Ultraviolet-initiated photografting of glycidyl methacrylate onto styrene–butadiene rubber

Photografting reaction onto styrene–butadiene rubber (SBR) as a function of monomer concentration, grafting method, irradiation time, and the carbon black content has been studied using ultraviolet (UV). Glycidyl methacrylate and benzophenone are used as monomer and initiator, respectively. The occurrence of graft reaction onto SBR surface is identified by infrared attenuated total reflection (IR-ATR) analysis. The degree of monomer graft increases with monomer concentration and tends to level off at high monomer concentration (>8.3M/L). Graft ratio also increases with UV irradiation time. Carbon black content is found as one of important factors that determine the monomer graft efficiency. The amount of monomer graft onto SBR decreases with increasing carbon black content and it is attributed to the reduction of irradiation absorbance due to the presence of carbon black. The occurrence of reaction between glycidyl methacrylate grafted SBR and nylon-6 via melt phase reaction is also identified using IR-ATR analysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1733–1739, 1999     

Vapor phase photografting on low-density polyethylene film in binary monomer systems

Vapor phase photografting of monomer mixtures on low-density polyethylene film, on which benzoyl peroxide is coated, was investigated at 60°C using various vinyl, allyl, and solid monomers. Styrene (St) itself was difficult to graft on the film substrate, but the combinations of St with vinyl monomers such as acrylonitrile (AN), glycidyl methacrylate (GMA), acrylic acid, and methacrylic acid led to the accelerated grafting, affording a maximum percent grafting at an certain monomer ratio. The same combination effect was observed for AN–N-vinyl pyrrolidone and –GMA monomer mixtures. The monomer combinations such as allyl aldehyde–St and allyl alcohol–maleic anhydride were useful for performing the grafting of allyl monomers effectively. Maleic anhydride and maleimide as solid monomers were also possible to introduce into the film substrate by means of the monomer combination, where St, N-vinyl pyrrolidone, vinyl ethers, and benzyl methacrylate were available as comonomers. Thus, the monomer combinations affording an accelerating effect on grafting may be monomer pairs rich in an alternative copolymerizability, suggesting that monomer reactivity ratio controls a major factor for the combination effect. It was confirmed from IR study on grafted films that both monomer components are introduced in the film substrate as the grafted chain component.     

The γ-radiation induced grafting of unsaturated segmented polyurethanes with N-vinyl pyrrolidone

Linear unsaturated segmented polyurethanes have been modified by hydrophilic grafting at 40°C with N-vinyl pyrrolidone, in N,N-dimethylformamide as solvent, using ⁶⁰cobalt γ-irradiation. Graft copolymers were isolated from homopolymers by selective solvent extraction using a Soxhlet apparatus. The effects of reaction time, total dose, temperature and monomer concentration, on the graft yields have been examined. Relatively high irradiation doses were avoided during the grafting experiments to prevent possible degradation of the segmented polyurethanes and gelation of the homopolymer, poly(N-vinyl pyrrolidone). The ungrafted and grafted copolymers were characterized, and the graft copolymers were shown to be more thermally stable than the original polyurethanes, by thermogravimetric analysis. An explanation for the observed variation of the graft yields with some of the experimental variables is suggested.     

Studies on the curing behaviour and mechanical properties of styrene/methyl methacrylate grafted deproteinized natural rubber latex

The graft copolymerization of styrene/methyl methacrylate (MMA) onto deproteinized natural rubber (DPNR) latex was carried out using ammonium peroxy disulfate (N₂H₈O₈S₂) as the initiator. The presence of the grafted polystyrene (PS) and polymethyl methacrylate (PMMA) on the rubber backbone was confirmed by FTIR spectroscopy. The effects of monomer concentrations on curing characteristics and mechanical properties were studied. It was found that the cure time and scorch time were increased with increasing monomer concentration whereas the torque_max–min value was slightly decreased. It was also noted that the increase in the monomer concentration resulted in stiffer rubber with increased modulus and reduced elongation at break.     

