Sharif Digital Repository

Acrylonitrile (AN) was grafted onto various natural and modified polysaccharides (i.e., gum arabic, gum tragacanth, xanthan gum, sodium alginate, chitosan, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose) by using ceric-carbohydrate redox initiating system. After overcoming practical problems, mainly from the high viscosity of the aqueous solutions of the different substrates, the graft copolymerization reactions were run either in air or in N2 atmosphere under similar conditions. Grafting was confirmed using chemical and spectral (FTIR) proofs. The reactions were kinetically investigated using semi-empirical expressions and time-temperature profiles. An anomalous... 

Chitosan was modified with polyacrylonitrile (PAN) through ceric-initiated graft copolymerization. The chitosan-g-PAN product was saponified using sodium hydroxide aqueous solution to prepare a novel superabsorbent hydrogel, H-chitoPAN. Duration of completing the saponification reaction as well as the water absorbency capacity of the hydrogel was decreased with increasing the alkaline concentration. Either chitosan-g-PAN or H-chitoPAN was characterized by FTIR spectroscopy and DSC, TGA, and DTG thermal methods. According to FTIR, all the nitrile groups were converted to carboxylate and carboxamide groups. Both modified chitosans exhibited enhanced thermal stability over chitosan. The... 

Polyacrylonitrile (PAN) grafted chitosan was prepared by ceric-initiated graft polymerization of acrylonitrile onto chitosan in a homogenous medium. The copolymer chitosan-g-PAN product was then hydrolyzed to yield a novel smart hydrogel (H-chitoPAN) with superabsorbing properties. The influence of add-on values as well as temperature and time of hydrolysis of the initial chitosan-g-PAN on swelling behavior of the hydrogel was evaluated in water and various salt solutions. The swelling kinetics of the superabsorbing hydrogel was studied as well. The hydrogels exhibited ampholytic and pH-sensitivity characteristics. Several sharp swelling changes were observed in lieu of pH variations in a... 

A non-terminated, low molecular weight, highly crystalline, linear aliphatic polyester was successfully synthesized via ester-interchange polycondensation of cis-2-butene-1,4-diol and diethyl oxalate by using of lead (II) oxide as the catalyst. No decarboxylation occurred during the optimized polymerization. Structural and Chemical identification was performed by elemental analysis, FTIR, 'H-NMR, and Mass spectroscopy. Some macrocyle species were detected in the product, according to GPC. Fragmentation patterns were suggested for the main m/e's of the mass spectrum. Thermal characterization was performed by DSC and TGA. It was found that the overall thermal stability of the polyester is... 

Tetraphenylthiophene diamine (TPTDA) was prepared through a modified three-step route to achieve an improved overall yield. TPTDA reacted with succinic, adipic, suberic, sebasic, and fumaric acids via the Yamazaki phosphorylation method to yield novel partially aromatic polyamides (TPT series). A counterpart polyamide series based on p-phenylene diamine (Ph series) was also synthesized under the same conditions. All of the polymers were characterized by means of spectrochemical (Fourier transform infrared spectroscopy, 1H-nuclear magnetic resonance (NMR), and 13C-NMR) and thermal (differential scanning calorimetry and thermogravimetric) methods of analysis. Solubility of TPT polyamides was... 

A novel kappa-carrageenan (C)-based superabsorbing hydrogel was synthesized through graft copolymerization of acrylamide (AAm) onto a C substrate in the presence of a crosslinking agent. The crosslinked C-poly(AAm) polymer graft was partially hydrolyzed in alkaline medium to yield a superabsorbent resin, H-carragPAM. The resin structure was confirmed using FTIR spectroscopy. The variables of graft copolymerization (monomer, initiator, polysaccharide and crosslinker concentration, reaction temperature and time as well as stirrer speed) that affected on the ultimate water-swelling capacity were optimized. The time-temperature variation of the copolymerization was investigated in terms of the... 

