Graft Copolymers of Acrylonitrile onto Dextrin for Use in Separation Technologies

The use of polymers in enrichment and separation technologies has attracted a lot of interest in recent times. To develop low-cost and environmentally friendly technologies for the removal of metal ions from water systems, graft copolymers based on dextrin were synthesized by grafting poly(acrylonitrile) onto it. The optimum grafting conditions were evaluated for grafting by varying the nature and amount of solvent, changes in concentration of monomer and initiator, reaction time and temperature. Graft copolymers were further functionalized by partial hydrolysis, and were characterized by water uptake, FTIR, SEM and elemental analysis. Sorption of Fe²⁺ and Cr⁶⁺ ions on graft copolymers were investigated as a function of percent grafting, change in metal ion concentration, temperature and pH, to define their end-uses in separation technologies.     

Cation exchange membranes by radiation-induced graft copolymerization of styrene onto PFA copolymer films. I. Preparation and characterization of the graft copolymer

PFA-g-polystyrene graft copolymers were prepared by simultaneous radiation-induced graft copolymerization of styrene onto poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) films. The effects of grafting conditions such as monomer concentration, dose, and dose rate were investigated. Three solvents, i.e., methanol, benzene, and dichloromethane, were used as diluents in this grafting system. Of the three solvents employed, dichloromethane was found to greatly enhance the grafting process, and the degree of grafting increased with the increase of monomer concentration until it reached its highest value at a styrene concentration of 60 (vol %). The dependence of the initial rate of grafting on the monomer concentration was found to be of the order of 1.2. The degree of grafting was found to increase with the increase in irradiation dose, while it considerably decreased with the increase in dose rate. The formation of graft copolymers was confirmed by FTIR analysis. The structural investigation by X-ray diffraction (XRD) shows that the degree of crystallinity content of such graft copolymers decreases with the increase in grafting, and consequently, the mechanical properties of the graft copolymers were influenced to some extent. Both tensile strength and elongation percent decreased with the increase in the degree of grafting. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2095–2102, 1999     

Competitive removal of heavy metal ions by cellulose graft copolymers

The effect of composition of graft chains of four types cellulose graft copolymers on the competitive removal of Pb²⁺, Cu²⁺, and Cd²⁺ ions from aqueous solution was investigated. The copolymers used were (1) cellulose‐g‐polyacrylic acid (cellulose‐g‐pAA) with grafting percentages of 7, 18, and 30%; (2) cellulose‐g‐p(AA–NMBA) prepared by grafting of AA onto cellulose in the presence of crosslinking agent of N,N′‐methylene bisacrylamide (NMBA); (3) cellulose‐g‐p(AA–AASO₃H) prepared by grafting of a monomer mixture of acrylic acid (AA) and 2‐acrylamido‐2‐methyl propane sulphonic acid (AASO₃H) containing 10% (in mole) AASO₃H; and (4) cellulose‐g‐pAASO₃H obtained by grafting of AASO₃H onto cellulose. The concentrations of ions which were kept constant at 4 mmol/L in an aqueous solution of pH 4.5 were equal. Metal ion removal capacities and removal percentages of the copolymers was determined. Metal ion removal capacity of cellulose‐g‐pAA did not change with the increase in grafting percentages of the copolymer and determined to be 0.27 mmol metal ion/g_copolymer. Although the metal removal rate of cellulose‐g‐p(AA–NMBA) copolymer was lower than that of cellulose‐g‐pAA, removal capacities of both copolymers were the same which was equal to 0.24 mmol metal ion/g_copolymer. Cellulose did not remove any ion under the same conditions. In addition, cellulose‐g‐pAASO₃H removed practically no ion from the aqueous solution (0.02 mmol metal ion/g_copolymer). The presence of AASO₃H in the graft chains of cellulose‐g‐p(AA–AASO₃H) created a synergistic effect with respect to metal removal and led to a slight increase in metal ion adsorption capability in comparison to that of cellulose‐g‐pAA. All types of cellulose copolymers were found to be selective for the removal of Pb²⁺ over Cu²⁺ and Cd²⁺. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2034–2039, 2003     

