Nanocomposites of PBAT and cellulose nanocrystals modified by in situ polymerization and melt extrusion

Cellulose nanocrystals (CNC) were successfully grafted with a low molecular weight poly(butylene glutarate) through an in situ polymerization procedure. The grafting treatment decreased the CNC hydrophilic character and increased the onset of their thermal degradation by approximately 20°C, thus increasing the possibilities of CNC application. Composites of grafted and nongrafted CNC with a poly(butylene‐adipate‐co‐terephthalate) (PBAT) matrix were prepared by melt extrusion. The CNC addition led to an increase of 50% of the tensile elastic modulus of the PBAT. In addition, dynamic mechanical thermal analysis showed that the composite with CNC retained its high modulus even at temperatures far above the glass transition temperature of PBAT. At 60°C the storage modulus of the composite with CNC was approximately 200% higher than that of the pure PBAT. Thus, in this work, nanocomposites of improved properties were obtained through a combination of in situ polymerization and melt extrusion. POLYM. ENG. SCI., 56:1339–1348, 2016. © 2016 Society of Plastics Engineers     

Characterization of acrylic acid grafted poly(ethylene terephthalate) fabric

The preirradiation grafting of acrylic acid (AA) onto poly(ethylene terephthalate) (PET) had been found to affect the thermal and physical characteristics of fabric. The grafted fabrics with various graft levels were characterized by thermal gravimetric analysis (TGA), ATR‐FTIR spectroscopy, contact angle, differential scanning calorimetry (DSC), X‐ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The initial decomposition temperature and T₅₀ were increased with the increase in degree of grafting. The percentage crystallinity was decreased as the degree of grafting increases. The detailed elemental analysis was done by X‐ray photoelectron spectroscopy (XPS). The atomic ratio (O_1s/C_1s) was found to increase significantly with increasing the degree of grafting and reached 0.64 at 14.5% grafting from 0.38 for virgin PET. The surface topography and morphology was strongly influenced as the degree of grafting was increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Chemical grafting of aniline and o‐toluidine onto poly(ethylene terephthalate) fiber

Graft copolymerization of poly(aniline) and poly(o‐toluidine) onto poly(ethylene terephthalate) fiber was conducted by using peroxydisulfate as a lone initiator under nitrogen atmosphere at various experimental conditions in aqueous hydrochloric acid medium. The grafting of poly(aniline) and poly(o‐toluidine) onto poly(ethylene terephthalate) fiber was verified by recording cyclic voltammetry of the grafted fiber, conductivity measurements, and thermal analysis. Graft parameters—such as % grafting, % efficiency, and the rate of grafting—were followed. Grafting was always accompanied by homopolymerization. The rate of homopolymerization was also followed in all experimental conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 121–128, 1999     

Surface grafting of poly(pentafluorostyrene) on the iron and iron oxide particles via reversible addition fragmentation chain transfer (RAFT) polymerization

A surface grafting technique is reported for synthesis of poly(pentafluorostyrene) via reversible addition fragmentation chain transfer onto iron (iron oxide) particles. 4‐Methoxydithiobenzoate is used for the RAFT chain transfer agent. The molecular weight, surface morphology, thickness, thermal properties, and monomer conversion of the grafted polymer are reported. The grafted poly(pentafluorostyrene)–iron particles show a higher thermal transition temperature compared to the nongrafted polymer because it is speculated that the covalent bond between the polymer backbone and the surface of the iron particles restricts the molecular mobility. The monomer conversion increases in proportion to the amount of chain transfer agent (CTA) concentration at early polymerization time. The grafted poly(pentafluorostyrene) shows a “hairy” like polymer architecture with fibril thickness in the range of 80 to 100 nm. A thin coating is expected to maintain the magnetic saturation properties of iron particles. To the best of our knowledge, this is the first time that poly(pentafluorostyrene) has been grafted onto the iron particles utilizing RAFT and 4‐methoxydithiobenzoate as a CTA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44898.     

