Amidoximation of acrylonitrile radiation‐grafted onto low‐density polyethylene and its physicochemical characterization

Membranes were prepared by the direct radiation grafting of acrylonitrile onto low‐density polyethylene films. These grafted membranes were amidoximated using hydroxylamine hydrochloride in basic medium. The influence of monomer concentration and swelling behaviour of grafted membrane, amidoximated grafted membrane, and its sodium salt were also studied. Amidoximated grafted membranes and their copolymer–metal complexes of Cu(II) or Cr(III) were prepared. These membranes were characterized using different analysis techniques such as IR, UV and ESR spectrometry. The UV and ESR analyses revealed that the geometry structure for Cu(II) is square planar, while for Cr(III) it is octahedral. The amidoxime ligand was used for separating metal ions from aqueous solutions by a complexation process. The thermal stability of different membranes was investigated through TG analysis. It was found that the amidoxime‐grafted membranes possess good hydrophilic properties that may make them promising candidated for some practical applications such as the recovery of metals from their aqueous systems. © 2000 Society of Chemical Industry     

Investigation of radiation‐grafted and radiation‐modified N‐vinyl‐2‐pyrrolidone onto polypropylene film

The radiation‐induced graft copolymerization of N‐vinyl‐2‐pyrrolidone (NVP) onto polypropylene films was investigated using the mutual method. The grafted polymer was modified with prepared α,β‐unsaturated nitrile (Scheme 1 ). The water uptake of the grafted and modified grafted films was found to increase with the degree of grafting. It was observed that the swelling behavior of the modified grafted films with α‐cyano‐β‐phenyl crotononitrile improved more than that of the film grafted and modified grafted with α‐cyano‐β‐(2‐thienyl)crotononitrile or α‐cyano‐β‐(2‐pyridyl)crotononitrile. The modification process for the grafted substrate was confirmed by IR spectroscopy. No significant improvement was observed in thermal stability for the modified grafted films compared to the grafted films. Scanning electron microscopy (SEM) of the grafted and modified grafted membranes heated to 150°C showed change in the structure and morphology. Improvement in the hydrophilicity and morphology of these membranes with carbonitriles may increase the permeability of those membranes for some practical applications.     

Iron(III) complexed with radiation‐grafted acrylic acid onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) films

To introduce functional moieties to a poly(tetrafluoroethylene‐co‐perfluorovinyl ether) film, graft copolymerization of vinyl monomers such as acrylic acid was attempted by a simultaneous technique in aqueous solution using γ‐irradiation. The graft copolymers were complexed with the Fe(III) in aqueous solution. The grafted copolymer–metal complexes were examined by infrared (IR), ultraviolet/visible, energy‐dispersive X‐ray spectroscopy, and electron spin resonance techniques. The effect of temperature on the trunk copolymer, untreated grafted, and treated grafted copolymer films was investigated by IR and thermogravimetric analysis. The overall results suggest octahedral structure for Fe(III) and revealed the high stability of the obtained ligand–metal complexes. Furthermore, scanning electron microscope investigation of the grafted and modified films, both unheated and heated (200°C), showed changes in the structure and surface morphology. Promising results were achieved enhancing the practical applications of modified grafted membranes in the recovery of metal ions from aqueous systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4065–4071, 2007     

Reactive mixing of PET and PET/PP blends with glycidyl methacrylate–modified styrene‐b‐(ethylene‐co‐olefin) block copolymers

Styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) and styrene‐b‐(ethylene‐co‐propylene) (SEP, SEPSEP) block copolymers with different styrene contents and different numbers of blocks in the copolymer chain were functionalized by melt radical grafting with glycidyl methacrylate (GMA) and employed as compatibilizers for PET‐based blends. Binary blends of PET with both functionalized (SEBS‐g‐GMA, SEP‐g‐GMA, SEPSEP‐g‐GMA) and neat (SEBS, SEP, SEPSEP) copolymers (75 : 25 w/w) and ternary blends of PET and PP (75 : 25 w/w) with various amounts (2.5–10 phr) of both modified and unmodified copolymers were prepared in an internal mixer, and their properties were evaluated by SEM, DSC, melt viscosimetry, and tensile and impact tests. The roles of the chemical structure, grafting degree, and concentration of the various copolymers on blend compatibilization was investigated. The blends with the grafted copolymers showed a neat improvement of phase dispersion and interfacial adhesion compared to the blends with nonfunctionalized copolymers. The addition of grafted copolymers resulted in a marked increase in melt viscosity, which was accounted for by the occurrence of chemical reactions between the epoxide groups of GMA and the carboxyl/hydroxyl end groups of PET during melt mixing. Blends with SEPSEP‐g‐GMA and SEBS‐g‐GMA, at concentrations of 5–10 phr, showed a higher compatibilizing effect with enhanced elongation at break and impact resistance. The effectiveness of GMA‐functionalized SEBS was then compared to that of maleic anhydride–grafted SEBS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2201–2211, 2005     

Study on the effect of acid‐ or iodine‐doping on the properties of copolymer C1–4poly‐phenylene‐vinylene‐ether

In this article, the new red‐colored copolymer, referred to as C_1–4poly‐phenylene‐vinylene‐ ether (C_1–4PPV‐ether) is built as a PPV polymer with some conjugated links (? CH?CH? ) that are changed into ethylic‐ether links (? CH₂? O? CH₂? ) and whose modified phenyl ring is grafted, respectively, in two and five positions with methoxy and butoxy groups. The C_{1– 4}PPV‐ether is doped with protonic acid or iodine. The infrared absorption (IR), optical density, X‐ray photoelectron spectroscopy (XPS), and electron spin resonance (ESR) show that there is a charge transfer complex formed between the copolymer and the doping species (iodine or acidic dopants). From IR, XPS, and ESR analysis, we deduced that the doping mechanism of the copolymer is, respectively, a protonation of the double links in PPV in the case of the protonic acid doping process and a grafting of the iodine to the ether links in the case of iodine‐doping process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1858–1866, 2002     

Adsorption of VO2+ by poly[(tetrafluoroethylene)‐co‐(perfluorovinyl ether)] copolymer grafted with acrylic acid using γ‐irradiation

Grafted films were prepared by the reaction of acrylic acid (AAc) onto poly[(tetrafluoroethylene)‐co‐(perfluorovinyl ether)] copolymer (PFA) using γ‐irradiation by the mutual technique. The grafted copolymer was complexed with the vanadyl group, VO²⁺, in aqueous solution. The grafted copolymer–metal complexes were examined by infrared and ultraviolet spectrometry, energy‐dispersive spectroscopy (EDS) and X‐ray diffraction (XRD). The amount of vanadium in the grafted films was estimated using EDS. The thermal stability of the films was investigated through thermogravimetric and differential scanning calorimetry measurements. The degree of crystallinity of the grafted and complexed films decreased by treatment with VO²⁺ ions and also by heating at 300 °C. When heated at a temperature above 300 °C, the grafted chains degraded till they disappeared and the original polymer was almost completely separated. XRD investigation revealed that the metal oxide may be formed as a separate phase with subsequent decrease in the crystallinity of the copolymer. Furthermore, scanning electron microscope (SEM) investigation of the grafted and modified films, both unheated and heated (300 °C), showed changes in the structure and morphology. The tendency of the graft copolymer to adsorb and/or bind to VO²⁺ from aqueous solution is of promising use in the field of waste treatment of rare metals in the environment. Copyright © 2004 Society of Chemical Industry     

Biodegradable amphiphiles of grafted poly(lactide) onto 2‐hydroxyethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers as drug carriers

