Synthesis of graft copolymers from a linear polyolefin through a combination of coordination polymerization and atom transfer radical polymerization

This article reports on a facile route for the preparation of methyl acrylate and methyl methacrylate graft copolymers via a combination of catalytic olefin copolymerization and atom transfer radical polymerization (ATRP). The chemistry first involved a transforming process from ethylene/allylbenzene copolymers to a polyolefin multifunctional macroinitiator with pendant sulfonyl chloride groups. The key to the success of the graft copolymerization was ascribed to a fast exchange rate between the dormant species and active radical species by optimization of the various experimental parameters. Polyolefin‐g‐poly(methyl methacrylate) and polyolefin‐g‐poly(methyl acrylate) graft copolymers with controlled architecture and various graft lengths were, thus, successfully prepared under dilute ATRP conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Internal plasticization of poly(vinyl chloride) by grafting acrylate copolymers via copper-mediated atom transfer radical polymerization

Internal plasticization of poly(vinyl chloride) (PVC) was achieved in one-step using copper-mediated atom transfer radical polymerization to graft different ratios of random n-butyl acrylate and 2–2-(2-ethoxyethoxy)ethyl acrylate copolymers from defect sites on the PVC chain. Five graft polymers were made with different ratios of poly(butyl acrylate) (PBA) and poly(2–2-(2-ethoxyethoxy)ethyl acrylate) (P2EEA); the glass transition temperatures (T_g) of functionalized PVC polymers range from − 25 to − 50°C. Single T_g values were observed for all polymers, indicating good compatibility between PVC and grafted chains, with no evidence of microphase separation. Plasticization efficiency is higher for polyether P2EEA moieties compared with PBA components. The resultant PVC graft copolymers are thermally more stable compared to unmodified PVC. Increasing the reaction scale from 2 to 14 g produces consistent and reproducible results, suggesting this method could be applicable on an industrial scale.     

Synthesis and characterization of polytriphenylamine based graft polymers for photorefractive application

Novel graft copolymers, PTPA-g-PEAs containing poly(triphenylamine) (PTPA) backbone and poly(ethyl acrylate) (PEA) branches were synthesized by the oxidative coupling polymerization of triarylamine monomers followed by grafting of ethyl acrylate via an atom transfer radical polymerization (ATRP). Photorefractive (PR) composites based on the graft copolymers showed good static PR properties and fast response time under moderate conditions. The highest diffraction efficiency (19.7% at 45 V/μm) was observed with the composite containing the graft polymer with 18 mol% of graft density and 27 wt% of PTPA. And the fastest response (8 ms at 50 V/μm) was achieved when PTPA content was 68 wt%.     

Comparison of thermomechanical properties of statistical, gradient and block copolymers of isobornyl acrylate and n-butyl acrylate with various acrylate homopolymers

Well-defined statistical, gradient and block copolymers consisting of isobornyl acrylate (IBA) and n-butyl acrylate (nBA) were synthesized via atom transfer radical polymerization (ATRP). To investigate structure-property correlation, copolymers were prepared with systematically varied molecular weights and compositions. Thermomechanical properties of synthesized materials were analyzed via differential scanning calorimetry (DSC), dynamic mechanical analyses (DMA) and small-angle X-ray scattering (SAXS). Glass transition temperature (T_g) of the resulting statistical poly(isobornyl acrylate-co-n-butyl acrylate) (P(IBA-co-nBA)) copolymers was tuned by changing the monomer feed. This way, it was possible to generate materials which can mimic thermal behavior of several homopolymers, such as poly(t-butyl acrylate) (PtBA), poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA) and poly(n-propyl acrylate) (PPA). Although statistical copolymers had the same thermal properties as their homopolymer equivalents, DMA measurements revealed that they are much softer materials. While statistical copolymers showed a single T_g, block copolymers showed two T_gs and DSC thermogram for the gradient copolymer indicated a single, but very broad, glass transition. The mechanical properties of block and gradient copolymers were compared to the statistical copolymers with the same IBA/nBA composition.     

