Approach to the fabrication of acrylic elastomer nanocomposites with high dielectric constants

Dielectric elastomers (DEs) are a type of electroactive polymer that can deform in an electric field. The possession of a high dielectric constant is critical for DEs if they are to be suitable materials for the application of actuators. A novel elastomeric nanocomposite (ACE‐g‐CuPc) was fabricated by copper phthalocyanine oligomer (CuPc) grafting directly onto an acrylic elastomer (ACE) backbone. Compared with other synthetic methods, esterification has several advantages; these include fewer impurities and a simpler synthetic route. Transmission electron microscopy showed that the size of the CuPc particles of the ACE‐g‐CuPc was in the range 15–30 nm; this range was significantly smaller than that of ACE/CuPc (500 nm). The results of thermogravimetric analysis show that the thermal stability of the grafting composite was higher than that of the blending composite. At 100 Hz, the dielectric constant of the grafting composite (with 11 wt % CuPc) reached 173 at room temperature. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43904.     

Thermal properties of proton-conducting radiation-grafted membranes

Proton-exchange membranes are required to exhibit chemical, mechanical, and thermal stability for fuel cell applications. The present investigation has been carried out to explore the thermal behavior of poly(ethylene-alt-tetrafluoroethylene) (ETFE)-based proton-conducting membranes, both uncrosslinked and crosslinked, prepared by radiation grafting and subsequent sulfonation. The influence of preparation steps (irradiation, grafting, sulfonation, crosslinking) on the thermal degradation, crystallinity, and melting behavior of membranes with varying degree of grafting was examined. ETFE base film and grafted films were studied as the reference materials. Furthermore, poly(tetrafluoroethylene-co-hexafluoropropylene)-based grafted films and membranes were investigated as well for comparison. Membrane preparation steps, degree of grafting, crosslinking, type of base polymer have considerable influence on the thermal properties of membranes. The crystallinity of the films decreases slightly by grafting, while a significant decrease was observed after sulfonation. For instance, crystallinity decreased from 37% (pristine ETFE) to 36% (uncrosslinked grafted film) and 23% (uncrosslinked ETFE-based membrane). On the other hand, the melting temperature of the base polymer was almost unaffected by irradiation and grafting. The crosslinked ETFE-based membranes exhibit a slightly higher melting temperature (262.5°C) than their corresponding grafted films (261.3°C) and the base film (260.6°C). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,characterization, and biodegradation of carboxymethylchitosan‐g‐medium chain length polyhydroxyalkanoates

Grafting of medium chain length polyhydroxyalkanoates (mcl‐PHA) produced by Comamonas testosteroni onto carboxymethylchitosan (CMCH) using ceric ammonium nitrate (CAN) as an initiator was carried out under nitrogen atmosphere in aqueous medium. The grafting composition was 2 g CMCH, 0.2M CAN, and 0.5 g mcl‐PHA. The reaction was carried out at 40°C ± 1°C for 4.5 h, and reaction product was extracted by acetone precipitation. The CMCH‐g‐mcl‐PHA copolymers were characterized by Fourier transform infrared spectroscopy, Thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. The data obtained showed successful grafting of mcl‐PHA onto CMCH polymer. TGA results indicated that the graft was stable up to 380°C, and the solubility studies revealed a high % grafting efficiency. Biodegradation studies of the graft in terms of microbial growth, extracellular protein concentration, and % weight loss in the graft were carried out for 30 days using a bacterial isolate Burkholderia cepacia 202 and a fungal isolate Aspergillus fumigatus 202. 93% weight loss of the graft was obtained in case of A. fumigatus 202, whereas B. cepacia 202 showed 76% loss in weight of the graft. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Graft polymerization of N‐tert‐butylacrylamide onto polypropylene during melt extrusion and biocidal properties of its products