This article describes the synthesis and characterization of 2‐hydroxylethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers, (HEMA‐co‐NVP), via free radical polymerization followed by grafting of poly(lactide) onto (HEMA‐co‐NVP) copolymers, via ring opening polymerization using tin octoate as a catalyst. The copolymers and the grafted copolymers (i.e., amphiphiles) were subjected to sustained release studies using salicylic acid, as a model drug. Characterization of the formed copolymers was performed using ¹H‐NMR, ¹³C‐NMR, FTIR, TGA, DSC, and SEM techniques. Derivative of TGA thermogram was used to determine %hydrophilicity and %hydrophobicity in the grafted and ungrafted copolymers. The SEM morphology revealed porous layers with crispy structure that were most likely due to the presence of poly(lactide) chains. At lower content of poly(lactide) moiety, grafted copolymers showed non‐Fickian diffusion release rate, whereas Fickian diffusion release rate at higher content of poly(lactide) was observed. The increase of poly(lactide) content (i.e., larger %hydrophobicity) in the copolymer increased the drug‐sustainability, due to the consistent but porous amphiphilic degradable structures that allow controllable release of drug in time interval. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of grafting polyacrylamide from PET films by SI‐ATRP via water‐borne system

The grafted homopolymer and comb‐shaped copolymer of polyacrylamide were prepared by combining the self‐assembly of initiator and water‐borne surface‐initiated atom transfer radical polymerization (SI‐ATRP). The structures, composition, properties, and surface morphology of the modified PET films were characterized by FTIR/ATR, X‐ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electronic microscopy (SEM). The results show that the surface of PET films was covered by equable grafting polymer layer after grafted polyacrylamide (PAM). The amount of grafting polymer increased linearly with the polymerization time added. The GPC date show that the polymerization in the water‐borne medium at lower temperature (50°C) shows better “living” and control. After modified by comb‐shaped copolymer brushes, the modified PET film was completely covered with the second polymer layer (PAM) and water contact angle decreased to 13.6°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and physical properties of liquid‐crystalline copolymers with azobenzene segments

To investigate the effects of photoisomerizable azobenzene segments on the liquid‐crystalline characteristics and thermal properties of polymers, a series of liquid‐crystalline homopolymers and copolymers with azobenzene segments was synthesized. The azobenzene contents of the copolymers were estimated with elemental analysis. The photoisomerization of the azobenzene derivatives was studied with ultraviolet–visible (UV–vis) spectroscopy. The UV–vis absorption of the copolymers was found to be parallel with the content of the azobenzene segments. UV irradiation was found to cause a decrease in the copolymer transmittance around 355 nm due to the photoinduced isomerization from entgegen (E) to zusammen (Z). The phase‐transition temperatures and molecular weights of the polymers were investigated with differential scanning calorimetry and gel permeation chromatography, respectively. The variation in the phase‐transition temperature of the homopolymers before and after UV (365 nm) irradiation was investigated. The bended Z structure was found to disturb the order of the orientation of liquid crystals and to lower the phase‐transition temperature. The appearance of the polymer film was changed from opaque to clear after sufficient UV irradiation. The image recording of the polymer films was achieved after UV irradiation through a mask with pictures. The stability and reliability of the Nematic‐Isotropic phase transition of the homopolymers was evaluated with repeated cycles of 365‐nm UV irradiation and heating at 130°C. After the recycle phase transition was repeated nine times, no significant decay in the response and transmittance could be found. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

Coefficient of friction reduction of ethylene‐co‐acrylic acid film: Effects of grafted 12‐aminododecanamide and solvent exposure