Functionalized carbon nanotubes with oligomeric intumescent flame retardant for reducing the agglomeration and flammability of poly(ethylene vinyl acetate) nanocomposites

A novel oligomeric phosphorous–nitrogen‐containing intumescent flame retardant poly (2,6‐diaminopyridine spirocyclic pentaerythritol bisphosphonate) (PDSPB) is synthesized, and subsequently multiwalled carbon nanotube (MWNT)‐grafted oligomeric intumescent flame retardant, MWNT‐g‐PDSPB, is fabricated via chemical grafting reaction and characterized. The grafting reaction was characterized by FTIR, NMR, and XPS. After high‐density PDSPB (88 wt%) were attached to the MWNTs, core‐shell nanostructures with MWNTs as the hard core and PDSPB as the soft shell were formed. The resultant MWNT‐g‐PDSPB was soluble and stable in polar solvents, such as DMF and DMSO. MWNT‐g‐PDSPB has excellent thermal stability and charring ability. The TEM results showed that the functionalized MWNTs could achieve better dispersion in poly(ethylene vinyl acetate) (EVA) matrix. The residue char of MWNT‐g‐PDSPB is as high as 70 wt%, and the grafting of intumescent flame retardant of PDSPB can improve both the dispersion of MWNTs in polymer matrix and flame retardancy of the nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Radiation‐induced graft copolymerization of methylmethacrylate onto poly(tetrafluoroethylene‐co‐ethylene) film

Modification of poly(tetrafluoroethylene‐co‐ethylene), Tefzel (ETFE), film has been carried out by grafting methylmethacrylate (MMA) by radiation method including preirradiation and double‐irradiation methods. Percentage of grafting has been determined as a function of the (i) total dose, (ii) monomer concentration, (iii) amount of liquor ratio, (iv) reaction time, and (v) temperature.The effect of different alcohols such as methanol, ethanol, 2‐propanol, n‐butanol, n‐pentanol, and 2‐ethoxy ethanol on percentage of grafting of MMA was also studied. The graft copolymers were characterized by IR spectroscopy and thermogravimetric analysis (TGA). Methylmethacrylate produces higher percentage of grafting by preirradiaton method than double‐irradiation method. MMA‐grafted ETFE films (S_irr), i.e., prepared by preirradiation involving single irradiation show better thermal stability than MMA‐grafted ETFE films (D_irr), i.e., prepared by double irradiation and unmodified ETFE film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Antibacterial,flame retardant,and physico‐chemical properties of cotton fabric graft copolymerized with a binary mixture of acrylonitrile and 4‐vinylpyridine

Modification of cotton fabric has been carried out through chemically induced graft copolymerization of binary mixture of acrylonitrile (AN) and 4‐vinyl pyridine (4‐VP) using ceric ammonium nitrate, (CAN) as initiator. Maximum percentage of grafting (151.28%) has been obtained at [4‐VP] = 0.376 mol L^?1 and [AN] = 1.221 mol L^?1, [CAN] = 0.0255 mol L^?1 and [HNO₃] = 0.9585 mol L^?1 in 25mL of water at 70°C in 180 min. Post quarternization and phosphorylation reactions of the grey and grafted cotton fabrics have been carried out to study their antibacterial and flame retardant properties respectively. The fabrics have been characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The physico‐chemical properties such as wettability, moisture regain, crease recovery and tensile strength of the grey and grafted cotton fabric have also been evaluated. The modified fabric has been shown to exhibit excellent antibacterial and flame retarding properties with improved physico‐chemical properties except for the mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40415.     

Modification of polypropylene via the free‐radical grafting ternary monomer in water suspension systems

Maleic anhydride, styrene, and butyl acrylate were grafted onto polypropylene (PP) via free‐radical polymerization. The grafted product, polypropylene‐g‐(maleic anhydride–styrene–butyl acrylate) (PP‐g‐PMSB), was prepared in a water suspension system, and a nongrafted polymer, poly(maleic anhydride–styrene–butyl acrylate) (PMSB′), was produced at the same time. The optimal synthesis conditions were determined by orthogonal experiments. The crystallinity, thermal stability, melt flow rate, and hydrophilicity of the grafting samples were investigated in the presence or absence of PMSB′. The results indicate that the grafting percentage (G_p) of PP‐g‐PMSB and the content of PMSB′ (C_m) increased as the monomer content increased under the optimum reaction conditions. All of these ternary monomers were grafted onto the PP backbone as long‐chain branches. With increasing G_p, PP‐g‐PMSB's polarity and thermal stability increased, the crystallinity decreased, and the molecular distribution became narrower. The contact angle decreased to 72.12° when G_p was 6.87%. With increasing C_m, the crystallinity and thermal stability of the grafting products decreased compared to PP‐g‐PMSB and the molecular distribution grew wider. The contact angle decreased to 63.51° when C_m was 3.64%; this indicated that the presence of PMSB′ further improved the hydrophilicity of the grafted products. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modification of jute fabric via laccase/t‐BHP‐mediated graft polymerization with acrylamide