Competitive removal of nickel (II), cobalt (II), and zinc (II) ions from aqueous solutions by starch‐graft‐acrylic acid copolymers

Graft copolymerization of acrylic acid (AA) onto starch was carried out with ceric ammonium nitrate as initiator under nitrogen atmosphere. The grafting percentages (GP%) of starch‐graft‐acrylic acid (St‐g‐AA) copolymers were determined. The effect of GP% of St‐g‐AA copolymers on the competitive removal of Co²⁺, Ni²⁺, Zn²⁺ ions from aqueous solution was investigated at different pH (2, 4, 6). The concentrations of each ion in aqueous solution 5 mmol/L. Effects of various parameters such as treatment time, initial pH of the solution and grafting percentage of starch graft copolymers were investigated. Metal ion removal capacities of St‐g‐AA copolymers increased with GP% of the copolymers and pH. The results show that the removal of metal ions followed as given in the order Co²⁺ > Ni²⁺ > Zn²⁺. In this study, metal ion removal capacities were determined by atomic absorption spectrophotometer (AAS). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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。     

Radiation-initiated graft copolymerization of individual monomer and comonomer onto polyethylene and polytetrafluoroethylene films

Preparation and some properties of the graft copolymers obtained by radiation-induced graft polymerization of methacrylic acid (MAA) and (acrylonitrile/MAA) comonomer onto polyethylene and polytetrafluoroethylene films, were investigated. The effect of reaction conditions, solvent, monomer, and inhibitor concentration, comonomer composition, and comonomer concentration, on the graft copolymerization process was studied. The grafting process was enhanced in the presence of comonomer (AN/MAA) as compared with individual grafting of MAA or acrylonitrile (AN). The optimum comonomer composition, at which the highest grafting yield was obtained, was found to be (80/20) wt % of (AN/MAA) comonomer. The graft copolymerization of (AN/MAA) comonomer was enhanced in presence of AN due to its higher polarity strength. The electrical and swelling properties of the graft copolymers were greatly affected by the contents of PAN and PMAA graft chains. Mechanical properties of the graft copolymers were significantly changed with the grafting yield.     

Competitive Removal of Heavy Metal Ions by Starch-Graft-Acrylic Acid Copolymers

Graft copolymerization of acrylic acid (AA) onto starch was carried out with ceric ammonium nitrate as initiator under nitrogen atmosphere. The structures of the synthesized graft copolymers were identified by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The grafting percentages (GP%) of starch-graft-acrylic acid (S-g-AA) copolymers were determined. Increasing the molar concentration of AA from 0.1 to 0.5 mol/L caused a significant increase in the GP%. The effect of GP% of S-g-AA copolymers on the competitive removal of Pb²⁺, Cu²⁺, Cd²⁺ ions from aqueous solution was investigated at pH 4.5. The concentrations of each ion in aqueous solution were equal to each other, which were kept constant at 4 mmol/L. Metal ion removal capacities were determined by atomic absorption spectrophotometer (AAS). Metal ion removal capacities of S-g-AA copolymers rose with the increase in GP% of the copolymers and the order of the removal of heavy metal ions was Pb²⁺ > Cu²⁺ > Cd²⁺.     

Synthesis and thermosensitive behavior of dextran graft copolymers containing poly (N-vinylcaprolactam) side chains

New graft copolymers were synthesized by grafting N-vinylcaprolactam onto dextran. Their composition and structure were investigated by elemental analyses, infrared spectra and thermogravimetric analyses. By optical transmittance measurements, it was found that the aqueous solutions of these graft copolymers showed a temperature-dependent transmittance change due to the introduction of thermosensitive poly (N-vinylcaprolactam) graft chains. Moreover, the lower critical solution temperature (LCST) of the graft copolymer in aqueous solution was dependent on its grafting extent and concentration. The LCST value was found to increase with the increase of the grafting extent and decrease with the increase of the copolymer concentration. With these stimuli-response properties, such polysaccharide derivative may hold potential applications in biomedicine and biotechnology.     

