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... 

Monomer grafting, a unique technique for polysaccharide modification, is always performed under inert (e.g., N2) atmosphere. This work is the first report related to evaluating the possibility and efficiency of the grafting of acrylonitrile (AN) onto starch in presence of oxygen. Thus, corn starch (in both granular and gelatinized states) as well as soluble starch were grafted by AN using a ceric-carbohydrate redox initiating system. Graft copolymerizations were performed under nitrogen, air, and oxygen atmospheres at similar conditions. Grafting occurrence was verified using chemical and spectral proofs. The polymerization mechanism and kinetics were investigated by recording the... 

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  

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),... 

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... 

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... 

Homopolymer hydrogel of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and its nanocomposite counterpart were prepared to study their swelling properties. The hydrogels showed ability to absorb and retain electrolytes as well as binary mixtures of water and organic solvents (i.e., methanol, ethanol, acetone, ethylene glycol (EG), polyethylene glycol, N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The nanocomposite gel exhibited lower swelling in all solvent compositions in comparison with non-composite gel. Unlike conventional acrylic acid-based hydrogels, the poly(AMPS) gels showed superabsorbing capacity in pure ethanol, methanol, EG, DMSO and NMP. Meanwhile, swelling... 

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... 

Polyacrylonitrile (PAN) was grafted onto carboxymethyl cellulose (CMC) sodium salt backbones by using cerie ammonium nitrate (CAN) as an initiator. The graft co-polymer, CMC-g-PAN, was hydrolyzed by NaOH solution to yield hydrogel, H-CMC-g-PAN. The nitrile groups of CMC-g-PAN were completely converted to a mixture of hydrophilic carboxamide and carboxylate groups during alkaline hydrolysis, followed by in situ crosslinking of the grafted PAN chains. The structure of the products was confirmed by FTIR spectroscopy. The synthetic parameters affecting the swelling capacity of the hydrogel (i.e., CMC-g-PAN add-on value, the hydrolysis time and temperature, and concentration of NaOH) were... 

A novel superabsorbent hydrogel composite based on kappa-carrageenan (κC) was prepared by graft copolymerisation of acrylic acid (AA) in the presence of kaolin using methylenebisacrylamide (MBA) as a crosslinking agent and ammonium persulfate (APS) as an initiator. The synthetic variables (i.e. AA, MBA and APS concentration, and the amount of kaolin) affecting the water absorbency of the resulting superabsorbent composite were studied. Evidence of grafting and kaolin interaction was obtained by comparing the FTIR spectra of the initial substrates and of the superabsorbent composite. A new absorption band at 1722 cm-1 in the composite spectrum confirmed the kaolin-organic polymer linkage.... 

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... 

A novel kappa-carrageenan (κC)-based superabsorbing hydrogel was synthesized through graft copolymerization of acrylamide (AAm) onto a κC substrate in the presence of a crosslinking agent. The crosslinked κC-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... 

Graft copolymerization of methacrylonitrile (MAN) onto carboxymethylcellulose (CMC) was carried out under argon atmosphere in a homogeneous aqueous medium by using ceric ammonium nitrate (CAN) as an initiator. The FTIR spectroscopy and solubility characteristics of the products were used for confirming the graft copolymer formation. The effect of the concentration of the initiator, monomer and polysaccharide as well as the reaction time and temperature on the graft copolymerization reactions were investigated to achieve the optimum grafting conditions (i.e. CAN 0.00065 mol/L, MAN 0.85 mol/L, CMC 1% W/V, reaction temperature 45°C, and reaction time 2 h). According to the empirical rates of... 

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... 

Chitin was extracted from shrimp shells and then deacetylated to obtain chitosan. The degree of deacetylation of the chitosan was determined to be 0.76 using pH-metric titration. A large number of cyanide functional groups were introduced onto chitosan by grafting with polyacrylonitrile as an efficient way of modification. The graft copolymerization reactions were carried out under argon atmosphere in a homogeneous aqueous phase (containing a small portion of acetic acid) by using eerie ammonium nitrate as an initiator. Evidence of grafting was obtained by comparing FTIR spectra of chitosan and the graft copolymer as well as solubility characteristics of the products. The synthetic... 

An eight-step synthetic strategy was followed to prepare a series of novel azobenzene-containing methacrylate monomers bearing spiroacetal-norbornene moiety and methylene spacers. Thus, the adduct 2, obtained from cyclopentadiene and acrolein, was converted to 1,3-diol 3. The diol was acetalized with nitrobenzaldehyde 4 under microwave irradiation to obtain nitro compound 5 that was then reduced to amino compound 6. Diazonium salt of 6 was coupled with phenol to produce phenolic compound 7 which was then reacted with n-dibromoalkanes (n = 2, 4, 6, 8, 10) to yield bromo compounds 9a-e. Nucleophilic substitution reaction of the bromo compounds with lithium methacrylate produced the methacrylic... 

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 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...