DNA adsorption on poly(N,N‐dimethylacrylamide)‐grafted chitosan hydrogels

In this study, poly(N,N‐dimethylacrylamide) grafted chitosan (PDMAAm‐g‐CT) hydrogels were prepared for deoxyribonucleic acid (DNA) adsorption. Instead of directly grafting the N,N‐dimethylacrylamide (DMAAm) monomer onto the chitosan (CT) chains, poly(N,N‐dimethylacrylamide) with carboxylic acid end group (PDMAAm‐COOH) was firstly synthesized by free‐radical polymerization using mercaptoacetic acid (MAAc) as the chain‐transfer agent and then grafted onto the CT having amino groups. The synthesis of PDMAAm‐COOH and its grafting onto the CT chains were confirmed by attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. From gel permeation chromatography measurements, the number‐average molecular weight (M _n) and polydispersity index of PDMAAm‐COOH were found as 2400 g/mol and 2.3, respectively. The PDMAAm‐g‐CT hydrogels were utilized as the adsorbents in DNA adsorption experiments conducted at +4°C in a trisEDTA solution of pH 7.4. The hydrogels produced with higher PDMAAm‐COOH content exhibited higher DNA adsorption capacity. The DNA adsorption capacity up to 4620 μg DNA/g dry gel could be achieved with the PDMAAm‐g‐CT hydrogels prepared in 80.0 wt % PDMAAm‐COOH feed concentration. This value is approximately seven times higher than that of CT alone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study of the synthesis of chitosan derivatives containing benzo‐21‐crown‐7 and their adsorption properties for metal ions

Three new chitosan crown ethers, N‐Schiff base‐type chitosan crown ethers (I, III), and N‐secondary amino type chitosan crown ether (II) were prepared. N‐Schiff base‐type chitosan crown ethers (I, III) were synthesized by the reaction of 4′‐formylbenzo‐21‐crown‐7 with chitosan or crosslinked chitosan. N‐Secondary amino type chitosan‐crown ether (II) was prepared through the reaction of N‐Schiff base type chitosan crown ether (I) with sodium brohydride. Their structures were characterized by elemental analysis, infrared spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. In the infrared spectra, characteristic peaks of C?N stretch vibration appeared at 1636 cm^?1 for I and 1652 cm^?1 for II; characteristic peaks of N? H stretch vibration appeared at 1570 cm^?1 in II. The X‐ray diffraction analysis showed that the peaks at 2θ = 10° and 28° disappeared in chitosan derivatives I and III, respectively; the peak at 2θ = 10° disappeared and the peak at 2θ = 28° decreased in chitosan‐crown ether II; and the peak at 2θ = 20° decreased in all chitosan derivatives. In the solid‐state ¹³C NMR, characteristic aromatic carbon appeared at 129 ppm in all chitosan derivatives, and the characteristic peaks of carbon in C?N groups appeared at 151 ppm in chitosan crown ethers I and III. The adsorption and selectivity properties of I, II, and III for Pd²⁺, Au³⁺, Pt⁴⁺, Ag⁺, Cu²⁺, and Hg²⁺ were studied. Experimental results showed these adsorbents not only had good adsorption capacities for noble metal ions Pd²⁺, Au³⁺, Pt⁴⁺, and Ag⁺, but also high selectivity for the adsorption of Pd²⁺ with the coexistence of Cu²⁺ and Hg²⁺. Chitosan‐crown ether II only adsorbs Hg²⁺ and does not adsorbs Cu²⁺ in an aqueous system containing Pd²⁺, Cu²⁺, and Hg²⁺. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1886–1891, 2002     

Chitosan and N‐carboxymethylchitosan: I. The role of N‐carboxymethylation of chitosan in the thermal stability and dynamic mechanical properties of its films

Chitosan (degree of deacetylation of 90.2%) and N‐carboxymethylchitosan (N‐CMCh) (degree of substitution of 18.5%) were analyzed using thermogravimetric analysis in order to determine their thermal stability. Also, their films were evaluated using scanning electron microscopy (SEM) and mechanical and dynamic mechanical analysis (DMA). Both polymers showed a thermal degradation peak at T_m ～ 250 °C, with T_onset and weight loss of 175 °C and 62% and 190 °C and 35% for chitosan and N‐CMCh, respectively. N‐CMCh showed a second thermal degradation peak at T_m = 600 °C, with an additional weight loss of 25%. Kinetic thermal analysis showed a slower process of degradation at 100 °C for N‐CMCh compared with chitosan, and an activation energy 13 times higher for the former, confirming the higher stability of N‐CMCh. Analysis of chitosan and N‐CMCh films showed that the latter support a high tension, with lower elasticity, and, as revealed by DMA, N‐CMCh has a more compact film structure, with a crossing arrangement of N‐CMCh fibers, as compared with the chitosan films which were determined from SEM analysis to have fibers in one direction only. Copyright © 2006 Society of Chemical Industry     