Synthesis and characterization of N‐vinyl pyrrolidone and cellulosics based functional graft copolymers for use as metal ions and iodine sorbents

To develop cost effective and eco friendly polymeric materials for enrichment and separation technologies, 1‐vinyl‐2‐pyrrolidone (N‐VP) was graft copolymerized onto cellulose, extracted from pine needles. Optimum conditions have been evaluated for the grafting of N‐VP onto cellulose and at these conditions it was also grafted onto cellulose phosphate, hydroxypropyl cellulose, cyanoethyl cellulose, and deoxyhydrazino cellulose. At the optimum grafting conditions for N‐VP, it was also cografted with maleic anhydride. Kinetics of radiochemical graft copolymerization has been studied and evaluation of the polymerization and grafting parameters as percent grafting, percent grafting efficiency, rate of polymerization, homopolymerization, and graft copolymerization have been evaluated. Graft copolymers have been characterized by elemental analysis, FTIR, and swelling studies. An attempt has been made to study sorption of some metal ions such as Fe²⁺ and Cu²⁺ and iodine on select graft copolymers to investigate selectivity in metal ion sorption and iodine sorption as a function of structural aspects of the functionalized graft copolymers to find their end uses in separation and enrichment technologies. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 373–382, 2005     

微波辐射下壳聚糖-丙烯酰胺接枝物的合成及其絮凝性能研究

以硝酸铈铵作为引发剂、丙烯酰胺为单体,用微波辐射法合成了壳聚糖-丙烯酰胺接枝共聚物。通过正交试验考察反应条件对接枝率和接枝效率的影响,得出最佳工艺条件为:反应时间12 min,引发剂浓度5 mmol/L,丙烯酰胺和壳聚糖质量比5:1,反应温度40℃。最佳条件下接枝率和接枝效率分别达到148.6%和44.0%。壳聚糖接枝物与聚丙烯酰胺(PAM)对高岭土悬浮液的絮凝对比试验表明:在酸性条件下接枝物与PAM的絮凝效果相近;在中性和碱性条件下接枝物的絮凝性能优于PAM。     

Grafting of low density poly(ethylene) with butyl acrylate: Synthesis and characterisation

Low density poly(ethylene) was grafted with butyl acrylate using benzoyl peroxide as free radical initiator in an inert atmosphere and toluene as solvent. Various parameters such as reaction time, temperature, initiator concentration and ratio of monomer to polymer were varied to study their effects on percentage of grafting and grafting efficiency of butyl acrylate on to low density poly(ethylene). The graft copolymers were characterised by IR spectroscopy. The change in the solubility behaviour of low density poly(ethylene) due to grafting was studied by turbidometric titration. Thermal stability of graft copolymers was found to be higher than that of LDPE. Intrinsic viscosity data showed an increase in viscosity with increasing grafting percentage.     

S-DMDAAC-AM阳离子型高分子絮凝剂的合成及性能研究

以淀粉(S)、二甲基二烯丙基氯化铵(DMDAAC)、丙烯酰胺(AM)为原料,采用氧化还原引发体系,合成r接枝共聚物S-DMDAAC-AM.考察了反应温度、反应时间、引发剂浓度、单体配比等因素对接枝共聚体系的接枝率、接枝效率和絮凝效果等因素的影响.试验结果表明,最优条件为淀粉(S):单体总量=3.5 g∶10.5 g,反...     

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。     

Radiation‐induced graft copolymerization of cellulosic fabric waste and its application in the removal of cyanide and dichromate from aqueous solution

Graft polymerization and crosslinking in radiation processing are attractive techniques for modification of the chemical and physical properties of the conventional polymer. The graft polymerization and subsequent chemical treatment can introduce a chelate agent function into a conventional polymer such as cellulosic fabric. Cellulosic graft copolymers were prepared by the reaction of the fiber with acrylonitrile (AN) and 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) in DMF initiated by γ‐radiation ⁶⁰Co. The grafted fabric was chemically treated with hydroxyl amine to obtain amidoxime from. Factors affecting the grafting such as radiation dose, monomer concentration and solvent concentration as well as monomer composition was investigated. The chemically modified graft fabric was applied for recovery of cyanide and dichromate from aqueous solution. CN^? shows 89% removal, whereas dichromate has 65% removal. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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。     