A novel pH-responsive superabsorbing hydrogel based on κ-carrageenan (κC) was prepared through polyacrylamide crosslinking grafting followed by alkaline hydrolysis. The hydrogel structure was confirmed using FT-IR spectroscopy. The hydrolysis conditions were systematically optimized to obtain a hydrogel with maximum swelling capacity. Thus, the reaction variables, including the hydrolysis time and temperature, concentration of sodium hydroxide, amount of hydrogel hydrolyzed and post-neutralization pH, were optimized. The swelling measurements of the hydrogels were conducted in 0.15 M aqueous solutions of LiCl, NaCl, KCl, CaCl2 and AlCl3. As observed for the hydrolyzed hydrogel (H-carragPAM),... 

Tetraphenylthiophene diamine (TPTDA) was prepared through a modified three-step route to achieve an improved overall yield. TPTDA reacted with succinic, adipic, suberic, sebasic, and fumaric acids via the Yamazaki phosphorylation method to yield novel partially aromatic polyamides (TPT series). A counterpart polyamide series based on p-phenylene diamine (Ph series) was also synthesized under the same conditions. All of the polymers were characterized by means of spectrochemical (Fourier transform infrared spectroscopy. 1H-nuclear magnetic resonance (NMR), and 13C-NMR) and thermal (differential scanning calorimetry and thermogravimetric) methods of analysis. Solubility of TPT polyamides was... 

Alcohol-specific superabsorbing gels (superalcogels) based on non-neutralized acrylic acid (AA, 60-94 mol%) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) were prepared via solution polymerization in water. Polyethylene glycol dimethacrylate and potassium persulfate were used as crosslinker and initiator, respectively. Characterization of samples was performed using FTIR, 1H-NMR and thermomechanical analyses. Glass transition temperature and modulus of dried samples were found to be directly changed with their AA content. The gels exhibited enormous ability for absorbing and retaining a variety of mono- and poly-hydric alcohols. For example, in lieu of one gram of a typical sample... 

Novel polyampholytic superabsorbing nanocomposites based on the zwitterionic sulfobetaine monomer [3-(methacrylamido)propyl)]dimethyl(3- sulfopropyl)ammonium hydroxide were synthesized through in situ polymerization in aqueous solution with different contents of an organo-modified clay (OMMT, Cloisite 30B). Structural and thermomechanical properties of hydrogels were characterized by FT-IR, XRD, and DMTA, respectively. Swollen gel strength of hydrogels was determined by a rheological method. Storage modulus of the hydrogels was considerably improved in comparison with its the clay-free counterpart. The nanocomposite hydrogel containing 15% OMMT possessed the highest gel strength. The glass... 

A semi-interpenetrating polymer network (semi-IPN) hydrogel composed of crosslinked chitosan and Polyacrylamide (PAAm) was prepared in the presence of formaldehyde as a crosslinker. The swelling capacity of hydrogel was shown to be affected by the crosslinker and the PAAm/chitosan ratio. The PAAm/chitosan semiIPN hydrogels are swelled at low pHs that attributed to both osmotic pressure and repulsion of -NH3+ groups on chitosan backbones. The swelling of hydrogel in acidic pHs showed that with increasing of chitosan content in the hydrogel, the swelling capacity was increased. But the swelling capacity of hydrogel in neutral pH is reversed, i.e. the higher the PAAm/chitosan ratio, the higher... 

Hydrogel hybrids were conveniently prepared from alkaline hydrolysis of chitosan-poly(acrylonitrile) mixture under highly practical conditions. The reaction of chitosan alkoxide anions with nitrile groups of poly(acrylonitrile) (PAN) forms crosslinking points and results in a three-dimensional network with superswelling ability in aqueous media. The hydrogel hybrid was identified using FTIR spectroscopy. The PAN content of the hydrolyzing feed affects proportionally the swelling capacity of the hydrogel hybrid. The swelling properties (capacity and rate) of the ampholytic hydrogel were investigated preliminarily. © 2005 Wiley Periodicals, Inc  

Novel hydrogels based on zwitterionic monomer [3-(methacrylamido)propyl] dimethyl (3-sulfopropyl) ammonium hydroxide (MPDSAH) and a strong acid monomer (2-acrylamido-2-methylpropane sulfonic acid, AMPS) were synthesized through solution polymerization under normal conditions to achieve nearly quantitative gel yield. The structure of the gels was confirmed using infrared spectroscopy. Thermal properties were simultaneously studied by differential scanning calorimetry and thermogravimetric analysis (DSC/TGA). The effects of the polymerization variables on the swelling capacity of the products were investigated. It was found that, in a certain range of the monomers mol ratio, increase of AMPS... 