Functionalization of polypropylene (PP) by radical graft polymerization with N‐tert‐butylacrylamide (NTBA) was successfully conducted during melt extrusion, and the grafted products were employed as precursors of biocidal N‐halamine polymers. Graft polymerization conditions, including monomer and initiator concentrations, addition of a comonomer styrene (St), were studied. Fourier transformed spectroscopy (FTIR) results and nitrogen analysis confirmed the graft polymerization on PP backbone during the reactive extrusion. The results also indicated that increase in initiator concentration led to more PP chain scission and reduction in mixing torque or polymer chain length. As the monomer concentration rose, grafted monomer content in the products improved, revealing increased grafting copolymerization in the system. Addition of St as a comonomer adversely affected grafting of NTBA, but significantly prevented polymer chain scission. This may be due to lower tendency of NTBA for copolymerization. The halogenated products exhibited potent antimicrobial properties against Escherichia coli, and the antimicrobial properties were durable and regenerable. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Novel microporous poly(vinylidene fluoride)‐graft‐poly(tert‐butyl acrylate) electrolytes for secondary lithium batteries

BACKGROUND: Much interest has recently been shown in improving the performance of lithium‐ion polymer batteries with gel polymer electrolytes (GPEs) due to a rapid expansion in industrial demand. Novel GPEs based on poly(vinylidene fluoride)‐graft‐poly(tert‐butyl acrylate) (PVDF‐g‐tBA) microporous mats are suggested in this study. RESULTS: Microfibrous polymer electrolytes were prepared using electrospinning and characterized for extent of grafting, morphology, crystallinity, electrochemical stability, ionic conductivity, interfacial resistance and cell cycleability. The degree of crystallinity was lower for tBA‐grafted PVDF mats than that of neat PVDF. The PVDF‐g‐tBA showed an improvement in the ionic conductivity, electrochemical stability, interfacial resistance and cyclic performance. CONCLUSION: The tBA‐grafted PVDF microporous electrolytes are promising candidates for enhancing the performance of lithium‐ion polymer batteries. Copyright © 2008 Society of Chemical Industry     

Synthesis of a novel linear water‐soluble β‐cyclodextrin polymer

A novel linear water‐soluble β‐cyclodextrin polymer has been prepared by grafting β‐cyclodextrin on poly[(methyl vinyl ether)‐alt‐(maleic anhydride)]. First, lithium hydride was used to obtain the mono‐alkoxide β‐CD. Grafting of β‐CD derivatives to the polymer backbone was then carried out by an esterification method. Using this method, polymers containing various amounts of β‐CD were synthesized. The resulting grafted polymers were characterized by two complementary methods, ¹H NMR and IR spectroscopy. The first was used to calculate the degree of substitution for the low amounts of β‐CD. The second method was very useful to evaluate the degree of substitution and the molar ratio of CD especially for high amounts of grafting. Our results indicate good agreement between both methods for intermediate rates. Copyright © 2004 Society of Chemical Industry     

Graft copolymerization studies. III. Methyl methacrylate onto polypropylene and polyethylene terephthalate

The tert‐butoxy radical‐facilitated grafting of methyl methacrylate (MMA) onto commercial polypropylene (PP) pellets and fiber was investigated in heterogeneous conditions similar to practical systems. Free‐radical grafting of several other monomers onto PP fiber was also investigated. Also, preliminary data from the grafting of MMA onto poly(ethylene terephthalate) pellets is presented. The PP‐graft‐PMMA residues were detected by solid‐state ¹³C‐NMR and photoacoustic IR spectroscopy. There was a good correlation between the degree of grafting (DG) determined from these spectroscopic techniques and the results from gravimetric methods. A maximum grafting efficiency of over 50% was found, whereas DG (20%) remained constant at various PP pellet, initiator, and monomer concentrations. However, at relatively low PP fiber concentrations, the DG was 27%; the increase was most likely due to the greater surface area of the fiber. There was also a reduction in DG (14%) at relatively low initiator concentrations. The reaction conditions were altered to favor grafting by the addition of more polymer substrate. When the ratio of tert‐butoxy radicals to PP was decreased, more of the substrate remained unmodified, and empirical calculations showed the formation of grafts with up to 40 monomer units. At high initiator concentrations, calculations showed that the graft residues were 1–2 units long. Therefore, variation of the polymer, initiator, and monomer concentrations was shown to have a significant effect on grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 898–915, 2002     

Interactions of a smart cationic polyelectrolyte based on hydroxypropylcellulose with an anionic surfactant