The effect of covalently bound 12‐aminododecanamide on the surface coefficient of friction (COF) of ethylene–acrylic acid copolymer (EAA) films was investigated. The reaction involved grafting 12‐aminododecanoic acid to the inherent carboxylic acid groups on the film, followed by amidation of the grafted amino acid. Conversion of film carboxylic acid groups to primary amide groups was also conducted to compare the impact of direct surface amidation. Subsequent measurements showed that both surface amidation schemes reduced the kinetic COF from 0.30 to 0.15 ～ 0.18. Repetitive COF testing revealed that amide‐modified EAA films maintained low COF values that were independent of the number of COF test runs. However, control experiments showed that COF values also depended greatly on simply exposing film to the various reaction solvents, which increased surface roughness. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2242–2248, 2005     

Removal of cesium‐134 and cobalt‐60 with radiation‐grafted copolymers from their liquid wastes

The introduction of new characteristics to some synthetic polymers was achieved through the γ‐radiation‐induced graft copolymerization of an acrylamide/vinyl acetate comonomer onto polypropylene films for the preparation of synthetic membranes. The influence of the reaction conditions on the grafting yield, such as the solvent and its composition and the inhibitor and its concentration, was investigated. An alkaline treatment was carried out for the prepared graft copolymer to improve its ion‐exchange property. The grafted and treated membranes were characterized to determine the structural changes with X‐ray diffraction and Fourier transform infrared spectroscopy. The mechanical properties, swelling behavior, and electrical conductivity for the graft copolymer were studied. Improvements in the tensile strength, electrical conductivity, and hydrophilicity with grafting were observed. The KOH‐treated membranes possessed greater hydrophilic properties than the untreated ones. The possibility of practical uses for these membranes in the removal of cesium‐134 and cobalt‐60 from their liquid wastes was also investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 936–945, 2005     

Synthesis and characterization of lactose grafted polycaprolactone‐polysiloxane‐polycaprolactone copolymers

To create new biofunctional materials, a polycaprolactone‐polysiloxane‐polycaprolactone (PCL‐PMVS‐PCL) carrying lactose was developed by ring‐opening polymerization and esterification reaction. ¹H NMR and Fourier transform IR spectroscopy confirmed synthesis of the product. Gel permeation chromatography and DSC were used to evaluate its molecular structure. With propagation of the PCL molecular chain, the copolymer transforms from the amorphous form to crystalline, and its solubility in chloroform is modified. Change of the lactose grafting ratio brings about little influence on the solubility of the grafted copolymer. The product exhibits good film‐forming ability after chain extension. The results suggest that the grafted copolymer not only can form composites with commercial biodegradable polyester but also can be processed alone to serve for biomedical engineering. © 2018 Society of Chemical Industry     

Drug release from electrospun fibers of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) grafted with poly(N‐vinylpyrrolidone)

Poly(N‐vinylpyrrolidone) (PVP) groups were grafted onto poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) backbone to modify the properties of PHBV and synthesize a new novel biocompatible graft copolymer. Based on these graft copolymers, electrospun fiber mats and commonly cast films were explored as drug delivery vehicles using tetracycline hydrochloride as a model drug. Toward that end, the fibers were electrospun and the films were cast from chloroform solutions containing a small amount of methanol to solubilize the drug. The Brookfield viscosities of the solution were determined to achieve the optimal electrospinning conditions. The vitro release of the tetracycline hydrochloride from these new drug delivery systems was followed by UV–vis spectroscopy. To probe into the factors affected on the release behavior of these drug delivery systems, their water absorbing abilities in phosphate buffer solution were investigated, together with their surface hydrophilicity, porosity and crystallization properties were characterized by water contact angles, capillary flow porometer, DSC, and WAXD, respectively. The morphological changes of these drug delivery vehicles before and after release were also observed with SEM. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electron‐beam modification of nitrile rubber in the presence of polyfunctional monomers

