Preparation of polypropylene‐graft‐cardanol by reactive extrusion and its composite material with bamboo powder

The polypropylene‐graft‐cardanol was prepared by reactive extrusion, which is solvent‐free melt process, continuous processing, and controllable over residence time. The effect of monomer and initiator concentration on grafting ratio, grafting efficiency, and melt flow index (MFI) was also studied. The yield was quantified by UV–vis spectrometer. The chemical structure was investigated by infrared spectroscopy and gel ratio. A possible mechanism was supposed. The particular structure of cardanol can retain the MFI value of matrix resins and prevent polypropylene (PP) from being decomposed. The grafting ratio could be easily obtained from an experimental formula deduced from the linearity relationship between grafting ratio and MFI. The effect of cardanol grafted onto PP on the compatibility of PP and bamboo powder was studied by contact angle measurements, scanning electron microscopy, and tensile properties test. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solid state mechano‐chemical grafting copolymerization of hydroxyethyl cellulose with acrylic acid

The effects of mechanochemical treatment on hydroxyethyl cellulose (HEC) and its grafting reaction with acrylic acid (AA) under solvent‐free conditions were studied through a vibratory ball‐milling machine, which was developed in our laboratory. Fourier transform infrared (FTIR) spectroscopy and ¹³C‐NMR analysis were used to investigate the structural development of HEC during vibromilling and the grafting mechanism. Further development of the structure and properties of the graft copolymer was characterized by viscosity measurement, wide‐angle X‐ray diffraction (WAXD), and thermal gravity (TG) analysis. The FTIR results showed a new peak at 1720 cm^?1, corresponding to the C?O absorbance peak of AA, which indicated that AA was successfully grafted onto HEC during the high‐energy vibromilling of the HEC/AA mixture at ambient temperature in the absence of a solvent and a catalyst. The WAXD showed the destruction of crystals of HEC during the milling, and the TG analysis demonstrated the improvement of the thermal stability of the copolymer. The effects of the processing conditions on the grafting rate and grafting efficiency were studied by chemical titration to determine the optimum grafting conditions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Graft copolymerization of N‐isopropylacrylamide onto poly(vinyl chloride)

Poly(vinyl chloride) (PVC) was dehydrochlorinated in alkali solution and then grafted with N‐isopropylacrylamide (NIPAM) using benzoyl peroxide as an initiator under a nitrogen atmosphere. The results show that grafting of NIPAM onto dehydrochlorinated PVC (DHPVC) by means of chemical initiation is easily performed. The influence of various reaction conditions such as NIPAM concentration, reaction time, initiator concentration, and PVC content on the grafting copolymerization was investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1234–1241, 1999     

Preparation and characterization of nano‐CaCO3 encapsulated with polyacrylic and its application in PVC toughness

The properties and morphology of nano‐calcium carbonate (nano‐CaCO₃) modified with the titanate coupling agent isopropyl trioleoyl titanate (IPTT) were characterized by Fourier transform infrared, thermogravimetric analyses, surface tension, and transmission electron microscopy. The results showed that the grafting ratio of IPTT on the surface of nano‐CaCO₃ (IPTT‐Ca) increased with IPTT content. IPTT‐Ca/PBA/PMMA (IPTT‐Ca/ACR, PBA/PMMA core‐shell polymer, referred to ACR) latexes were prepared by seeded emulsion polymerization. They were then used to mix with PVC resin. The outer layer (PMMA) enhanced the dispensability of IPTT‐Ca/ACR in the PVC matrix by increasing the interfacial interaction of these composite particles with PVC. The notched impact strengths of the blends were influenced by the weight ratio of IPTT‐Ca to BA/MMA monomers, the weight ratio of BA/MMA. The relationships between the mechanical properties and the core‐shell composite structures were elaborated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of High‐Energy Vibromilling on Interfacial Interaction and Mechanical Properties of PVC/Nano‐CaCO3 Composites

Summary: The effects of interfacial interaction between nano‐CaCO₃ and PVC on mechanical properties and morphology of PVC/nano‐CaCO₃ composites were studied. Nano‐CaCO₃ was treated with vibromilling in the presence of PVC and coupling agents. The mechanical properties of PVC/treated nano‐CaCO₃ are remarkably improved. Transmission electron microscopy results revealed that vibromilled nano‐CaCO₃ particles are well dispersed in PVC matrix with good homogeneity and well adhered to PVC matrix. Molau test indicated that chemical reaction between newly formed surface of nano‐CaCO₃ and PVC or coupling agent took place. Theoretical calculation results show that the interfacial interaction between PVC and nano‐CaCO₃ are substantially improved through vibromilling treatment of nano‐CaCO₃ in the presence of PVC and coupling agent.