Novel thermosensitive, cationic polyelectrolyte was obtained by grafting N‐vinylformamide onto hydroxypropylcellulose followed by the hydrolysis of the formamide groups to the amine groups. The effect of the ionic strength on the lower critical solution temperature of the polymers was studied. The interactions of the polymers with sodium dodecyl sulfate (SDS) as a model anionic surfactant were studied. It was found by the measurements of the light scattering and fluorescence spectroscopy that the graft copolymers obtained strongly interact with SDS with the formation of polymer‐surfactant complexes. The values of critical association concentration (cac) of these polymer‐surfactant systems were found to be of the order of 10^?5 mol/dm³ at pH = 6.5 and of the order of 10^?6 mol/dm³ at pH = 2.5. The polymer was shown to be potentially useful for the purification of water from anionic surfactants. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of sulfonated ETFE‐g‐polyvinyltoluene membranes for application in fuel cells

A new polymer electrolyte membrane prepared by radiation grafting of vinyltoluene into poly(ethylene‐co‐tetrafluoroethylene) (ETFE) film and subsequent sulfonation was developed for application in fuel cells. The effect of grafting condition on the degree of grafting was investigated in detail. Results indicated that the degree of grafting can be controlled over a wide range. The grafted films were sulfonated in a chlorosulfonic acid solution to obtain the polymer electrolyte membranes, which were characterized with respect to their use in fuel cells. It is concluded that the substituted methyl group on the vinyltoluene can improve the chemical stability of the resulting membranes, and the crosslinked ETFE‐g‐poly(vinyltoluene‐co‐divinylbenzene) membranes can be proposed for the future development of alternative low‐cost and high‐performance membranes for fuel cells. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2661–2667, 2006     

Effect of interfacial area on heterogeneous free radical grafting of vinyl monomers in supercritical carbon dioxide: Grafting of acrylic acid on poly(vinylidenefluoride) nanoparticles

The role of the polymer interfacial area on free radical grafting of acrylic acid (AA) onto poly(vinylidenefluoride) (PVDF) was studied at 65°C using supercritical carbon dioxide (scCO₂) as a solvent and swelling agent, benzoylperoxide (BPO) as chemical initiator and PVDF nanoparticles as polymer matrix. Under adopted conditions PVDF particles do not melt neither dissolve in the reaction medium and FTIR analyses performed on carefully washed nanoparticles confirmed the achievement of high grafting levels. The mass fraction of grafted AA increased with the grafting time and the BPO concentration while it decreased when the density of the fluid phase was enhanced. Collected results suggest that the grafting level obtained by free radical grafting of vinyl monomers onto solid polymer in scCO₂ can be significantly enhanced by increasing the interfacial area of the matrix. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41541.     

Preparation and characterization of polyhydroxyurethane/silica nanocomposites via in situ surface‐initiated polymerization

The polyhydroxyurethane/silica nanocomposite (PHU/SN) was prepared by the in situ surface‐initiated polymerization of a five‐membered cyclic carbonate, 2,2‐bis[p‐(1,3‐dioxolan‐2‐one‐4‐yl‐methoxy)phenyl]propane (B5CC) and hexamethylene diamine, from the surfaces of the aminopropyl silica nanoparticles (APSN) for the first time. The percentage of grafting (PG%) and the grafting efficiency (GE%) of 27% and 19% were calculated from the results of thermogravimetric analysis (TGA), respectively, after the free polyhydroxyurethane was washed off. The chemical grafting of the polymer was also confirmed using Fourier transform infrared (FTIR) and the morphology of the silica nanoparticles in the nanocomposite was characterized by transmission electron microscope (TEM). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Novel multimonomer‐grafted polypropylene preparation and application in polypropylene/poly(vinyl chloride) blends

A novel grafted polymer was prepared in one step through free‐radical melt grafting in a single‐screw extruder. It was shown that the addition of styrene (St) to the melt‐grafting system as a comonomer could significantly enhance the grafting degree of methyl methacrylate (MMA) onto polypropylene (PP) and reduce the degradation of the PP matrix by means of Fourier transform infrared and melt flow rate testing, respectively. Then, the potential of using multimonomer‐grafted PP, which was designated PP‐g‐(St‐co‐MMA), as the compatibilizer in PP/poly(vinyl chloride) (PVC) blends was also examined. In comparison with PP/PVC blends, the average size of the dispersed phase was greatly reduced in grafted polypropylene (gPP)/PVC blends because of the addition of the PP‐g‐(St‐co‐MMA) graft copolymer. The tensile strength of the gPP/PVC blends increased significantly, and the impact strength was unchanged from that of the pure PP/PVC blends. The results of differential scanning calorimetry and scanning electron microscopy suggested that the compatibility of the PP/PVC blends was improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Synthesis and characterization of polyethylene modified through phase‐transfer‐catalyzed graft copolymerization