Enzymatic processes provide new perspectives for the modification of lignocellulose materials. Lignin is an excellent substrate for laccase, and the modification of lignin‐rich jute fabric via graft polymerization with acrylamide (AAm) mediated by laccase and tert‐butyl hydroperoxide (t‐BHP) was investigated in this study. The products obtained were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The grafting rate was determined in terms of elemental analysis. The hydrophilicity and thermal and dyeing properties of the modified jute fabric were studied. The results supported the conclusion that the polyacrylamide was grafted on the lignin of the jute fiber by laccase in coordination with t‐BHP, representing a grafting rate of 2.87%. The hydrophilicity, thermostability, dye uptake, and dyeing depth of the jute fiber were increased after the enzymatic graft modification with AAm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40387.     

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

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

Application of poly(diphenolic acid‐phenyl phosphate)‐based layer by layer nanocoating in flame retardant ramie fabrics

Poly(diphenolic acid‐phenyl phosphate) [poly(DPA‐PDCP)], obtained from diphenolic acid (a well‐known biomass chemical), was used together with polyethylenimine (PEI) to construct a flame retardant surface coating for ramie fabric using layer‐by‐layer self‐assembly. Attenuated total reflection Fourier transform infrared spectroscopy (ATR‐FTIR) and scanning electron microscope (SEM) equipped with an energy dispersive X‐ray spectrometer (EDX) were used to confirm the successful formation of layer by layer assembly. Assessment of the thermal and flammability properties for poly(DPA‐PDCP)/PEI‐coated ramie fabrics showed that the thermal stability, flame retardancy, and residual char were enhanced as the concentration of poly(DPA‐PDCP) and the BL number in the LbL process increased as well as the treatment of KH550 was applied. SEM and EDX analysis of the char residue confirmed further the intumescent flame retardant mechanism. This work demonstrated the great potentials of poly(DPA‐PDCP)/PEI flame retardant nanocoating constructed by LbL assembly method in the application of ramie fabric. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44795.     

Synthesis of carborane acrylate and flame retardant modification on silk fabric via graft copolymerization with phosphate‐containing acrylate

A novel carborane acrylate monomer (1‐acryloyloxyethyl carborane) was synthesized by addition reaction, hydrolysis, and esterification and characterized by proton nuclear magnetic resonance (¹H NMR) spectroscopy and Fourier transform infrared spectroscopy (FT‐IR) analysis. Subsequently, the carborane monomer and a phosphate‐containing methacrylate monomer were applied on the modification of a silk fabric. The heat resistance and flame retardancy of the silk fabric before and after modification were compared. Energy‐dispersive X‐ray spectrometer (EDS) and FT‐IR showed that carborane monomer and phosphate‐containing methacrylate were grafted onto the surface of the fibers. The cross‐sectional morphology of silk fabrics after burning was observed by scanning electron microscope (SEM), and the flame‐retardant mechanism was analyzed. Thermal‐gravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis revealed that the thermal stability of the modified silk increased with the increase of the grafting yield. The MCC‐2 microcalorimeter (MCC) test showed that, when using 1‐acryloyloxyethyl carborane as monomer and blending with phosphate‐containing methacrylate, the maximum heat release rate (PHRR) of the modified silk fabric decreased from 97.6 W/g (before grafting) to 51.3 and 45.8 W/g, respectively, and the total heat release (THR) decreased from 10.2 kJ/g (before grafting) to 5.9 and 5.2 kJ/g, respectively. The limiting oxygen index (LOI) test revealed that using 1‐acryloyloxyethyl carborane and phosphate‐containing methacrylate as mixed monomers to modify the silk fabric obtained good flame retardancy, whose LOI value reached 29.8%.     

