Grafting of methyl methacrylate onto Antheraea pernyi silk fiber with the assistance of supercritical CO2

Graft copolymerization of methyl methacrylate (MMA) onto Antheraea pernyi silk fibers, initiated by benzoyl peroxide in the supercritical CO₂ was investigated. The grafting degree was determined as a function of impregnating pressure, impregnating time, monomer concentration, initiator concentration, and reaction time. The structural properties of MMA‐grafted fiber were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Grafted MMA was chemically bonded and/or physically adhered to the surfaces of the fibers. The grafted silk fibers exhibited two steps of weight loss according to the characteristic of each component as demonstrated by the thermogravimetric analysis. The water‐retention values indicated that the hydrophobic nature of the fibers was improved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1299–1305, 2006     

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     

Grafting of methyl methacrylate (MMA) onto Antheraea assama silk fiber

Graft copolymerization of methyl methacrylate (MMA) onto nonmulberry silk fiber Antheraea assama was investigated in aqueous medium using the KMnO₄–oxalic acid redox system. Grafting (%) was determined as a function of the reaction time, temperature, and monomer and initiator concentrations. The rate of grafting increased progressively with increase of the reaction time up to 4 h and then decreased. The extent of grafting was maximum at 55°C. The extent was also dependent upon monomer and initiator concentrations up to 75.5 × 10^?2 and 6 × 10^?3 M, respectively. The grafted products were evaluated by infrared spectroscopy and their thermal decompositions were studied by TG and DTG techniques in static air at 20°C min^?1 and 30°C min^?1 in the range 30–800°C. The kinetic parameters for ungrafted and grafted fibers were evaluated using the Coats and Redfern method. The grafted products were found to be thermally more stable than were those of the ungrafted fibers. The surface characteristics of the ungrafted and grafted fibers were evaluated by scanning electron microscopy. The water‐retention values (WRVs) of the grafted fibers were in decreasing order with increase in the grafting (%). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2633–2641, 2001     

Synthesis and kinetics of ascorbic acid initiated graft copolymerized delignified cellulosic fiber

Graft copolymerization of delignified Grewia optiva fiber with methyl methacrylate (MMA) as vinyl monomer was attempted using ascorbic acid/H₂O₂ as redox initiator. Different reaction conditions affecting the grafting percentage (P_g) were optimized to get the maximum P_g (32.56%) of MMA onto delignified Grewia optiva fibers. Grafted and ungrafted fibers were subsequently subjected to evaluation of physico‐chemical properties such as swelling behavior and acid and alkali resistance. The rate expression for the grafting reaction (R_g = k [ASC]^0.12 [H₂O₂]^0.53 [MMA]^0.05) was evaluated and a suitable mechanism for grafting was suggested. The overall activation energy of the copolymerization reaction was found as 11.97 kJ mol^?1 at temperature range 25–65°C. Further, morphological and structural analysis of raw, delignified, and grafted Grewia optiva‐g‐poly(MMA) were studied by using Fourier‐transform Infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis.The tensile properties of grafted and ungrafted fiber samples were also reported. POLYM. ENG. SCI., 55:474–484, 2015. © 2014 Society of Plastics Engineers     

Radiation‐modified copolymer for the extraction of metal ions from water

The modification of heavy‐duty polyethylene films was carried out through the graft copolymerization of acrylamide and vinyl acetate mixtures of different compositions with the simultaneous radiation method. The influence of the synthesis conditions (the irradiation dose, comonomer composition, and dilution) on the degree of grafting was investigated. The grafted samples were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, and differential scanning calorimetry. The effect of the grafting degree on the thermal stability of the modified polymer was examined. The extraction of heavy and toxic metals such as cadmium, cobalt, copper, nickel, and lead by the modified heavy‐duty polyethylene was evaluated, and the metal‐ion uptake by the grafted and chemically treated samples seemed better than that of the grafted and untreated ones. Both the rate and amount of the metal‐ion uptake were affected by the temperature of the feed solution and the grafting degree. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Controlling the phase stability of polymer blends through the introduction of impenetrable interfaces

In this work, the effect of the introduction of modified solid surfaces into polymer blends on the phase‐separation process was investigated. Glass fibers with surfaces having different chemistries were introduced into polystyrene–poly(methyl methacrylate) blends. The glass fibers used either had fully hydrated surfaces or had surfaces covered with a random copolymer, poly(styrene‐co‐methyl methacrylate). The copolymer was synthesized by free‐radical polymerization of styrene and methyl methacrylate in the presence of previously vinyl silane‐treated glass fibers. The copolymerization and grafting procedures were investigated by FTIR and thermal analysis. Blends containing the fibers were studied using FTIR microscopy and optical microscopy. FTIR microscopy results showed that the composition of the phases in the blends was shifted by using fibers with different surface chemistries. Fibers with grafted copolymers were capable of narrowing the immiscibility region in the phase diagram, while fully hydrated fibers were able to expand the gap. It was proposed that interfacial interactions regulated by a hydrophilic–hydrophobic type of forces were responsible for guiding the described phase‐separation process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1619–1627, 2003     