In an effort to impart biodegradability, polyethylene (PE) was modified through the graft copolymerization of vinyl monomers such as acrylamide (AAm) and acrylic acid (AAc) by a phase‐transfer‐catalyst method. The grafting percentage of AAm and AAc for PE was found to be dependent on the dibenzoyl peroxide concentration, monomer concentration, time, temperature, and concentration of the phase‐transfer catalyst. Some AAm‐ and AAc‐grafted PE samples were prepared by chemical, UV, and γ‐radiation methods. The biodegradation of samples of PE, polyethylene‐g‐polyacrylamide, and polyethylene‐g‐poly(acrylic acid) prepared by all these methods was studied. The weight loss of the samples over a period of time was observed with soil‐burial tests. The grafted samples prepared by the phase‐transfer‐catalyst method showed better biodegradation results than those prepared by other methods of grafting. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Grafting of poly-β-alanine onto carbon black: The hydrogen transfer polymerization of acrylamide catalyzed by n-butyllithium in the presence of carbon black

The hydrogen transfer polymerization of acrylamide (AAm) catalyzed by n-butyllithium in the presence of carbon black was carried out at 80–100°C and the grafting of poly-β-alanine (nylon 3) was investigated. It was suggested that the growing polymer anion was captured by the quinonic oxygen group on the surface of carbon black. Furthermore, the growing polymer anion reacted with the phenolic hydroxyl group on the surface to give ungrafted polymer and the lithium phenolate (? O^?Li⁺) group (chain transfer to phenolic hydroxyl group). The ? O^?Li⁺ group formed was considered to be capable of initiating the hydrogen transfer polymerization of AAm. Accordingly, during the hydrogen transfer polymerization in the presence of carbon black, poly-β-alanine was effectively grafted by the termination of growing polymer anion and the propagation of the polymer from the ? O^?Li⁺ group on the surface. The grafting ratio was determined to be 60–80%. The carbon black obtained from the polymerization gave a stable colloidal dispersion in water, N,N-dimethylformamide, and formic acid. Furthermore, it was found that the ratio of hydrogen transfer polymerization to normal vinyl polymerization (T ratio) increased with an increase in polymerization temperature.     

Polymer-leather composites. I. Process and location study for the deposition of selected acrylate monomers by polymerization into chrome-tanned cattlehide

Three acrylate monomer systems were deposited by redox emulsion polymerization at room temperature into the fibrous matrix of 2-mm-thick chrome-tanned cattlehide over a wide range of composition. Polymer not bound to the matrix was separated by hot benzene extractions. Monomers used were methyl methacrylate, a mixture of n-butyl acrylate and methyl methacrylate and n-butyl acrylate, each selected to produce composites having wide variation in glass-transition temperature. The same three systems were introduced into the free space of leather by bulk and solution polymerization. All conversions were close to 100%. When the emulsion technique was used, with feed composition variable, overall deposition efficiency depended on the characteristic rate of deposition for the individual acrylate monomers. Observed orders in deposition rate and overall efficiency were: methyl methacrylate > comonomer > n-butyl acrylate. However, specific deposition efficiencies declined roughly monotonically with feed or time increase, but maintained the same order. Microscopic examination of thin sections revealed polymer only in the outer region of the leather cross section. Information on polymer location and its influence on specimen thickness for composites prepared by both emulsion and solution methods of deposition were obtained by correlating experimental densities with theoretical density–composition curves for various assumed models. The foregoing, together with observations of greatly reduced grafting frequency, in view of the maximum theoretically attainable, made a dominant grafting mechanism unattractive. A mechanism involving diffusion controlled monomer transport to occluded radicals in localized polymer deposits was suggested as an alternative.     

