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     

Chemically induced graft copolymerization of acrylonitrile onto lignocellulosic fibers

The grafting of vinyl monomers is an important method for replacing hydrophilic hydroxyl groups present on the surface of natural fibers by hydrophobic polymer chains. It improves the compatibility of natural fibers with polymer matrixes during the fabrication of natural‐fiber‐reinforced polymer composites. This article deals with the graft copolymerization of acrylonitrile onto Agave americana fibers in air in the presence of ceric ammonium nitrate as a redox initiator. A maximum percentage grafting of 24% was obtained after the optimization of various reaction parameters, including the reaction time, temperature, and concentrations of nitric acid, initiator, and monomer. The graft copolymers obtained under the optimum conditions were then subjected to the evaluation of different physicochemical properties, including swelling behavior in different solvents, moisture absorption behavior under different humidity levels, and chemical resistance. The graft copolymers were further characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermal analysis (thermogravimetric analysis/differential thermal analysis), and X‐ray diffraction techniques. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

黄原胶与丙烯酰胺接枝共聚反应的研究

以过硫酸铵为引发剂,在氮气保护下,研究了黄原胶与丙烯酰胺的接枝共聚反应。考察了单体浓度、引发剂浓度、反应温度和反应时间等因素对接枝率及接枝效率的影响,探讨了过硫酸铵引发黄原胶接枝丙烯酰胺共聚反应的基本规律。采用红外光谱、X射线粉末衍射对接枝共聚物的结构进行研究,用热重分析法表征了产物的热性能,并初步探讨了接枝机理。结果表明,过硫酸铵能有效地引发黄原胶与丙烯酰胺的接枝共聚反应,并且接枝率和接枝效率随单体浓度、引发剂浓度、反应温度的变化出现极大值,随反应时间的延长不断上升,直至基本不变。     

Analysis of the solid phase copolymerization grafting process

Solid phase grafting, which is an emerging process for the production of graft copolymers, was analyzed and reviewed as an environmentally friendly and inexpensive graft copolymerization process. The effect of the process variables; amount of initiator, catalyst, interfacial agent, monomer, reaction temperature and reaction time were examined. Two graft copolymers, produced by solid phase grafting, were used to show differences in graft percentage by changing the process conditions. The two graft copolymers used were maleic anhydride graft onto polypropylene and acrylic acid graft onto polystyrene. A proposed mechanism was given for each example and characteristic bonds proposed in the PP-g-MA mechanism was positively identified by NMR spectroscopy. Graft levels of 4 wt% PS-g-AAc and 9.6 wt% PP-g-MA were obtained providing comparable or superior graft levels to other grafting processes. Successful scale-up of the solid phase technique proved that this process is efficient and marketable.     

聚碳酸酯-g-聚苯乙烯共聚物的合成与表征

研究了聚碳酸酯（ＰＣ）与苯乙烯（ＳＴ）的悬浮接枝共聚合,考察了ＰＣ／ＳＴ质量比、引发剂质量分数、反应时间对共聚合的影响,获得了接枝率为３５％,接枝效率为６５％的接枝共聚物,并对接枝共聚物进行ＩＲ、ＤＳＣ、ＤＭＡ等表征,测定了支链ＰＳ的分子量及支链数。     

Synthesis and characterization of dual responsive graft copolymers composed of casein and poly(N-isopropylacrylamide)

A series of novel temperature- and pH- responsive water-soluble graft copolymers, casein-g-poly(N-isopropylacrylamide)(PNIPAAm), were prepared via a direct graft copolymerization of N-Isopropylacrylamide (NIPAAm) from casein. The polymerization was induced by tert-butyl hydroperoxide (TBHP) in water at general condition. Chemical structures of the graft copolymers were characterized by Fourier transform infrared spectra (FTIR), Thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect elements on graft copolymerization, such as concentration of initiator, reaction time, reaction temperature and ratio of NIPAAm to casein were investigated in terms of NIPAAm conversion, grafting percentage (GP) and grafting efficiency (GE), respectively. The graft copolymers are stimuli-sensitive with respect to both temperature and pH in aqueous solutions. It could self-assembly into core-shell particles in aqueous solution with collapsed PNIPAAm as core as well as inverse core-hair particles with expanded casein as core on changing temperature or pH, as indicated by transmission electron microscopy (TEM).     