Molau test results of the samples in THF.     

Synthesis and characterization of dextrin‐grafted polypropylene

We carried out the graft copolymerization of the water‐soluble natural polymer dextrin onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. PP was irradiated by γ rays from a Co⁶⁰ source at a constant dose rate of 3.40 kGy/h to introduce hydroperoxide linkages, which served as the sites for grafting. The graft copolymerization was studied as a function of different reaction parameters, and the maximum percentage grafting (P_g; 55%) of dextrin onto PP was obtained at optimum conditions of [BPO] = 5.165 × 10⁻² mol/L, temperature = 60°C in 120 min with 15 mL of water. Different grafting parameters, such as the percentage apparent grafting, percentage grafting, and percentage true grafting have been evaluated. The graft copolymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Swelling studies were carried out in pure, binary, ternary, and quaternary solvent systems composed of water, ethanol (EtOH), dimethyl sulfoxide (DMSO), and N,N‐dimethylformamide (DMF) at different ratios. The maximum swelling percentage PP‐g‐dextrin (both composite and true graft) was observed in pure DMSO and DMF followed by EtOH and water. Water‐retention studies of PP and PP‐g‐dextrin (both composite and true graft) were investigated at different time periods, temperatures, and pH values. The maximum percentage water retention of PP‐g‐dextrin (composite, 124%) was observed at 8 h and 50°C in a neutral medium (pH 7). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Grafting of iPP powder with methacrylate monomers in water medium

The grafting of different methacrylates on iPP in the solid state has been studied under various reaction conditions using a radical initiation. Three peroxides and five grafting agents representing methyl‐, ethyl‐, butyl‐, ethyl hexyl‐, and dodecyl methacrylate were tested. The grafting efficiency (GE) performed in water medium (slurry) as possible heat transfer medium was compared with the GE obtained without using water. The iPP powder was first impregnated with monomer and peroxide initiator and then water solution of NaCl was added. Obtained GEs were much higher for all peroxides and monomers used when compared with GE performed without water. Quantity of grafted monomer was determined by Fourier transform infrared spectroscopy (FTIR). The products were characterized by differential scanning calorimetry (DSC) and surface energies of grafted iPP films were measured. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Graft Copolymerization of Styrene‐Maleic Anhydride Onto Poly(Vinyl Chloride) and Its Cross‐linking by Toluene Diisocyanate: Characterization,Thermal, and Mechanical Properties

In this work, styrene‐maleic anhydride (St‐MA) copolymer was successfully grafted onto poly(vinyl chloride) (PVC) by means of chemical method in cyclohexanone medium. In this manner, the effects of various parameters such as total monomer content, monomers ratio, and initiator concentration on the grafting percentage (GP) and acid value (AV) were examined. The graft copolymers were characterized by Fourier‐transform infrared and nuclear magnetic resonance spectroscopy methods. Afterward, the cross‐linking reaction was carried out through MA hydrolysis and condensation reaction between maleic acid and produced diamines, by toluene diisocyanate (TDI) at the presence of hot water. The results showed that the GP and AV of PVC‐g‐(St‐MA) copolymers were considerably higher than those of PVC‐g‐MA and PVC‐g‐St with significant molecular weight. A gel content of 56% was attained with 1 phr TDI in PVC‐g‐(St‐MA) copolymer. The glass transition temperatures and mechanical properties of PVC‐g‐(St‐MA) samples were increased compared to pure PVC. Cross‐linked PVC‐g‐(St‐MA) showed improved mechanical properties than other samples, but the glass transition temperature of PVC backbone in this cross‐linked copolymer was disappeared due to its heavily dense structure. J. VINYL ADDIT. TECHNOL., 25:377–384, 2019. © 2019 Society of Plastics Engineers     

Graft copolymerization of an itaconic acid/acrylamide monomer mixture onto poly(ethylene terephthalate) fibers with benzoyl peroxide