The structural changes of nitrile rubber in both the presence and the absence of polyfunctional monomers, such as trimethylolpropane triacrylate (TMPTA), tripropyleneglycol diacrylate (TPGDA), and trimethylolmethane tetraacrylate (TMMT), at different doses of electron beam irradiations, were investigated with the help of FTIR spectroscopy (in the ATR mode), solid‐state NMR, dynamic mechanical thermal analysis, and sol–gel analysis. There was a significant decrease in the concentration of olefinic groups for modified system with 3% TMPTA compared to that of the unmodified nitrile rubber on irradiation. This was also confirmed by the increase in the carbon resonances attributed to C? C linkages from solid‐state NMR for the modified system, indicating more crosslinkages. The increase in crosslinking was also revealed by the increase in % gel content and dynamic storage moduli with radiation dose. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs, were determined for both grafted and ungrafted nitrile rubber using a mathematical model. The ratio of scissioning to crosslinking for nitrile rubber was determined using the Charlesby–Pinner equation. Mechanical properties were studied for the modified and the unmodified systems and the tensile strength was found to increase with grafting of polyfunctional monomers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 435–447, 2005     

Surface modification of polypropylene sheets by UV‐radiation grafting polymerization

1,6‐Hexanediol diacrylate (HDDA) was grafted onto polypropylene (PP) substrates in the presence of benzophenone (BP) and isopropylthioxanthone (ITX) photoinitiators, and then polyurethane acrylate formulations were coated onto the HDDA‐g‐PP substrates, using UV radiation. The amount grafted and the grafting efficiency of the polymerizations were determined gravimetrically. The effects of the photoinitiator concentration and the UV radiation intensity on the physicochemical surface properties and the grafting efficiency of the UV‐radiation grafting polymerizations were characterized in detail using contact‐angle measurements, Fourier transform infrared spectroscopy with attenuated total internal reflection, and scanning electron microscopy. The results showed that the amount grafted and the surface polarity of the HDDA‐g‐PP substrates both increased linearly with increasing BP photoinitiator concentration and UV radiation intensity, and that the addition of a small amount of ITX markedly enhanced both parameters, probably due to photosensitization. The adhesion of the UV‐cured coating onto the HDDA‐g‐PP substrates was evaluated using the crosshatch adhesion test. The results indicated that the amount of HDDA grafted onto the PP substrates should exceed about 1 mmol/cm² for satisfactory adhesion with the UV‐cured coating. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1446–1461, 2006     

Synthesis and characterization of temperature‐responsive copolymers based on N‐vinylcaprolactam and their grafting on fibres

BACKGROUND: Responsive materials are able to respond reversibly to an environmental stimulus. When the stimulus is temperature in the physiological range, the responsive material is particularly interesting for textile applications. We describe here the synthesis and characterization of reactive temperature‐responsive copolymers and their subsequent grafting on cotton fabrics. RESULTS: Copolymers of N‐vinylcaprolactam and various reactive monomers were synthesized via free radical polymerization in solution. The copolymers were characterized in terms of chemical structure, molecular weight and temperature‐responsive properties. The copolymer of N‐vinylcaprolactam and methacrylic acid (11 or 22 wt%) and the hydrolysed copolymer of N‐vinylcaprolactam and acryloyl chloride were found to be temperature responsive. They were subsequently grafted on cotton fabrics. The grafting was studied using X‐ray photoelectron spectroscopy and scanning electron microscopy measurements and was found to be effective. Finally, the modified cotton fabrics were found to exhibit temperature‐responsive water regain and water vapour transmission rates. CONCLUSION: Temperature‐responsive copolymers were synthesized, characterized and successfully grafted on cotton fabrics, yielding responsive fabrics. Such fabrics can hence be used to modulate the skin microclimate under textiles. Copyright © 2009 Society of Chemical Industry     

Dyeability and swelling properties of graft copolymers of LDPE with 2‐hydroxypropyl methacrylate monomer prepared by gamma radiation

