2 mmol/L). A polymerization medium of pH 2 and temperature of 70°C constituted the optimal conditions for grafting. The methanol/water mixture constituted the most favorable reaction medium for grafting MMA onto cotton fabric by using the Fe²⁺–cellulose thiocarbonate–AIBN redox system. MMA was superior to other monomers for grafting. The unmodified cotton cellulose showed very little tendency to be grafted with MMA compared with the chemically modified cellulosic substrate. A tentative mechanism for the grafting reaction was proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1261–1274, 2004     

Graft copolymerization of vinyl monomers onto chitin with cerium (IV) ion

Graft copolymerization of vinyl compounds onto chitin was studied, and an efficient and reproducible procedure has been established, cerium (IV) being used as the initiator. The reactions with acrylamide and acrylic acid onto powdery chitin were carried out under various conditions to elucidate the polymerization behavior in terms of grafting percentage. The amount of cerium (IV) affected the polymerization most strikingly, and grafting percentages showed maxima with suitable amounts of initiator for both the monomers. As a solvent water proved to be superior to aqueous nitric acid except the reaction with a small amount of initiator. Under appropriate conditions, around 240 and 200% grafting percentages were achieved for acrylamide and acrylic acid, respectively. The resulting graft copolymers showed much improved affinity for solvents and hygroscopicity compared to the original chitin.     

Peroxydiphosphate–metal ion–cellulose thiocarbonate redox system‐induced graft copolymerization of vinyl monomers onto cotton fabric

The grafting of methacrylic acid (MAA) and other vinyl monomers onto cotton cellulose in fabric form was investigated in an aqueous medium with a potassium peroxydiphosphate–metal ion–cellulose thiocarbonate redox initiation system. The graft copolymerization reaction was influenced by peroxydiphosphate (PP) concentration, the pH of the reaction medium, monomer concentration, the duration and temperature of polymerization, the nature of vinyl monomers, and the nature and concentration of metallic ions (activators). On the basis of a detailed investigation of these factors, the optimal conditions for the grafting of MAA onto cotton fabric with the said redox system were as follows: [Fe²⁺] = 0.1 mmol/L, [PP] = 2 mmol/L, [MAA] = 4%, pH‐2, grafting time = 2 h, grafting temperature = 70°C, and material/liquor ratio = 1 : 50. Under these optimal conditions, the graft yields of different monomers were in the following sequence: MAA ? acrylonitrile > acrylic acid > methyl acrylate > methyl methacrylate. The unmodified cellulosic fabric (the control) had no ability to be grafted with MAA with the PP–Fe²⁺ redox system. The percentage of grafting onto the thiocarbonated cellulosic fabric was more greatly enhanced in the presence of iron salts than in their absence. This held true when the lowest concentrations of these salts were used separately. A suitable mechanism for the grafting processes is suggested, in accordance with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1879–1889, 2003     

Synthesis and characterization of graft copolymers of ethyl acrylate/acrylamide mixtures onto starch

Graft copolymerization of ethyl acrylate/acrylamide onto corn starch using potassium permanganate–citric acid initiation system was investigated. Major factors affecting the polymerization reaction were thoroughly investigated in terms of initiator concentration, monomer concentration, polymerization time, polymerization temperature, and starch/liquor, and the obtained results implied that the polymer yield which were expressed by total monomer conversion, grafting ratio, and grafting efficiency were determined by these factors. The optimum reaction conditions were as follows: starch, 30 g; potassium permanganate (based on weight of starch), 0.1%; citric acid (based on weight of starch), 0.5%; ethyl acrylate, 20%; acrylamide, 0.4 g; time, 3 h; temperature, 40°C; starch/liquor, 1:3. We concluded that the initiator of potassium permanganate–citric acid system could be used as a cheap initiator in manufacturing the starch graft copolymer. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of vegetable tannin-vinyl graft copolymers part I. Cutch-poly(methyl acrylate) graft copolymers

New graft copolymers were synthesized by grafting methyl acrylate onto cutch, a vegetable tanning agent, in acetic acid medium with hydrogen peroxide as the initiator. The graft copolymers were characterized by infrared spectroscopy and thermogravimetric analysis. The dependence of the percentage of grafting, monomer conversion, efficiency of grafting and rate of grafting on the concentrations of initiator, acetic acid, and cutch were investigated. The optimum experimental conditions for grafting were obtained. A probable mechanism of grafting was also proposed.     

Thermal behavior of graft copolymers of cotton cellulose and acrylate monomers

Cotton cellulose yarn was grafted with methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate at various percentages of grafting. The effects of concentration of the initiator, concentration of the acid, and of temperature on grafting was studied and the mechanism discussed. The effect of reactivity of the monomer on the percentage graft-on is pointed out. Thermal behavior of natural and grafted cotton yarn was studied using dynamic thermogravimetry in air at a heating rate of 6°C/min up to a temperature of 500°C. The thermal stabilities of the samples grafted with various acrylate monomers to various percentages of grafting were computed from their primary thermograms by calculating the values of IDT, IPDT, and E^*. The results show that the thermal stability increases with increase in graft-on per cent, and the thermal stabilities of natural cotton and cotton grafted with different monomers are in the order ethyl > methyl > natural cellulose > methyl methacrylate > n-butyl acrylate.     

丙烯酰氧基螺噁嗪接枝羧甲基甲壳素反应条件的研究

采用接枝共聚法合成了一种具有螺噁嗪侧基的羧甲基甲壳素水溶性衍生物。讨论了反应温度、反应时间、引发剂用量、溶剂用量、单体用量对丙烯酰氧基螺噁嗪接枝羧甲基甲壳素反应的影响。接枝效率最高时反应条件为:羧甲基甲壳素0.4 g,溶剂水50.0 mL,引发剂0.35 mmol,单体3.0 mmol,反应温度70℃,反应时间4.0 h,接枝率为65.0%,接枝效率为25.2%。