A mixture of acrylamide (AAm) and itaconic acid (IA) was grafted onto poly(ethylene terephthalate) (PET) fibers with benzoyl peroxide in aqueous media. The effects of polymerization conditions such as the temperature, polymerization time, initiator concentration, and monomer mixture ratio on grafting were investigated. The maximum graft yield was 76.1% with an AAm/IA mixture ratio of 90/10 (mol/mol). The graft yield was as low as 3% in the single grafting of IA, whereas the use of AAm as a comonomer increased the amount of IA that entered the fiber structure to 33.5%. An increase in the temperature from 65 to 85°C increased the grafting rate and saturation graft yield. However, an increase in the temperature above 85°C decreased the saturation graft yield. The graft yield increased up to an initiator concentration of 1.0 × 10^?2 M and decreased afterwards. The grafting rate was 0.65th‐ and 0.74th‐order with respect to the initiator and AAm concentrations, respectively. The densities, diameters, and moisture‐regain values of the AAm/IA‐grafted PET fibers increased with the graft yield. Similarly, there was an increase in the dyeability of the AAm/IA‐grafted fibers with acidic and basic dyes. The grafted fibers were characterized with Fourier transform infrared and thermogravimetric analysis, and their morphologies were examined with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1795–1803, 2005     

Photografting of PVC containing N,N‐diethyldithiocarbamate groups with vinyl monomers

Poly(vinyl chloride) (PVC) with pendent N,N‐diethyldithiocarbamate groups (PVC–SR) was prepared through the reaction of PVC with sodium N,N‐diethyldithiocarbamate (NaSR) in butanone and used as a photoinitiator for the grafting polymerization of three vinyl monomers [styrene (St), methyl methacrylate (MMA), and acrylamide (Am)]. The effects of ultraviolet (UV) irradiation time, PVC–SR amount, and the monomer amount on grafting and grafting efficiency were investigated. The results showed that PVC–SR could initiate the polymerization of three vinyl monomers effectively and obtained crosslinked copolymers. The grafting and grafting efficiency of styrene and methyl methacrylate were higher than those of acrylamide. The polymerization activity of three monomers was acrylamide > methyl methacrylate > styrene. By analyzing the UV spectrum of PVC–SR with a different irradiation time, it was confirmed that PVC–SR was dissociated mainly into macromolecular the sulfur radical PVC–S · and the small molecular carbon radical · C(S)N(C₂H₅)₂; the grafting polymerization mechanism was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2569–2574, 2000     

Surface treatment of plasticized poly(vinyl chloride) to prevent plasticizer migration

In this investigation, plasticized poly(vinyl chloride) (PVC) was treated with poly(azido acrylate)s to prevent plasticizer migration. This was achieved by modification of PVC sheets with poly(azido acrylate)s in a dichloromethane solution followed by irradiation under UV light. The surface‐modified PVC sheets with poly (azido acrylate)s were characterized with Fourier transform infrared spectroscopy and scanning electron microscopy analyses. The migration of the plasticizer was prevented to a large extent from modified PVC in comparison with unmodified PVC. The amount of plasticizer migration with respect to the irradiation time, incubation time, and number of dipping times was evaluated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface‐initiated nitroxide‐mediated radical polymerization of 4‐vinylpyridine on magnetite nanoparticles

Poly (4‐vinylpyridine) (P4VP) brushes had been prepared by the surface‐initiated nitroxide‐mediated radical polymerization of 4‐VP on the surface of 3‐methacryloxyproyltrimethoxysilane (3‐MPS)‐modified magnetite nanoparticles with an average diameter of 30 nm. The grafting polymerization was accomplished by nitroxide‐mediated polymerization of 4‐VP, using 4‐hydroxyl‐2,2,6,6‐tetramethyl‐1‐piperidinyl‐oxy (HTEMPO·) free radical as capping agent and benzoyl peroxide (BPO) as initiator. X‐ray photoelectron spectra (XPS) measurement demonstrated that the alkoxysilane initiator layer had formed on the magnetite surface. Gel permeation chromatograph analysis and XPS measurement suggested that the amount of grafted P4VP increases with increasing grafting time. The amount of P4VP grafted on the surface could be determined to be 0.09 chains/nm² by thermogravimetric analysis. The P4VP‐grafted magnetite particles exhibited the characteristics of multidomain system, distinct from the single domain attributes of the pure magnetite particles. Atomic force‐microscopy analysis revealed the diameter of the grafted P4VP magnetic latex particles is in the range of 120 nm to 150 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

One simple and stable coating of mixed‐charge copolymers on poly(vinyl chloride) films to improve antifouling efficiency