Chemical and mechanical properties of butyl methacrylate grafted wool fiber

Because polymer‐grafted wool fibers had been reported to have better functional performance, a K₂S₂O₈–NaHSO₃ redox system was used as the initiator for the grafting copolymerization of butyl methacrylate (BMA) onto wool fibers. Grafted samples of wool‐g‐BMA with different grafting percentages (5.2–25.86) were obtained through variations in the monomer concentration in the reaction system. The evidence for grafting was provided by scanning electron microscopy and infrared spectroscopy. After the grafting, the moisture retention of the wool‐g‐BMA fibers decreased slightly. Optical measurements showed that the birefringence decreased, indicating a lower degree of molecular orientation of the wool‐g‐BMA fibers. The tensile strength increased as the grafting percentage increased. Beyond an 18–25% grafting percentage, the elongation at break decreased, and this indicated a reduction of the elastic deformation, which meant that the flexibility of the modified fibers may have deteriorated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3813–3817, 2004     

Study of methyl‐methacrylate‐viscose fiber graft copolymerization and the effect of grafting on thermal properties

The graft copolymerization of methyl‐methacrylate onto viscose fibers was studied under photoactive conditions with visible light using Ce⁴⁺/Ti³⁺ combination as redox initiator in a limited aqueous medium. Polymerization conducted in the presence of light at 30 ± 1°C produced significant grafting, compared with that conducted in the dark under the same conditions. The % grafting, % total conversion, and % grafting efficiency were studied by varying time, monomer concentration, initiator concentration, and pH of the medium. The mechanism of polymerization and graft copolymer formation have been discussed. Characterization of the grafted fibers was done by Fourier transform infrared spectroscopy and scanning electron microscopy. The effect of % grafting on thermal properties was studied by thermogravimetric analysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 135–140, 1999     

Chemical modification of jute fibers. II: A study on the Fe2+/H2O2-initiated graft copolymerization of methyl methacrylate,acrylonitrile, and acrylamide onto jute fibers

The study of graft copolymerization of methyl methacrylate, acrylonitrile, and acrylamide onto both defatted and bleached jute fibers using the ferrous ammonium sulfate / H₂O₂ redox initiator system has been made. To determine the optimum conditions of grafting, the effects of concentrations of ferrous ammonium sulfate, monomer, H₂O₂; time and temperature on percentage of graft yield have been studied. Acrylamide was found to graft onto the fiber only at a fixed ferrous ammonium ion concentration (5 × 10^?4M). Kinetic studies showed that the rates of grafting follow the second-order mechanism. The activation energies of the reactions were found to be 3.351 and 2.53 kcal/mol in the methyl methacrylate and acrylonitrile systems, respectively. The grafted fibers have been characterized by thermogravimetric analysis, IR spectroscopy, and XRD studies.     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001     

Modification of pristine multiwalled carbon nanotube by grafting with poly(methyl methacrylate) using benzoyl peroxide initiator

Multiwalled carbon nanotube was successfully grafted with poly(methyl methacrylate) by free radical mechanism using benzoyl peroxide initiator. The reaction was carried out in situ, where the initiator and methyl methacrylate monomer generated the polymer‐free radical that was subsequently grafted to the surface of the pristine multiwalled carbon nanotube. The multiwalled carbon nanotube grafted poly(methyl methacrylate) (MWCNT‐g‐PMMA) were characterized using Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, ¹³ C‐solid NMR spectroscopy, X‐ray photoelectron spectroscopy, and scan electron microscopy. From the result of the characterizations, the grafting of poly(methyl methacrylate) on to multiwalled carbon nanotube was confirmed, and a percentage grafting of 41.51% weight was achieved under optimized conditions with respect to the temperature and the amount of the initiator. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43270.     

Grafting of poly (methyl acrylate) onto sulfite pulp fibers and its effect on water absorbance

To prepare super water absorbent hydrogels of wood cellulose fibers, poly (methyl acrylate) (PMA) was copolymerized onto softwood sulfite pulp fibers using free radical initiator followed by alkaline hydrolysis. Ceric ammonium nitrate (CAN) was used as the free radical initiator. Effects of various parameters such as fiber concentration, monomer/pulp (M/pulp) ratio, CAN concentration, and reaction time on the grafting yield and on other grafting parameters were investigated. The graft conversion was the same from low to medium fiber concentration. The amount of initiator required was found to be independent of fiber concentration to achieve maximum grafting yield. Different fiber fractions (classified based on their length) have no effect on the grafting yield. The evidence of graft copolymerization was determined by using ATR‐IR spectroscopy. The X‐ray diffraction (XRD) analysis shows that grafting takes place both in amorphous and crystalline regions of cellulose fibers and the decrease in crystallinity of the grafted fibers with an increase in grafting yield was confirmed. The surface morphology of the PMA‐g‐cellulose was characterized by scanning electron microscopy (SEM). The water retention value of the hydrolyzed grafted pulp was determined based on a centrifugation technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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     