Comparative study of the radiation‐induced grafting of styrene onto poly(tetrafluoroethylene‐co‐perfluoropropylvinyl ether) and polypropylene substrates. I: Kinetics and structural investigation

A comparative study has been made of the radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐perfluoropropyl vinyl ether) (PFA) and polypropylene (PP) substrates, using the simultaneous irradiation method. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate and irradiation dose on the grafting yield were investigated. Under the same grafting conditions it was found that a higher degree of grafting of styrene was obtained using a mixture of dichloromethane/methanol solvents for PFA and methanol for PP and the degree of grafting was higher in PP than in PFA at all doses. However, the micro‐Raman spectroscopy analysis of the graft revealed that, for the same degree of grafting, the penetration depth of the grafted polystyrene into the substrate was higher in PFA than in PP substrates. In both polymers the crystallinity was hardly affected by the grafting process and the degree of crystallinity decreased slightly with grafting dose. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be 0.6 and 1.4 order for PFA and 0.15 and 2.2 for PP, respectively. The degree of grafting increased with increasing radiation dose in both polymers. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield for PFA and PP was accompanied by a proportional increase in the penetration depth of the graft into the substrates. Copyright © 2003 Society of Chemical Industry     

Grafting of poly(acrylic acid) onto cellulosic microfibers and continuous cellulose filaments and characterization

Results from the grafting of poly(acrylic acid) (PAA) onto cellulosic microfibers and continuous cellulose filaments are presented. The grafting of PAA onto cellulosic fibers offers the possibility of developing enhanced ion exchange and fluid absorbency on the fibers. The grafting of PAA was carried out with a two‐step procedure. First, vinyl‐terminated ethoxy silane was deposited on the surface of the fiber. This was followed by a grafting polymerization reaction in aqueous media of acrylic acid with different concentrations of potassium persulfate (KPS), which acted as the initiator. The percentage of grafting increased with increasing KPS concentration and reached a maximum value at a concentration of about 0.4 wt % with respect to the weight of the fiber. The grafted copolymer was characterized by Fourier transform infrared spectroscopy. Strong evidence that the grafting reaction was successful was given by the presence of a band, with a maximum at 1732 cm^?1, that was characteristic of carbonyl group absorption and was not initially present in the cellulosic fibers. The water absorption of the cellulosic microfibers grafted with PAA was three times greater than the water absorption of the nongrafted microfibers. The mechanical properties of continuous cellulose filaments did not change drastically with PAA grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 386–393, 2002     

Modification of Tefzel film through graft copolymerization

The graft copolymerization of styrene (st) and methacrylonitrile (MAN) onto Tefzel film in aqueous media by the preirradiation method has been studied. In order to follow the effect of preswelling of the backbone polymer, grafting was attempted onto preirradiated Tefzel film and monomer preswollen, preirradiated Tefzel film. Optimum conditions pertaining to maximum percentage of grafting of st and MAN have been evaluated. Grafting onto preswollen, preirradiated Tefzel film displayed better results. The effect of different alcohols of increasing chain length on the percentage of grafting of st and MAN was also studied. Graft copolymerization of st showed an increase, while grafting with MAN exhibited a decrease, in the percentage of grafting in the presence of alcohols as compared to that obtained in the aqueous medium. Characterization of the graft copolymers was made by IR and thermogravimetric studies. Tefzel‐graft‐polystyrene showed improved thermal stability while the MAN grafted onto preswollen, preirradiated Tefzel film produced graft copolymer with poor thermal stability. Copyright © 2004 Society of Chemical Industry     

Study of the effect of natural rubber‐graft‐o‐aminophenol on the thermal stability and mechanical properties of nitrile rubber

The grafting copolymerization of natural rubber and o‐aminophenol was carried out by using two‐roll mill machine. The prepared grafted antioxidant, NR‐graft‐o‐AP, analyzed by using Infrared and ¹H‐NMR Spectroscopy techniques. The thermal stability, mechanical properties, and ultrasonic attenuation coefficient were evaluated for NBR vulcanizates containing the commercial antioxidant, PBN, and the prepared grafted antioxidant, NR‐graft‐o‐AP, and the control vulcanizate. Results of the thermal stability indicate that the prepared NR‐graft‐o‐AP can protect NBR vulcanizate against thermal treatment much better than the commercial antioxidant, PBN, and control mix, respectively. The prepared grafted antioxidant improves the mechanical properties of NBR vulcanizate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of N,N-dimethylformamide and polymer grafting on the morphology of polyester fibers in fabric substrate