An antifouling surface is highly desirable for many biomedical applications. In this study, poly(vinyl chloride) (PVC) films were endowed with the improved properties of resisting nonspecific protein adsorption and platelet adhesion simply through being coated with a kind of mixed‐charge zwitterionic polymer, poly(3‐sulfopropyl methacrylate–methacrylatoethyl trimethyl ammonium chloride–glycidyl methacrylate) (PSTG), with random moieties of negatively charged 3‐sulfopropyl methacrylate potassium, positively charged [2‐(methacryloyloxy)‐ethyl] trimethylammonium chloride, and glycidyl methacrylate. The PSTG‐grafted PVC films were formed by the simple immersion of an amino‐functionalized PVC film into a PSTG solution. A grafting density of 220.84 µg/cm² of PSTG4‐grafted PVC film was successfully obtained. The PSTG4‐grafted PVC film showed a lower contact angle (37.5 °) than the ungrafted PVC film (98.3 °). The in vitro protein adsorption results show that the bovine serum albumin adsorption amount decreased 6.72 µg/cm² in the case of the PSTG4‐grafted PVC film, whereas that on the ungrafted PVC film was 28.54 µg/cm². So, PSTG‐grafted PVC films could be promising materials for medical devices. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44632.     

固相接枝物PE—g—DEM的制备,分析及应用

采用固相接枝技术,以马来酸二乙酯为单体对ＰＥ进行功能化改性,研究了单体用量,引发剂用量,反应温度,反应时间对接枝率及反应体系熔体流动速率的影响,用红光谱对接枝进行了表征。将接枝物用于ＰＶＣ合金的制备,结果表明,在ＰＶＣ／ＰＥ－Ｃ合金中接枝物引起了增韧,增强的双重作用。     

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

A novel redox system, potassium ditelluratoargentate(III) (DTA)–cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA–cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two‐step single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X‐ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry     

Tensile properties of a poly(vinyl chloride) composite filled with poly(methyl methacrylate) grafted to oil palm empty fruit bunches

The influence of oil palm empty fruit bunch (OPEFB) fiber and oil palm empty fruit bunches grafted with poly(methyl methacrylate) (OPEFB‐g‐PMMA) on the tensile properties of poly(vinyl chloride) (PVC) was investigated. The OPEFB‐g‐PMMA fiber was first prepared with the optimum conditions for the grafting reaction, which were determined in our previous study. To produce composites, the PVC resin, OPEFB‐g‐PMMA fiber or ungrafted OPEFB fiber, and other additives were first dry‐blended with a laboratory blender before being milled into sheets on a two‐roll mill. Test specimens were then hot‐pressed, and then the tensile properties were determined. A comparison with the composite filled with the ungrafted OPEFB fiber showed that the tensile strength and elongation at break increased, whereas Young's modulus decreased, with the incorporation of 20 phr OPEFB‐g‐PMMA fiber into the PVC matrix. The trend of the tensile properties obtained in this study was supported by functional group analysis, glass‐transition temperature measurements, and surface morphological analysis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Melt grafting of n‐butyl methacrylate onto poly(vinyl chloride): Synthesis and characterization*

The graft copolymerization of n‐butyl methacrylate monomer onto compounded poly(vinyl chloride) was carried out by melt‐mixing process in a Brabender plasticorder (BPCR) using a free‐radical initiator. The reaction conditions such as initiator and monomer concentration, shear rate (rpm), residence time, and temperature were optimized in the mixing head of BPCR attached to a torque rheometer. The graft copolymers were Soxhlet extracted with cyclohexane and were characterized by intrinsic viscosity, FTIR, and ¹³C‐NMR spectroscopy. A maximum of 14% grafting was obtained. The graft copolymer showed significant improvement in processibility and both thermal and mechanical properties. Scale‐up studies of the optimized recipe were carried out in a single‐screw extruder for commercial trials/evaluation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2442–2449, 2004     

A Study on Morphological Structure of Low Molecular Weight PVC Prepared by Vibromilling Degradation

The effects of vibromilling on particle size, crystalline structure, optical density, and the plasticizer absorption of poly(vinyl chloride) (PVC) were studied through Fourier-transform infrared spectroscopy, scanning electron microscopy and physical property tests. The experimental results show that the intensity of the FTIR absorption band at 635 cm^?1 of PVC becomes weaker and tends to disappear during vibromilling. The particle size of PVC is decreased, and the surface area and the amount of plasticizer absorption increase with increased vibromilling time. The low molecular weight PVC so prepared has lower crystallinity and glass transition temperature, and higher plasticizer absorption capacity; it should have good processability.     

Different factors in the supercritical CO2‐assisted grafting of poly(acrylic acid) to polypropylene

The grafting of poly(acrylic acid) to polypropylene was realized with supercritical CO₂ as a substrate swelling agent and a monomer/initiator carrier. The effects of different supercritical CO₂‐assisted impregnation conditions on the substrate mass increment and grafting efficiency were studied. The original isotactic polypropylene and the grafting product were characterized through IR spectroscopy, differential scanning calorimetry, and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4280–4285, 2006