Thermoresponsive and biocompatible poly(vinyl alcohol)‐graft‐poly(N,N‐diethylacrylamide) copolymer: Microwave‐assisted synthesis,characterization, and swelling behavior

Novel thermoresponsive poly(vinyl alcohol)‐graft‐poly(N,N‐diethylacrylamide) (PVA‐g‐PDEAAm) copolymers were prepared by microwave‐assisted graft copolymerization using a potassium persulfate/N,N,N′,N′‐tetramethylethylenediamine (KPS/TEMED) initiator system. The structures of PVA‐g‐PDEAAm copolymers were characterized by ¹H‐NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry/thermogravimetric analysis, gel permeation chromatography, X‐ray diffraction, and scanning electron microscopy. The effects of various process parameters on grafting were systematically studied: microwave power, KPS, monomer and PVA concentrations, and ultraviolet irradiation. Under optimal conditions, the maximum grafting percent and graft efficiency were 101% and 93%, respectively. Furthermore, a lower critical temperature of copolymers was measured in the range 29–31 °C by ultraviolet spectroscopy. The swelling behavior of graft membranes was carried out at various temperatures, and the results showed that the swelling behavior of membranes was dependent on the temperature. In vitro cell culture studies using L929 fibroblast cells confirmed cell compatibility with the PVA‐g‐PDEAAm copolymer and its membrane, making them an attractive candidate for drug delivery systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45969.     

Novel Poly(linolenic acid) Graft Copolymers: Synthesis,Characterization and Electrical Properties

A poly(linolenic acid)‐g‐poly(tert‐butyl acrylate) graft copolymer was synthesized from polymeric linolenic acid peroxide possessing peroxide groups in the main chain by free radical polymerization of tert‐butyl acrylate. Graft copolymers having structures of poly(linolenic acid)‐g‐poly(caprolactone)‐g‐poly(tert‐butyl acrylate) were synthesized from polymeric linolenic acid, possessing peroxide groups on the main chain by the combination of free radical polymerization of tert‐butyl acrylate and ring‐opening polymerization of ε‐caprolactone in one‐pot. The obtained graft copolymers were characterized by proton nuclear magnetic resonance, gel permeation chromatography, thermal gravimetric analysis, differential scanning calorimetry, and scanning electron microscopy techniques. Furthermore, Au/n‐Si diodes were fabricated with and without poly(linolenic acid)‐g‐poly(caprolactone)‐g‐poly(tert‐butyl acrylate)‐4 to form a new interfacial polymeric layer for the purpose of investigating this polymer's conformity in electronic applications. Some main electrical characteristics of these diodes were investigated using experimental current–voltage measurements in the dark and at room temperature.     

A facile,green, versatile protocol to prepare polypropylene‐g‐poly(methyl methacrylate) copolymer by water‐solid phase suspension grafting polymerization using the surface of reactor granule technology polypropylene granules as reaction loci

A facile and environment friendly process, called water‐solid phase suspension grafting polymerization, was developed to prepare polypropylene‐g‐poly(methyl methacrylate) (PP‐g‐PMMA) copolymer with a submicrometer microdomain. In this approach, graft polymerization was elaborately regulated to occur within micropores of polypropylene particles prepared by reactor granule technology. FTIR spectra of the samples after extraction demonstrated that PMMA was successfully grafted onto the PP. The results showed grafting percentage (GP) of PMMA increased with the increasing monomer ratios to PP and that could reach 13.6%. Whereas the grafting efficiency decreased as the monomer ratio increased. The addition of second monomer styrene improved GP up to 24.5%. Differential Scanning Calorimetry tests showed that the grafting of PMMA have a slight effect on the melting point and the relative crystallinity of PP. TEM micrographs demonstrated PMMA domains distributed in PP matrix with sizes ranging from about 100 to 300 nm. In addition, Shear viscosity increased with the growing GP indicated by rheological measurement. The preliminary evaluation showed PP‐g‐PMMA was effective in improving the compatibility of PP/acrylonitrile‐styrene‐acrylate blends. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