Synthesis of graft copolymers of binary vinyl monomer mixtures onto acetylated Saccharum spontaneum L and characterization

Methylmethacrylate (MMA) + acrylamide (AAm), MMA + acrylonitrile (AN), and MMA + acrylic acid (AA) binary vinyl monomer mixtures were graft copolymerization onto acetylated Saccharum spontaneum L, was carried out and maximum graft yield (185.6 %) was found with MMA+AAm binary mixture. Synthesized graft co‐polymers were characterized with FT‐IR spectrophotometry, scanning electron microscopy (SEM), thermal analysis TGA/DTA/DTG, and X‐ray diffraction (XRD) techniques. Thermal stability of Ss‐g‐poly(MMA + AAm) was found to be more than that of natural, acetylated S. spontaneum fiber and other graft copolymers. Although on grafting, percentage crystallinity and crystallinity index were found to decrease but graft copolymers were found to exhibit more moisture, chemical, and thermal resistance. Also, it can be observed that the surface of the grafted fibers is highly rough in comparison with the ungrafted fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Grafting of maleic anhydride onto polypropylene: Synthesis and characterization

Isotactic polypropylene was grafted with maleic anhydride using benzoyl peroxide as an initiator and toluene as a solvent. Effects of various parameters such as monomer and initiator concentration, reaction time, and reaction temperature on percentage grafting were studied. Effect of various solvents on extent of grafting was also studied. The maximum extent of grafting achieved was 5.3%. The graft copolymers were characterized by i.r., thermal, viscometric, and contact angle studies. Improved thermal stability and decreased intrinsic viscosity and critical surface tension were observed for graft copolymers. © 1994 John Wiley & Sons, Inc.     

Grafting Study and Antifungal Activity of a Carboxymethyl Cellulose Derivative

Graft copolymerization of appropriate monomers onto cellulose and its derivatives can enhance their characteristics and consequently expand their potential applications. Carboxymethyl cellulose (CMC) was prepared and characterized by FTIR spectroscopy and XRD. Graft copolymerization of acrylic acid sodium salt (AAs) onto CMC using ammonium persulfate (APS) as a free radical initiator was carried out under nitrogen atmosphere in aqueous solution. Occurrence of grafting was confirmed by comparison of FTIR spectra of CMC and the graft copolymers as well as the XRD patterns and thermal analysis. The effects of concentration of AA, temperature, concentration of APS and reaction time on the grafting yield were investigated by determining the grafting percentage and grafting efficiency. With other conditions kept constant, the obtained optimum grafting conditions were: CMC = 0.2 g, [AAs] = 2 mM, [APS] = 7.5 mM, temperature = 70°C and reaction time = 2 h. A preliminary study was then carried out to evaluate the antifungal activity of the prepared graft copolymer. This preliminary investigation of the prepared graft copolymers showed that they may be tailored and exploited to expand the utilization of these systems in medical applications.     

Solid state grafting copolymerization of acrylamide onto poly(vinyl alcohol) initiated by redox system

A solid state grafting copolymerization of acrylamide (AM) onto poly(vinyl alcohol) (PVA) was conducted with ammonium persulfate and sodium bisulfite redox system as initiators. Before the reaction the PVA powder and required amount of AM were mixed evenly, and sprayed with water to swell the PVA powder and to dissolve AM. Then the swollen PVA powder was sprayed with the redox solution, and the reaction temperature was controlled at a temperature between 30°C and 80°C for 120 min. The grafting percentage and efficiency were determined as functions of monomer/PVA ratio, initiator concentration and reaction temperature. The structure and performance of the graft copolymers were confirmed by FTIR‐ATR, XRD, ¹³C NMR, and thermogravimetric analysis, together with mechanical property and apparent viscosity measurements. It has been confirmed that grafting copolymerization of AM onto PVA initiated by this redox system occurred with higher grafting percentage and efficiency in the solid state. The thermal stability and water‐solubility of grafted PVA were found to be better than those of unmodified PVA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39938.     