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     

Grafting of vinyl monomers onto natural rubber,II. Graft copolymerization of methyl methacrylate onto natural rubber using tetravalent ceric ions

The use of tetravalent ceric ions to initiate graft-copolymerization of methyl methacrylate onto natural rubber (NR) has been investigated. The rate of grafting has been determined by varying the concentration of monomer and cerium(IV), the temperature and the solvents. The graft yield increases with increasing monomer concentration up to 1.877 M, with further increase of the monomer, the graft yield decreases. The percentage of grafting increases with increasing cerium(IV) concentration up to 0.035 M, thereafter it decreases. With increasing temperature the graft yield increases. The effect of CuSO₄ on the rate of grafting has also been investigated. A plausible mechanism has been suggested and the kinetic rate expressions have been derived.     

Hydrogel coating of RVNRL film by electron‐beam irradiation

The tackiness properties of radiation‐vulcanized natural rubber latex (RVNRL) film surfaces coated by various monomers were investigated in order to define the suitable hydrogels which reduce the tackiness of the film. In this context, different types of monomers, namely, N‐vinyl‐2‐pyrrolidone (NVP), N,N‐dimethylaminoethylamide (DMAEA), acrylic acid (AAc), n‐butyl acrylate (n‐BA), and 2‐hydroxyethyl methacrylate (HEMA) as well as the monomer mixtures were tried with varying degrees of success. Coating the RVNRL film with 80% HEMA/20% n‐BA by irradiation at 80 kGy using a low‐energy electron beam gave a remarkable reduction in the surface tackiness of the RVNRL film. Several other attempts were made such as priming the RVNRL film with acid and aluminum sulfate prior to coating, mixing the aluminum sulfate into the monomer mixtures, and dipping the partially wet RVNRL film into the monomer to enhance the wettability of the monomers with the film. The photomicrographs taken illustrate that the decrease in tackiness with the coating is due to the increase of the surface roughness at an 80‐kGy irradiation dose. The studies also revealed that the reduction in the contact angle and the increase in water absorption of the RVNRL film after irradiation are due to the formation of the hydrogel layer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1421–1428, 1999     

Free radical solution copolymerization of glycidyl methacrylate with n-vinyl pyrrolidinone

Copolymers of glycidyl methacrylate (monomer 1) with N-vinyl pyrrolidinone (monomer 2) were prepared at 70°C in low yield by free radical initiated solution polymerizations in ethyl acetate, 1,4-dioxane and mixtures of the two solvents. Copolymer compositions were determined by proton nuclear magnetic resonance spectroscopy. Monomer reactivity ratios were then derived using the method of Kelen & Tudos. The magnitude of r₁ was relatively unaffected by solvent composition, and ranged from 4.32 to 4.53 in a random fashion. In contrast, values of r₂ showed a greater relative (but still random) spread from 0.0075 to 0.0147. Copolymers prepared by batch polymerization are selectively enriched with GMA monomer.     

Wood-Plastic Composite with Methylmethacrylate in Presence of Novel Additives

Wood–plastic composites (WPC) were prepared with kadom and mango wood of Bangladesh under Co-60 gamma irradiation using methylmethacrylate (MMA) as the bulk monomer mixed with methanol (swelling solvent) at different proportions in presence of a number of additives such as N-vinyl pyrrolidone, tripropylene glycol diacrylate, trimethylol propane triacrylate, copper sulfate, sulfuric acid, and urea. Composites prepared with urea, NVP, and CuSO₄ possess better tensile and protective properties.     

Process variables and their effects on grafting reactions of styrene and methyl methacrylate onto natural rubber

The graft copolymerization of styrene and methyl methacrylate onto natural rubber latex was studied under various reaction conditions using a cumene hydroperoxide redox initiator. The monomer conversion, graft copolymer compositions, and grafting efficiency were determined. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis and differential scanning calorimetry (DSC). A 2 fractional factorial experimental design was applied to study the main effects on the grafting. The variables investigated in this work were the amount of the initiator and emulsifier, the presence or absence of a chain‐transfer agent, the styrene‐to‐methyl methacrylate ratio, the monomer‐to‐rubber ratio, and the reaction temperature. The measured response for the experimental design was the grafting efficiency. The analysis of the results from the design showed the sequence of the main effects on the observed response of the grafting of styrene and methyl methacrylate onto natural rubber, in ascending order. The amount of the chain‐transfer agent and the reaction temperature in the range of the test had significant effects and one marginally significant effect was the monomer‐to‐rubber ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 63–74, 2003     

Graft copolymers of microcrystalline cellulose as reinforcing agent for elastomers based on natural rubber