“Smart” membrane materials: Preparation and characterization of PVDF‐g‐PNIPAAm graft copolymer

In this research, a smart membrane material of graft copolymer of poly(vinylidene fluoride) with poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) was synthesized by atom transfer radical polymerization (ATRP) using poly(vinylidene fluoride) (PVDF) as a macroinitiator and direct initiation of the secondary fluorinated site PVDF facilitates grafting the N‐isopropylacrylamide comonomer. The copolymers were characterized by Fourier transform infrared (FTIR), ¹H NMR, gel‐permeation chromatography (GPC), and X‐ray photoelectron spectroscopy (XPS). The temperature‐sensitive membrane was prepared from the PVDF‐g‐PNIPAAm graft copolymers by the phase inversion method. The effects of temperature on the flux of pure water of membrane was investigated. The results showed that alkyl fluorides were successfully applied as ATRP initiators in the synthetic condition and the flux of pure water through the PVDF‐g‐PNIPAAm membrane depended on the temperature change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1482–1486, 2007     

Synthesis of polypropylene graft copolymers from a hydroxyl‐groups‐containing polypropylene precursor via atom‐transfer radical polymerization

Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl₂‐supported TiCl₄ as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Graft copolymers from commercial chlorinated polypropylene via Cu(0)‐mediated atom transfer radical polymerization

Commercially available chlorinated polypropylene has been used as a macroinitiator for the Cu(0)‐mediated atom transfer radical polymerization of methyl methacrylate and tert‐butyl acrylate to obtain well‐defined graft copolymers. The relatively narrow molecular weight distribution in the graft copolymers and linear kinetic plots indicated the controlled nature of the copolymerization reactions. Both Fourier transform infrared and ¹H NMR studies confirmed that the graft reactions had taken place successfully. After graft copolymer formation, tert‐butyl groups of poly(tert‐butyl acrylate) side chains were completely converted into poly(acrylic acid) chains to afford corresponding amphiphilic graft copolymers. © 2016 Society of Chemical Industry     

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 of N‐vinyl‐2‐pyrrolidone onto sodium carboxymethylcellulose with azobisisobutyronitrile as the initiator

Graft copolymers of sodium carboxymethylcellulose with N‐vinyl‐2‐pyrrolidone were prepared in aqueous solutions with azobisisobutyronitrile as the initiator. The graft copolymers [sodium carboxymethylcellulose‐g‐poly(N‐vinyl‐2‐pyrrolidone)] were characterized with Fourier transform infrared spectroscopy, elemental analysis, nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and scanning electron microscopy. The grafting parameters, including the graft yield of the graft copolymer and the grafting efficiency of the reaction, were evaluated comparatively. The effects of reaction variables such as the time, temperature, and monomer and initiator concentrations on these parameters were studied. The graft yield and grafting efficiency increased and then decreased with increasing concentrations of N‐vinyl‐2‐pyrrolidone and azobisisobutyronitrile and increasing polymerization temperatures. The optimum temperature and polymerization time were 70°C and 4.30 h, respectively. Further changes in the properties of grafted sodium carboxymethylcellulose, such as the intrinsic viscosity, were determined. The overall activation energy for the grafting was also calculated to be 10.5 kcal/mol. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 936–943, 2007     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatonickelate(IV)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) with a potassium diperiodatonickelate(IV) [Ni(IV)]–PVA redox system as an initiator was investigated in an alkaline medium. The grafting parameters were determined as functions of the temperature and the concentrations of the monomer and initiator. The structures of the graft copolymers were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The Ni(IV)–PVA system was found to be an efficient redox initiator for this graft copolymerization. A single‐electron‐transfer mechanism was proposed for the formation of radicals and the initiation. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate, n‐butyl acrylate, and n‐butyl methacrylate, were used as reductants for graft copolymerization. These reactions definitely occurred to some degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 529–534, 2003     