Synthesis and characterisation of PP-g-butyl acrylate copolymers

Butyl acrylate was grafted onto isotactic polypropylene using benzoyl peroxide as an initiator and toluene as a solvent. Effects of various parameters such as monomer and initiator concentration, reaction time and temperature on rates of polymerization, percentage grafting and grafting efficiency were studied. The extent of grafting achieved was 2.85%. The graft copolymers were characterized by IR, thermal, viscometric and contact-angle studies. Improved thermal stability and decreased intrinsic viscosity and critical surface tension were observed for graft copolymers.     

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     

Studies on the grafting of methyl methacrylate onto polyacrylonitrile

Grafting of methyl methacrylate onto polyacrylonitrile was carried out using benzoyl peroxide as initiator and dimethylformamide as solvent. The occurrence of grafting was confirmed by IR spectroscopy and SEM analysis. Effects of various parameters such as reaction time, reaction temperature, initiator concentration, and monomer concentration on rate of polymerization, percentage grafting, and grafting efficiency were studied. The graft copolymers were found to have the similar thermal and structural properties like virgin polyacrylonitrile. Decreasing extent of swelling was observed for the polymers of higher percentage graft in polar solvents. © 1993 John Wiley & Sons, Inc.     

Graft copolymerization of acrylonitrile and methacrylonitrile onto gelatin by mutual irradiation method

In order to improve upon certain properties of gelatin graft copolymerization of acrylonitrile (AN) and methacrylonitrile (MAN) onto gelatin has been studied in aqueous medium using γ rays as a source of initiation. Optimum conditions for affording maximum percentage of grafting have been evaluated as a function of various reaction parameters. The grafted polyacrylonitrile (PAN) was isolated from the graft copolymer by acid hydrolysis, and the average molecular weight (M_v) of the isolated polymer has been determined viscometrically. The graft copolymers were characterized by IR spectroscopic methods and thermogravimetric analysis (TGA). Acrylonitrile was found to be more reactive than methacrylonitrile toward graft copolymerization. © 1994 John Wiley & Sons, Inc.     

Optimized conditions for the grafting reaction of poly(methyl methacrylate) onto oil‐palm empty fruit bunch fibers

This article describes the graft copolymerization of poly(methyl methacrylate) (PMMA) onto oil‐palm empty fruit bunches (OPEFBs) with a fiber length of less than 75 μm. The graft copolymerization was carried out under a nitrogen atmosphere by a free‐radical initiation technique in an aqueous medium. Hydrogen peroxide and ferrous ions were used as a redox initiator/cocatalyst system. The PMMA homopolymer that formed during the reaction was removed from the grafted copolymers by Soxhlet extraction. Determining the effects of the reaction period, reaction temperature, and monomer concentration on the grafting percentage was the main objective, and they were investigated systematically. The optimum reaction period, reaction temperature, monomer concentration, and initiator concentration were 60 min, 50°C, 47.15 × 10^?3 mol, and 3.92 × 10^?3 mol, respectively. The maximum percentage of grafting achieved under these optimum conditions was 173%. The presence of PMMA functional groups on OPEFB and the enormous reduction of the hydroxyl‐group absorption band in PMMA‐g‐OPEFB spectra provided evidence of the successful grafting reaction. The improvement of the thermal stability of PMMA‐g‐OPEFB also showed the optimal achievement of the grafting reaction of PMMA onto OPEFB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chitin/poly(methyl methacrylate) hybrid materials

Summary Graft copolymerization of methyl methacrylate onto mercapto-chitin has been examined. The copolymerization reaction proceeded efficiently in dimethyl sulfoxide at 80°C to give chitin-graft-poly(methyl methacrylate)s. The grafting percentage increased with the amount of the monomer and reached above 1200% under appropriate conditions. The resulting graft copolymers exhibited remarkable affinity for various common organic solvents.     