In the present study, free radical graft copolymerization of acrylic monomers and microcrystalline cellulose (MCC) was applied to develop a biopolymer for natural rubber reinforcements. The copolymerization was carried out in aqueous media. Cerium ammonium nitrate was employed as the initiator in the presence of nitric acid. Acrylic monomers used in the copolymer synthesis were ethyl acrylate (EA) and butyl acrylate (BA). Effects of monomer concentration, initiator concentration, polymerization time, and polymerization temperature on the obtained graft copolymers were investigated. The graft parameters were obtained by thermal gravimetric analysis method. The obtained copolymers (MCC‐g‐PEA, MCC‐g‐PBA) were characterized by attenuated total reflection, wide‐angle X‐ray diffraction, field‐emission electron microscopy, and thermal gravimetric analysis. In comparison to native MCC, better thermal stability of graft copolymers were observed. In addition, the graft copolymers reinforced natural rubber composites were produced, and sulfur was used as the vulcanizing agent. Their vulcanization and mechanical properties were characterized. Comparing to the native MCC reinforced natural rubber composites, the copolymers reinforced natural rubber composites shows improved mechanical properties, indicating the copolymer's potential application as rubber reinforcements. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43087.     

Graft copolymerization onto rubber. VII. Graft copolymerization of methyl methacrylate onto rubber using potassium peroxydisulfate catalyzed by silver ion

The graft copolymerization of methyl methacrylate onto natural rubber (NR) was carried out varying the concentration of monomer, initiator, thiourea, and silver nitrate over a wide range. The grafting reaction was temperature-dependent. From the Arrhenius plot, the overall energy of activation was computed. A suitable reaction scheme and rate expression for the rate of polymerization was suggested.     

Effects of electron irradiation on physical properties of rubber/cellulose fibre composites

Short term stress–strain properties were investigated for natural rubber reinforced with short cellulose fibres at various fibre loads. Stress–strain measurements were also performed on natural rubber composites containing cellulose fibres, electron irradiated in the presence of butadiene or N-hydroxymethylacrylamide, where the latter monomer produced the greatest improvement in stress–strain properties. Chemiluminescence analysis indicated the existence of a surface layer on the fibres after irradiation treatments, and water absorption measurements showed a decrease in water uptake for composites containing irradiated fibres. The results demonstrate the improvement of mechanical properties with a reduced sensitivity to moisture.     

Graft copolymerization of methyl methacrylate from brominated poly(isobutylene‐co‐isoprene) via atom transfer radical polymerization

Commercial brominated poly(isobutylene‐co‐isoprene) (BIIR) rubber has been directly used for the initiation of atom transfer radical polymerization (ATRP) by utilizing the allylic bromine atoms on the macromolecular chains of BIIR. The graft copolymerization of methyl methacrylate (MMA) from the backbone of BIIR which was used as a macroinitiator was carried out in xylene at 85 °C with CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as a catalytic complex. The polymerization conditions were optimized by adjusting the catalyst and monomer concentration to reach a higher monomer conversion and meanwhile suppress macroscopic gelation during the polymerization process. This copolymerization followed a first‐order kinetic behavior with respect to the monomer concentration, and the number‐average molecular weight of the grafted poly(methyl methacrylate) (PMMA) increased with reaction time. The resultant BIIR‐graft‐PMMA copolymers showed phase separation morphology as characterized by atomic force microscopy, and the presence of PMMA phase increased the polarity of the BIIR copolymers. This study demonstrated the feasibility of using commercial BIIR polymer directly as a macromolecular initiator for ATRP reactions, which opens more possibilities for BIIR modifications for wider applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43408.     

Synthesis and characterization of microcrystalline cellulose‐graft‐poly(methyl methacrylate) copolymers and their application as rubber reinforcements

In this study, redox‐initiated free radical graft copolymerization of microcrystalline cellulose (MCC) and methyl methacrylate (MMA) has been carried out in aqueous media to develop a novel cellulose‐based copolymer. Cerium ammonium nitrate was used as the initiator in the presence of nitric acid. Effects of monomer concentration, initiator concentration, polymerization time, and polymerization temperature on the graft parameters of copolymers were studied. The successful grafting copolymerization between MCC and MMA was validated through attenuated total reflection, wide‐angle X‐ray diffraction, field‐emission scanning electron microscopy, and thermal gravimetric analysis. In comparison to native MCC, the resultant copolymers exhibited enhanced thermal stability and better compatibility with natural rubber, suggesting its potential application as reinforcement material in rubber industry. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42666.     