Surface modification of acrylonitrile copolymer membranes by grafting acrylamide. I. Initiation by ceric ions

Surface modification of membranes of an acrylonitrile copolymer (PAN) containing 5.5% methyl methacrylate (MMA) and 4.0% sodium methylpropylenesulfonate by grafting acrylamide (AAm) with cetric ammonium nitrate as initiator in the aqueous medium has been studied. Results showed that the extent of grafting was varied with some parameters, such as dimethyl formamide and Tween-20 amount in the reaction solution, concentration of AAm, and reaction time. The grafted copolymer was verified by infrared spectra and X-ray photoelectron spectroscopy. Both of these methods also showed that the ester group of MMA unit on the surface of PAN membranes may be partially hydrolyzed into carboxyl group in the copolymerization condition. Surface and pore structures of PAN membranes after grafting were viewed under a scanning electron microscope (SEM). From SEM photos we know that AAm homopolymer branches were grafted onto the surface of the membrane and the morphology of membrane did not change. Results of contact angle of isooctane on the membrane under water showed that the wettability of the modified membrane was improved. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1521–1529, 1997     

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.     

Fe~(2+)-H_2O_2-二氧化硫脲引发绒毛浆与MMA接枝共聚的研究

研究了Fe2+-H2O2-二氧化硫脲体系引发绒毛浆与甲基丙烯酸甲酯的接枝共聚。考察了该引发体系下反应温度、反应时间、过氧化氢用量、二氧化硫脲用量、单体浓度和液比对接枝率和接枝效率的影响。并用红外光谱对接枝纤维产物进行了鉴定。结果表明,二氧化硫脲的加入能有效地使接枝共聚得以顺利进行;适当地提高温度,增加单体浓度,控制合适的二氧化硫脲用量都能提高接枝率和接枝效率,并在较短的时间就能成功接枝;接枝效率几乎不受液比的影响,一般维持在90%以上,接枝过程产生的均聚物极少。     

Photograft copolymerization of methyl methacrylate on silk fiber using titanium(III) chloride–potassium persulphate redox initiator in a limited aqueous system. I

Graft copolymerization of methyl methacrylate (MMA) onto mulberry silk fibers has been investigated in a limited aqueous system employing titanium(III) chloride–K₂S₂O₈ as the redox initiator under a photoactive condition with visible light. Polymerization in the presence of light at 32 ± 1°C has been found to be more pronounced than in the dark under identical conditions. The percentage of grafting, the percentage of total conversion, and the percentage of grafting efficiency have been studied by varying the reaction time, concentration of monomer, initiator concentration, solvent composition, and pH of the medium. A high percentage of grafting (∼ 93%), high grafting efficiency (∼ 97%), and the percentage of total conversion (∼ 25%) have been obtained with little homopolymer formation. Characterization of the grafted fibers has been investigated by Fourier transform infrared spectroscopy and scanning electron microscopy. Finally, the reaction mechanism has been discussed by considering hydrogen bonding. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2187–2193, 1999     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000     

Methyl methacrylate modification of polyolefin in a batch mixer and a twin‐screw extruder experiment and kinetic model

Free radical grafting with methyl methacrylate onto molten polypropylene was investigated in both an internal mixer and a modular co‐rotating twin‐screw extruder. There has been little open literature on melt free radical grafting copolymerization of methyl methacrylate. There is also little information on the evolution of grafting reaction with respect to reaction time in an internal mixer and along the screw axes with methyl methacrylate. The influence of residence time on the degree of grafting in an internal mixer and a twin‐screw extruder was studied through measuring reaction yields with respect to reaction time in a mixer and evolution of reaction yield along the screw axis. The degree of grafting increased with initial monomer and peroxide concentration. The grafting reactions with three different peroxides were also investigated. The grafting levels were similar to maleic anhydride and suggested that only an individual methyl methacrylate unit be grafted. The melt viscosity was dramatically reduced with addition of peroxide. A kinetic scheme of our reaction system for methyl methacrylate was proposed and compared with the experimental results.     

Atmospheric plasma‐aided biocidal finishes for nonwoven polypropylene fabrics. I. Synthesis and characterization

Novel biocidal fabrics were synthesized by the graft copolymerization of glycidyl methacrylate (GMA) onto plasma‐treated nonwoven polypropylene (PP) to produce PP/GMA grafts. Atmospheric oxygenated helium plasma was used to enhance the PP fabrics' initiation before GMA grafting. The grafted PP/GMA epoxide group was reacted with β‐cyclodextrin, monochlorotrizynyl‐β‐cyclodextrins, or a quaternary ammonium chitosan derivative [N‐(2 hydroxy propyl) 3‐trimethylammonium chitosan chloride]. Some interesting biocidal agents were complexed into the cyclodextrin (CD) cavity of PP/GMA/CD grafted fabrics. Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and optical and scanning electron microscopies were used to characterize the grafted complexed fabrics. These synthesized biocidal fabrics proved to be antistatic, antimicrobial, and insect‐repelling (see part II of this study). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1900–1910, 2007