淀粉丙烯酰胺表面控制反应机理及接枝产物结构表征

以木薯淀粉和丙烯酰胺为主要原料,采用反相乳液聚合方法合成淀粉丙烯酰胺接枝共聚物,并通过红外光谱、电镜扫描、X射线衍射、热分析等手段对接枝共聚产物进行结构分析和聚合机理探讨。实验结果显示,淀粉与丙烯酰胺的反应主要发生在淀粉团粒表面,符合表面控制反应机理;接枝共聚物中含有淀粉和丙烯酰胺成分;共聚反应改变了原淀粉的聚集形态,接枝产物基本上为无定形的聚集态结构;但对淀粉的热稳定性影响不显著。     

The Synthesis of Chitin-g-Poly(vinyl acetate) Copolymers with a Redox Initiator

Vinyl acetate monomer was graft polymerized onto chitin with a redox initiator, cerium ammonium nitrate. Both the graft copolymerization and emulsion polymerization of pure poly(vinyl acetate) (PVAc) were observed during the reaction and a stable dispersion solution was obtained after the reaction. After the PVAc homopolymer was removed by acetone extraction, the grafting efficiency and grafting percentage were calculated from the weight balance. Transmission and scanning electronic microscope were used to observe the morphologies of the reaction product. Experimental results indicated that at initial stage of reaction, graft copolymerization, which occurred on the surface of chitin particles, dominated over the emulsion polymerization. After that, the rate of emulsion polymerization increased greatly and became dominant. The existence of chitin not only provided the stability of the emulsion particles, but also increased the polymerization rate. Structures of copolymers were evidenced with the techniques of Fourier transform infrared and differential scanning calorimeter.     

Ceric‐initiated free radical graft copolymerization of acrylonitrile onto kappa carrageenan

The polysaccharide, kappa carrageenan (kC), was modified using ceric‐initiated graft copolymerization of acrylonitrile (AN) under inert atmosphere in a homogeneous aqueous medium. Grafting was confirmed using FTIR spectroscopy, solubility test, elemental analysis, acid hydrolysis, and thermogravimetric analysis (TGA). kC‐graft‐poly(AN) products had a higher thermal stability than kC as revealed by TGA analysis. The polyacrylonitrile branches were isolated by acidic degradation of the carrageenan main chains and characterized by size exclusion chromatography (SEC). Residual monomers were not found by HPLC in graft copolymers stored even for longer periods. The effect of various factors affecting on grafting, i.e., concentration of the initiator, monomer, and polysaccharide as well as the reaction time and temperature were studied by conventional methods to achieve the optimum grafting parameters. The graft copolymerization reactions were kinetically investigated using semi‐empirical expressions and a suitable rate expression has been derived. According to the empirical rates of the polymerization and the graft copolymerization of AN onto kC backbone, the overall activation energy of the graft copolymerization reaction was estimated to be 20.96 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

黄原胶与丙烯酸接枝共聚反应的研究

以过硫酸钾为引发剂,在氮气保护下,研究了黄原胶（XG）与丙烯酸（AA）的接枝共聚反应。考察了单体浓度、引发剂浓度、反应温度和反应时间等因素对接枝率及接枝效率的影响,探讨了过硫酸钾引发黄原胶接枝丙烯酸共聚反应的基本规律。采用红外光谱（FT—IR）对接枝共聚物的结构进行研究,并初步探讨了接枝机理。