Antifouling microfiltration membranes prepared from poly(vinylidene fluoride)‐graft‐Poly(N‐ vinyl pyrrolidone) powders synthesized via pre‐irradiation induced graft polymerization

Poly(vinylidene fluoride) (PVDF) powders were grafted with N‐vinyl pyrrolidone using the pre‐irradiation induced graft polymerization technique. The effects of reaction time, absorbed dose, and monomer concentration on the degree of grafting were investigated, and the grafted PVDF powders were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. The grafted PVDF powders were also cast into microfiltration (MF) membranes via the phase‐inversion method. The contact angle and water uptake were measured. The membrane morphology was studied by scanning electron microscopy, and the water filtration properties of the membranes were tested. The antifouling properties were determined through measurements of the recovery percentage of pure water flux after the MF membranes were fouled with bovine serum albumin solution. The results confirmed that the existence of poly(N‐vinyl pyrrolidone) (PVP) graft chains improved the hydrophilicity and antifouling properties of the MF membranes cast from PVDF‐g‐PVP powders. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

N-vinyl pyrrolidone-assisted free radical functionalization of glycidyl methacrylate onto styrene-b-(ethylene-co-butylene)-b-styrene

N-vinyl pyrrolidone (NVP)-assisted free radical functionalization of glycidyl methacrylate (GMA) onto styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) was investigated to attempt to overcome the low grafting reactivity of GMA and the low efficiency of the styrene (St)-assisted functionalization method. By using the optimal amount of NVP, the degree of GMA grafting was increased by at least 7.5 and 2.5-fold when compared to GMA alone and the St-assisted grafting procedure, respectively. Also, no apparent cross-linking or degradation reactions of SEBS were observed. It was proposed that NVP reacted first with SEBS macroradicals, and then the resulting NVP-macroradicals copolymerized with GMA to produce high degrees of grafting of both GMA and NVP onto SEBS.     

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.     

Synthesis of graft copolymers from natural rubber using cumene hydroperoxide redox initiator

The graft copolymerization of 50/50 (w/w) styrene/methyl methacrylate mixtures onto natural rubber seed latex were carried out by using cumene hydroperoxide/sodium formaldehyde sulfoxylate dihydrate/EDTA‐chelated Fe²⁺ as a redox initiator. The effects of the process factors such as the amount of initiator, emulsifier, and chain‐transfer agent; monomer‐to‐rubber ratio; and temperature on the grafting efficiency (GE) and grafting level (GL) are reported. The mechanism of graft copolymerization was investigated. The synthesized graft copolymers were purified and then characterized by proton nuclear magnetic resonance (¹H‐NMR) analysis. Transmission electron microscopy (TEM) was used to study the morphology of the graft copolymers. It appears that the formation of graft copolymers occurs on the surface of the latex particles through a chain‐transfer process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2993–3001, 2002; DOI 10.1002/app.2328     

From a laboratory to a pilot scale production of natural rubber grafted with PMMA

Graft copolymers of natural rubber and poly (methyl methacrylate) (NR‐g‐PMMA) were prepared in a laboratory scale, and then extended to a pilot scale production. Reaction conditions were first assessed based on a preparation in the laboratory scale with a reactor capacity of 1.5 l. An optimum grafting efficiency was obtained when cumene hydroperoxide/tetraethylenepentamine (CHP/TEPA) redox initiator was used at the reaction temperature and time of 50°C and 3 h, respectively. MMA monomer was used without purification in the polymerization process comparing with the purified one by means of extraction. It was found that only a slight decrease of grafting efficiency was observed when the nonpurified monomer was used in the reaction. The nonpurified monomer was therefore used to prepare the NR‐g‐PMMA in a pilot scale production with a reactor capacity of 260 L. Various weight ratios of NR/MMA at 50/50, 60/40, 70/30, and 85/15 were studied. The resulting graft copolymers were characterized by FTIR and ¹H‐NMR techniques. It was found that increasing concentration of MMA caused an increase of free PMMA (i.e., homopolymer) but a decrease of free NR (i.e., ungrafted NR) and grafting efficiency. Quantity of grafted PMMA on the NR backbone was estimated using the integrated peak areas of ¹H‐NMR spectra and quantitative analysis by extraction method. The results were found to be in good agreement. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009