Cure kinetics of an epoxidized hemp oil based bioresin system

A novel epoxidized hemp oil (EHO) based bioresin was synthesized by epoxidation in situ with peroxyacetic acid. In this research the cure kinetics of an EHO based bioresin system cured with triethylenetetramine (TETA) was studied by differential scanning calorimetry using both isothermal and nonisothermal data. The results show that the curing behavior can be modeled with a modified Kamal autocatalytic model that accounts for a shift to a diffusion‐controlled reaction postvitrification. The total order of the reaction was found to decrease with an increase in temperature from ～ 5.2 at 110°C to ～ 2.4 at 120°C. Dynamic activation energies were determined from the Kissinger (51.8 kJ/mol) and Ozawa‐Flynn‐Wall (56.3 kJ/mol) methods. Activation energies determined from the autocatalytic method were 139.5 kJ/mol and ?80.5 kJ/mol. The observed negative activation energy is thought to be due to an unidentified competitive reaction that gives rise to the appearance of k₂ decreasing with increasing temperature. The agreement of fit of the model predictions with experimental values was satisfactory for all temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Recycling of reactive dye using semi‐interpenetrating polymer network from sodium alginate and isopropyl acrylamide

A sequence of semi‐interpenetrating polymer network (semi‐IPN) were synthesized by free radical photo copolymerizing acrylic acid and isopropyl acrylamide (NIPAAm) in aqueous sodium alginate (NaAlg). Their structures (FT‐IR), thermal stability (TG/DTG), morphology (SEM), mechanical properties, reactive blue 4 (RB 4) dye adsorption (624 mg/g) and its dying characteristics, reusability of dye and adsorbent were evaluated. TG thermograms of semi‐IPN in air revealed zero order kinetics for initial step thermal degradation with an activation energy of 68.68 kJ/mol. Dye adsorption showed best fit for Langmuir adsorption isotherm and the kinetics followed pseudo‐second‐order model. The water and dye diffusion kinetics followed non‐Fickian mechanism. The changes in thermodynamic parameters namely Gibbs free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated that the adsorption was spontaneous and exothermic process for RB 4/semi‐IPN system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40968.     

Poly(ethylene terephtalate) films modified with N,N‐dimethylacrylamide: Incorporation of disperse dye

Poly(ethylene terephtalate), PET, can be modified with N,N‐dimethylacrylamide to obtain a better incorporation of disperse dye (Disperse Blue 79). Minimal variations in the decomposition at 10% level, melting, and glass transition temperatures, show that the thermal stability of modified PET films does not change when compared to nonmodified PET. The atomic force images show nanopeaks formation on the surface due to the modification. Modified PET films show a decrease in the contact angle and then, an increase in the superficial tension measurements, when compared to the value of 37 ± 1 dynes · cm⁻¹(nonmodified), with values liying in the range of 42–46 ± 0.5 dynes · cm⁻¹. The data obtained by photoacoustic spectroscopy (PAS) for dyed PET films show a dye peak at 580 nm. The data analysis of the peak area show that PET films modified with N,N‐dimethylacrylamide for 15 min at 85°C, dyed for 6 h at 85°C with a dye concentration of 0.333 g/L, incorporate three times more dye than the nonmodified films dyed in the same conditions. By the data obtained from PAS, it was possible to calculate the depth profile of dyeing with values around 54 μm. Factorial analyses show that the dyeing time was the most important variable. The major amount of incorporated dye was obtained by the following combination of variables: temperature and time of modifier treatment were, respectively, 72.5°C and 15 min; time and temperature of dyeing were, respectively, 90°C and 195 min for a dye concentration of 0.133 g/L. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 269–282, 2000     

Synthesis and functionalities of poly(N‐vinylalkylamide). XIV. Polyvinylamine produced by hydrolysis of poly(N‐vinylformamide) and its functionalization

The molecular weights of poly(N‐vinylformamide) [poly(NVF)] obtained by free‐radical polymerization were expanded from being in the range of thousands to hundreds of thousands. Primary amino groups were introduced by the hydrolysis of poly(NVF) under both acidic and basic conditions. After 2 h polyvinylamine [poly(VAm)] was given at 60°C under a 2N NaOH solution. The apparent activation energy of poly(NVF) hydrolysis was 61.8 kJ/mol. Furthermore, alkyl side chains were partly introduced by a polymer modification reaction in poly(VAm) with carboxylic acid, using WSC (water‐soluble carbodiimide) as the activating agent to produce the stimuli‐responsive poly(VAm) derivative. The effects of external stimuli such as temperature and pH on the phase‐transition behavior of the copolymers were then studied. The lower critical solution temperature at pH 12 decreased depending on the alkyl group content. The phase‐transition behavior of the resulting polymers was also found to vary depending on the side‐chain length of the alkyl groups. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1277–1283, 2003     