Chitosan was modified with polyacrylonitrile (PAN) through ceric-initiated graft copolymerization. The chitosan-g-PAN product was saponified using sodium hydroxide aqueous solution to prepare a novel superabsorbent hydrogel, H-chitoPAN. Duration of completing the saponification reaction as well as the water absorbency capacity of the hydrogel was decreased with increasing the alkaline concentration. Either chitosan-g-PAN or H-chitoPAN was characterized by FTIR spectroscopy and DSC, TGA, and DTG thermal methods. According to FTIR, all the nitrile groups were converted to carboxylate and carboxamide groups. Both modified chitosans exhibited enhanced thermal stability over chitosan. The... 

Carboxymethylcellulose sodium salt (CMC) was doubly modified to prepare a novel poly(acrylamidoxime) chelating resin. Acrylonitrile was firstly graft polymerized onto CMC using cerium ammonium nitrate as an initiator. The polyacrylonitrile (PAN) grafted CMC was then amidoximized via treatment with hydroxylamine to prepare the ion exchange resin. The sorption capacity of the resin towards bivalent metal ions was evaluated while varying the pH, the loading of the PAN and the initial metal ion concentration. The adsorption kinetics were investigated for the cupric ion. The chelating resin exhibited very high metal sorption capacity in comparison with either synthetic or polysaccharide-based... 

Various natural and modified polysaccharides (i.e. arabic gum, tragacanth gum, xanthan gum, sodium alginate, chitosan, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose) were modified using ceric-initiated graft polymerization of acrylonitrile under inert atmosphere. Grafting was confirmed using spectral (FT-IR) proofs. The grafting parameters were determined by conventional methods. Thermal characteristics of the homopolymer-free copolymers were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) under nitrogen atmosphere. The major thermal transitions as well as the activation energy of the major decomposition stages were... 

Various natural and modified polysaccharides (i.e. arabic gum, tragacanth gum, xanthan gum, sodium alginate, chitosan, sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose) were modified using cericinitiated graft polymerization of acrylonitrile under inert atmosphere. Grafting was confirmed using spectral (FT-IR) proofs. The grafting parameters were determined by conventional methods. Thermal characteristics of the homopolymer-free copolymers were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) under nitrogen atmosphere. The major thermal transitions as well as the activation energy of the major decomposition stages were... 

Two series of alkali hydrolyzed starch-g-polyacrylonitrile (H-SPAN) superabsorbents were prepared from granular and gelatinized corn starches. The grafting parameters of SPAN copolymers were determined and the polymers were analyzed by FTIR spectroscopy. A combination of three influencing factors (i.e. thermal pre-treatment of the initial starch, presence or absence of oxygen in the stage of ceric-initiated PAN grafting, and neutralization after alkali treatment) on swelling characteristics of the final hydrogel was evaluated in a practical viewpoint. The superabsorbents were discriminated according to their swelling behavior in water and different aqueous salt solutions. The swelling... 

The present article deals with super-swelling behavior of crosslinked homopolymer of 2-acrylamido-2-methylpropane sulfonic acid, poly(AMPS), in binary mixtures of dimethyl sulfoxide (DMSO) and various polar solvents including water, mono-, and polyhydric alcohols, and amide solvents such as N-methyl pyrrolidone. Extraordinary phase transition sequences including a new unusual swelling phenomenon, referred to as "overentrant" swelling, was observed for this polymeric organogel in the solvent/DMSO mixtures. The swelling behaviors were preliminarily explained based on the major interactions involved in the solvation process and dielectric constant of the swelling media. It was established that... 

As the first part of a continued research on conversion of carboxymethyl cellulose-sodium salt (CMC) to useful biopolymer-based materials, large numbers of cyanide functional groups were introduced onto CMC by grafting with polyacrylonitrile (PAN). The graft copolymerization reactions were carried out under nitrogen atmosphere using ceric ammonium nitrate (CAN) as an initiator. Evidence of grafting was obtained by comparing FTIR spectra of CMC and the graft copolymer as well as solubility characteristics of the products. The synthetic conditions were systematically optimized through studying the effective factors including temperature and concentrations of initiator, acrylonitrile monomer,...