Low density polyethylene (LDPE) films were grafted with 2‐hydroxypropyl methacrylate (HPMA) monomer by gamma radiation. The LDPE graft copolymer was characterized by FTIR spectroscopy, tensile mechanical testing, and thermogravimetric analysis (TGA). The dye affinity of LDPE graft copolymers for different dyestuffs was studied. Also, the effect of temperature on the swelling characters of LDPE‐g‐HPMA was investigated. The TGA study showed that the LDPE graft copolymers, over the studied graft yields, possessed higher thermal stability than pure LDPE polymer. While, LDPE has no dye affinity for any of the known dyestuffs, LDPE graft copolymers displayed a unique dye affinity for a wide range of dyestuffs belonging to different classes. The results showed that the equilibrium swelling of LDPE graft copolymers in water reached after 7 h. In addition, the results showed that the swelling of LDPE graft copolymers was influenced by temperature within the temperature range 10–40°C. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Grafting of Hindered Amine Stabilizer in Poly(propylene) Films under γ‐Irradiation

Summary: In this paper, the grafting of a hindered amine stabilizer (HAS) is studied in isotactic poly(propylene) (PP) films under γ‐irradiation. The HAS used has a definite structure that combines a hindered amine functionality and a UV‐absorbing unit (benzylidene malonate ester group) detectable at 308 nm in the UV spectrum of PP film and 314 nm in chloroform. The stabilizer is added to the polymer at various concentration ratios: 0.1, 0.2, and 0.3 wt.‐%. The percentage of HAS grafting in the PP film at various additive concentrations is determined as a function of γ‐radiation dose in the range of 0–100 kGy by direct spectroscopic measurements through the absorption band of the stabilizer in the UV spectra of the PP film. The percentage of free HAS extracted with chloroform from the PP film versus the radiation dose is determined by UV spectroscopy for all the additive concentrations used. This study reveals that only 80% of the HAS is grafted on the 100 kGy irradiated PP matrix independent of the additive concentration used. However, the percentage of HAS grafted on PP films displays an exponential dependence on γ‐radiation dose. These results are consistent with the data obtained on the free HAS content. γ‐Irradiation grafting of HAS in the PP is accompanied by the oxidative degradation of the polymer substrate that is evaluated by increasing the carbonyl index and reducing significantly the oxidation induction time of the PP films.

The percentage of hindered amine stabilizer grafted to the PP film as a function of γ‐radiation dose.     

Preparation and characterization of acrylonitrile‐ethyl methacrylate copolymers and the effect of LiClO4 salt on electrical properties of copolymer films

Copolymers of poly(acrylonitrile‐co‐ethyl methacrylate), P(AN‐EMA), with three different EMA content and parent homopolymers were synthesized by emulsion polymerization. The chemical composition of copolymers were identified by FTIR, ¹H‐NMR and ¹³C‐NMR spectroscopy. The thermal properties of copolymers were modified by changing the EMA content in copolymer compositions. Various amounts of LiClO₄ salt loaded (PAN‐co‐PEMA) copolymer films were prepared by solution casting. The dielectric properties of these films at different temperatures and frequencies were investigated. It was found that the dielectric constant and ac‐conductivity of copolymer films were strongly influenced by the salt amounts and EMA content in copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Surface microphase separation in PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films

Well‐defined poly(dimethylsiloxane)‐block‐poly(methyl methacrylate)‐block‐poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) (PDMS‐b‐PMMA‐b‐PHFBMA) triblock copolymers were synthesized via atom transfer radical polymerization (ATRP). Surface microphase separation in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films was investigated. The microstructure of the block copolymers was investigated by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Surface composition was studied by X‐ray photoelectron spectroscopy (XPS). The chemical composition at the surface was determined by the surface microphase separation in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films. The increase of the PHFBMA content could strengthen the microphase separation behavior in the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymer films and reduce their surface tension. Comparison between the PDMS‐b‐PMMA‐b‐PHFBMA triblock copolymers and the PDMS‐b‐PHFBMA diblock copolymers showed that the introduction of the PMMA segments promote the fluorine segregation onto the surface and decrease the fluorine content in the copolymers with low surface energy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011