Thermoresponsive poly(ϵ‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) graft copolymers prepared by a combination of ring‐opening polymerization and sequential azide–alkyne click chemistry

A straightforward strategy is described to synthesize poly(?‐caprolactone)‐graft‐poly(N‐isopropylacrylamide) (PCL‐g‐PNIPAAm) amphiphilic graft copolymers consisting of potentially biodegradable polyester backbones and thermoresponsive grafting chains. PCL with pendent chlorides was prepared by ring‐opening polymerization, followed by conversion of the pendent chlorides to azides. Alkyne‐terminated PNIPAAm was synthesized by atom transfer radial polymerization. Then, the alkyne end‐functionalized PNIPAAm was grafted onto the PCL backbone by a copper‐catalyzed azide–alkyne cycloaddition. PCL‐g‐PNIPAAm graft copolymers self‐assembled into spherical micelles comprised of PCL cores and PNIPAAm coronas. The critical micelle concentrations of the graft copolymers were in the range 7.8–18.2 mg L^?1, depending on copolymer composition. Mean hydrodynamic diameters of micelles were in the range 65–135 nm, which increased as the length of grafting chains grew. PCL‐g‐PNIPAAm micelles were thermosensitive and aggregated upon heating. © 2014 Society of Chemical Industry     

Synthesis of water‐soluble polyphenol‐graft‐poly(ethylene oxide) copolymers via enzymatic polymerization and anionic polymerization

Water‐soluble polyphenol‐graft‐poly(ethylene oxide) (PPH‐g‐PEO) copolymers were prepared using grafting‐through methodology. Polyphenol chains were synthesized via enzymatic polymerization of phenols, and the graft chains were synthesized via living anionic polymerization of ethylene oxides. The polymers were characterized using gel permeation chromatography, static light scattering and ¹H NMR, infrared and ultraviolet spectroscopies. The PPH‐g‐PEO graft copolymers are soluble in several common solvents, such as water, ethanol, N,N‐dimethylformamide, tetrahydrofuran and methylene dichloride. The solubility of the PPH‐g‐PEO graft copolymers is improved significantly compared with that of polyphenol. Copyright © 2009 Society of Chemical Industry     

Graft copolymerization of oleic acid onto low‐density polyethylene in the molten state

A graft copolymer of oleic acid (OA) onto low‐density polyethylene (LDPE) was prepared using dicumyl peroxide (DCP) as an initiator in the molten state. The grafting was carried out in a Haake rheometer. The effects of the reaction time and the amount of DCP and the monomer on the percentage of grafting were studied. The rheological behavior and the melt‐flow rate of the graft copolymer (LDPE‐g‐OA) were also investigated. FTIR spectroscopy and a mass spectrum were used to characterize the structure of LDPE‐g‐OA. The experimental results showed that when the OA amount was 10 wt % and the DCP amount was 0.4 wt % based on the LDPE the percentage of grafting of LDPE‐g‐OA, prepared by maintaining the temperature at 170°C and the roller speed at 80 rpm, was about 6 wt %. It was found that both LDPE and LDPE‐g‐OA were pseudoplastic fluids. OA was grafted onto LDPE in the form of a monomer and a dimer. The grafted LDPE is expected to act as a compatibilizer between starch and polyethylene. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3299–3304, 2003     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

DGEBA‐grafted polyaniline: Synthesis,characterization and thermal properties

The utilization of conducting emeraldine salt (PANI‐ES) and intrinsic leucoemeraldine polyaniline (PANI‐LEB) in the synthesis of DGEBA‐grafted PANI via anionic copolymerization is described. The structures of copolymers obtained were characterized by FTIR, ¹³C and ¹H NMR. The extent of grafting was verified by THF Soxhlet (solvent extraction). The thermal properties of these new copolymers were described and their conductivities were reported. Results obtained indicated that the graft copolymer exhibited higher electrical and thermal conductivities than that of the blend counterpart. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).