Radiation‐induced graft copolymerization of acrylic acid/acrylonitrile onto LDPE and PET films and its biodegradability

Graft copolymerization of acrylic acid/acrylonitrile (AAc/AN) comonomer onto low‐density poly(ethylene) (LDPE) and poly(ethylene terephthalate) (PET) films using direct radiation grafting technique has been investigated. The effect of different reaction conditions on the grafting yield was studied. The structure of the grafted films at different compositions was characterized by FTIR, TGA, SEM, and XRD. Biodegradation of grafted LDPE and PET was investigated by burial method in two types of Egyptian soils (agricultural and desert soils). The bacteria responsible for biodegradation were isolated and characterized, and the capacities for the growth on these polymers as substrates were compared. The isolates from agricultural soil were characterized as Pseudomonas, Alcaligenes, Bacillus, Proteus, and Enterobacter, whereas the isolates from desert soil were characterized as Alcaligenes, Bacillus, and Pseudomonas. The highest degradation rate was found to be achieved using agricultural soil. It is found that the isolated strains belonging to the genus Pseudomonas were mainly responsible for the degradation of both polymers. It has also been found that the increase of AAc ratio in the composition increases the hydrophilicity of the films and the degradation rate. PET polymer is generally found to be more resistant to the biodegradation than LDPE in the two types of soils tested. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of cellulose acetate reverse osmosis membranes by radiation grafting

Large excesses of a chain transfer agent, carbon tetrachloride, were introduced to a recipe for the mutual radiation grafting of styrene to cellulose acetate film. The effect of the carbon tetrachloride on the molecular characteristics as well as the reverse osmosis and time dependent mechanical properties of resulting graft copolymers was determined. Extremely short side chains were generated as a consequence of the high concentrations of chain transfer agent and the composite results further suggest that the morphology of the grafted films is best described as “destructured” or internally plasticized consequent to grafting in the presence of CCl₄. Reverse osmosis fluxes increased with percent graft; salt rejection was high and unaffected by per cent graft up to 40% graft; and the tensile creep under wet conditions was significantly retarded by the grafting. These effects were shown to accrue from grafting per se by control experiments involving α-methylstyrene which will not propagate to form a polymer under these conditions. These results are compared and contrasted with earlier work on grafting in the absence of CCl₄ where long side chains of polystyrene were generated resulting in a structuring of the polymer involving domains of polystyrene-rich material and domains of cellulose acetate rich polymer.     

Influence of an annealing treatment on the solid‐state grafting of styrene onto spherical isotactic polypropylene granules

The main place of solid‐state graft polymerization in polypropylene (PP) granules has been believed to be the amorphous region of PP. In this work, the solid‐phase morphology of nascent spherical PP (N‐PP) granules was found to be markedly changed by an annealing treatment. The crystallinity of PP granules was almost doubled after annealing at 150°C for 12 h, whereas the porosity of the granules was unchanged. Solid‐state grafting polymerizations of styrene initiated by tert‐butyl perbenzoate in both N‐PP and annealed polypropylene (A‐PP) granules were compared under different reaction conditions. The formation of gel in the product could be completely depressed at a low concentration of the initiator when A‐PP granules were used as the matrix and graft‐polymerized at 120°C. Both the introduction of styrene and the annealing treatment of the PP granules led to a depression of polymer degradation in the process of the grafting reaction. However, using A‐PP as the matrix caused an increase in the grafting degree at a relatively high concentration of the initiator. A reduction in the amorphous phase in the PP granules was thought to be the main reason for the effects of the annealing treatment on the structure of the graft polymerization products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Vinyl–carbon nanotubes for composite polymer materials

We report herein a simple method for attaching vinyl groups onto the sidewalls of carbon nanotubes (CNTs) and the application of vinyl–carbon nanotubes (CNT–C?C) in fabricating polymer composites. The synthesis of CNT–C?C was monitored with IR spectroscopy, Raman spectroscopy, and thermogravimetric analysis. The obtained CNT–C?C showed good compatibility with the in situ polymerization of poly(methyl methacrylate) (PMMA) and exhibited no tendency for phase separation in the final composite. A transmission electron microscopy study revealed a uniform coating on the CNT–C?C tubes, indicating good grafting efficiency of PMMA. The uniform dielectric PMMA coating was responsible for the lower electrical conductivity of the CNT–C?C/PMMA composites versus that of the CNTs without vinyl modification. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008