Photo-induced graft polymerization of acrylic acid (AA) and methyl acrylate (MA) in the liquid and vapor phase, respectively, onto N,N-dimethyformamide (DMF)-pretreated poly(ethylene terephthalate) (PET) fibers in fabric substrate was studied. The effect of various synthesis conditions and DMF pretreatment on the graft yields on PET was investigated. The internal morphology and properties of DMF-pretreated and grafted PET fibers in the fabric were characterized using density and birefringence measurements, differential thermal analysis (DTA), Fourier transform infrared spectroscopy (FTIR), dyeing methods, and critical dissolution times. The grafting was promoted by increasing DMF pretreatment temperature and the amount of DMF retention in the PET. Increasing biacetyl and monomer flow time and irradiation time enhanced grafting. DMF pretreatment resulted in increases in total void content, degree of crystallinity, trans-isomer content, chain folding, segmental mobility, and molecular packing of the PET, but caused decreases in its amorphous orientation, intermolecular forces, and individual void size through longitudinal shrinkage, lateral swelling, and removal of oligomers. Subsequent graft copolymerization led to further changes in the internal morphology and properties of the PET. PET grafted with AA had a higher cohesive energy density, lower degree of molecular packing, and larger individual void size, but less total void content, lower segmental mobility, less chain orientation, and a lower degree of crystallinity. PET grafted with MA showed increases in total void content, individual void size, segmental mobility, and molecular packing, but showed decreases in chain orientation and degree of crystallinity. © 1996 John Wiley & Sons, Inc.     

Modification of cellulosic fabrics to impart flame retardancy properties

Graft copolymerization of dimethylaminoethyl methacrylate (DMAEMA) onto cotton‐cellulose in the fabric form was carried out using a cellulose‐thiocarbonate‐ammonium persulphate redox initiation system. Effects of the concentration of the monomer, effect of liquor ratio, grafting time, and temperature were studied. The results point out the following important aspects of flame retardation of cellulose fabrics. (1) The graft polymerization of DMAEMA can improve the flame retardant properties of cellulose fabrics. (2) Tertiary amine grafted to cellulosic fabrics is suitable for nitrogen compounds that can effectively operate as synergists. The flame retardant properties of the poly‐DMAEMA‐ grafted‐phosphorylated cellulosic materials were found to be excellent even after 25 dry clean washings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Zwitterionic sulfobetaine‐modified non‐woven fabric for blood filtration

Blood filtration requires a high removal ratio of leukocytes and with simultaneous high recovery ratio of platelets and other beneficial components. Problems are often encountered with blood filter materials in terms of high platelet loss. Zwitterions such as phosphorylcholine, sulfobetaine and carboxybetaine show effective resistance against protein adsorption and platelet adhesion. The study reported was aimed at achieving surface modification of poly(butylene terephthalate) non‐woven fabric (PBTNF) using UV radiation‐induced graft copolymerization of a zwitterionic sulfobetaine, N‐(3‐sulfopropyl)‐N‐methacroyloxyethyl‐N,N‐dimethylammonium betaine (SMDB), in order to improve the wettability and platelet recovery ratio of the PBTNF. Attenuated total reflection Fourier transform infrared and X‐ray photoelectron spectroscopy results showed that SMDB was successfully grafted onto the PBTNF. Photoinitiator concentration, monomer concentration and UV irradiation time affected markedly the degree of grafting. Critical wetting surface tension, water wetting time and hemolysis tests showed an improvement in wettability and blood compatibility as a result of graft copolymerization of SMDB. A blood filter material composed of SMDB‐modified PBTNF reduced platelet adhesion and had higher platelet recovery compared to poly(acrylic acid)‐modified PBTNF. It was found that SMDB monomer was successfully grafted onto PBTNF using UV radiation. The degree of grafting of SMDB could be controlled by varying the photoinitiator concentration, monomer concentration and UV irradiation time. SMDB‐modified PBTNF showed significant improvement in wettability and blood compatibility. The zwitterionic structure of SMDB is resistant to platelet adhesion. The SMDB‐modified PBTNF could be a candidate for a blood filter material and in other medical applications. Copyright © 2010 Society of Chemical Industry     

Chemical and mechanical properties of butyl methacrylate grafted wool fiber

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