淀粉接枝丙烯酰氧乙基三甲基氯化铵共聚物的合成

以玉米淀粉为原料,在水介质中通过硝酸铈铵引发淀粉与丙烯酰氧乙基三甲基氯化铵(DAC)接枝共聚,制备系列含阳离子季铵基团的淀粉-DAC接枝共聚物,系统考察了反应条件对接枝共聚物接枝率(PG)的影响。结果表明:在本实验体系内可制备较高接枝率的阳离子接枝共聚物。当硝酸铈铵的浓度为1.5×10-2mol/L,m(DAC)∶m(淀粉)=3,反应温度40℃,反应时间4 h时,接枝共聚物的接枝率最高可达118.67%。用FTIR、1HNMR、XRD对接枝共聚物结构进行了表征。     

Turbulent drag effectiveness and shear stability of xanthan-gum-based graft copolymers

A number of graft copolymers of xanthan gum and polyacrylamide have been synthesized by grafting acrylamide onto xanthan gum using the ceric-ion-initiated solution polymerization technique. The effects of various synthesis parameters such as amount of catalyst, reaction time, and ratio of xanthan and acrylamide on drag reduction effectiveness of the graft copolymers have been studied. The scaling up of grafting reaction has been accomplished in 40-L reactor. The drag reduction effectiveness of the graft copolymers is investigated over a wide range of concentrations and Reynolds numbers. It is shown that the maximum drag reduction obtainable in xanthan gum solutions above 300 ppm can be obtained in solutions of graft copolymers at concentrations of 100–150 ppm. The grafting also improves the shear stability at higher Reynolds numbers. The shear stability of the graft copolymers at constant wall stress has been found to be superior to polyacrylamide and the mixtures of polyacrylamide and xanthan gum. In general, the shear stability of graft copolymers and polyacrylamide is shown to increase with concentration. The drag reduction characteristics and shear stability have been discussed in terms of structural features of the graft copolymers. The drag reduction characteristics of the graft copolymers are found to be similar to those of flexible polymers.     

超声-微波共辐射法合成纤维素-MMA接枝共聚物

引言纤维素作为一种天然的可再生高分子材料,存在于丰富的绿色植物中,是自然界取之不尽用之不竭的清洁资源。因此,在煤、石油、天然气的储量日益减少的今天,纤维素可作为一种可持续发展的绿色资源来研究和开发。而且天然植物纤维资源丰富、价格低廉,并且具有较好的生物可降解性,在     

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.     

Starch–acrylics graft copolymers and blends: Synthesis,characterization, and applications as matrix for drug delivery

A series of acrylic monomers–starch graft copolymers were prepared by ceric ion initiation method by varying the amount of monomers. These graft copolymers were characterized by IR and ¹³C‐NMR spectroscopy. It was seen that as the concentration of monomer [acrylic acid (AA), methacrylic acid (MA), and methyl methacrylate (MMA)] increased the percent add‐on increased in all the graft copolymers, whereas grafting efficiency increased initially but showed a slight decrease with further increase in the monomer concentration (except for MMA). The release rate of paracetamol as a model drug from graft copolymers as well as their blends was studied at two different pH, 1.2 and 7.4, spectrophotometrically. The release of paracetamol in phosphate buffer solution at pH 1.2 was insignificant in the first 3 h for St‐g‐PAA‐ and St‐g‐PMA‐graft copolymers, which was attributed to the matrix compaction and stabilization through hydrogen bonding at lower pH. At pH 7.4, the release rate was seen to decrease with increase in add‐on. The tablet containing poly(methyl methacrylate) (PMMA) did not disintegrate at the end of 30–32 h, which may be attributed to the hydrophobic nature of PMMA. These results indicate that the graft copolymers may be useful to overcome the harsh environment of the stomach and can be used as excipients in colon‐targeting matrices. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009