High‐Temperature Deformation Mechanisms in Monolithic 3YTZP and 3YTZP Containing Single‐Walled Carbon Nanotubes

Monolithic 3YTZP and 3YTZP containing 2.5 vol% of single‐walled carbon nanotubes (SWCNT) were fabricated by Spark Plasma Sintering (SPS) at 1250°C. Microstructural characterization of the as‐fabricated 3YTZP/SWCNTs composite shows a homogeneous CNTs dispersion throughout the ceramic matrix. The specimens have been crept at temperatures between 1100°C and 1200°C in order to investigate the influence of the SWCNTs addition on high‐temperature deformation mechanisms in zirconia. Slightly higher stress exponent values are found for 3YTZP/SWCNTs nanocomposites (n~2.5) compared to monolithic 3YTZP (n~2.0). However, the activation energy in 3YTZP (Q = 715 ± 60 kJ/mol) experiences a reduction of about 25% by the addition of 2.5 vol% of SWCNTs (Q = 540 ± 40 kJ/mol). Scanning electron microscopy studies indicate that there is no microstructural evolution in crept specimens, and Raman spectroscopy measurements show that SWCNTs preserved their integrity during the creep tests. All these results seem to indicate that the high‐temperature deformation mechanism is grain‐boundary sliding (GBS) accommodated by grain‐boundary diffusion, which is influenced by yttrium segregation and the presence of SWCNTs at the grain boundary.     

Radical copolymerization between methyl methacrylate and N‐cyclohexylmaleimide with thiol as an inifer

N‐dodecanethiol (RSH) was found efficient to initiate the radical copolymerization of methyl methacrylate (MMA) with N‐cyclohexylmaleimide (NCMI) at 40–60°C. The initial copolymerization rate, R_p, increases respectively with increasing [RSH] and the mol fraction of NCMI in the comonomer feed, f_NCMI. The molecular weight of the copolymer decreases with increasing [RSH]. The initiator transfer constant of RSH was determined to be C_I = 0.21. The apparent activation energy of the overall copolymerization was measured to be 46.9 kJ/mol. The monomer reactivity ratios were determined to be r_NCMI = 0.32 and r_MMA = 1.35. The glass transition temperature of the copolymer increases obviously with increasing f_NCMI, which indicates that adding NCMI may improve the heat resistance of plexiglass. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1417–1423, 1999     

Equilibrium,kinetics, and thermodynamics of Pd(II) adsorption onto poly(m‐aminobenzoic acid) chelating polymer

This study describes the equilibrium, kinetics, and thermodynamics of the palladium(II) (Pd(II)) adsorption onto poly(m‐aminobenzoic acid) (p‐mABA) chelating polymer. The p‐mABA was synthesized by the oxidation reaction of m‐aminobenzoic acid monomer with ammonium peroxydisulfate (APS). The synthesized p‐mABA chelating polymer was characterized by FTIR spectroscopy, gel permeation chromatography (GPC), thermal analysis, potentiometric titration, and scanning electron microscopy (SEM) analysis methods. The effects of the acidity, temperature, and initial Pd(II) concentration on the adsorption were examined by using batch adsorption technique. The optimum acidity for the Pd(II) adsorption was determined as pH 2. In the equilibrium studies, it was found that the Pd(II) adsorption capacity of the polymer was to be 24.21 mg/g and the adsorption data fitted better to the Langmuir isotherm than the Freundlich isotherm. The kinetics of the adsorption fitted to pseudo‐second‐order kinetic model. In the thermodynamic evaluation of the adsorption, the ΔG° values were calculated as ?16.98 and ?22.26 kJ/mol at 25–55°C temperatures. The enthalpy (ΔH°), entropy (ΔS°), and the activation energy (E_a) were found as 35.40 kJ/mol, 176.05 J/mol K, and 61.71 kJ/mol, respectively. The adsorption of Pd(II) ions onto p‐mABA was a spontaneous, endothermic, and chemical adsorption process which is governed by both ionic interaction and chelating mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42533.     

Thermo‐ and pH‐responsive behaviors of graft copolymer and blend based on chitosan and N‐isopropylacrylamide

Thermo‐ and pH‐sensitive polymers were prepared by graft polymerization or blending of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm). The graft copolymer and blend were characterized by Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction measurements, and solubility test. The maximum grafting (%) of chitosan‐g‐(N‐isopropylacrylamide) (NIPAAm) was obtained at the 0.5 M NIPAAm monomer concentration, 2 × 10⁻³ M of ceric ammonium nitrate initiator and 2 h of reaction time at 25°C. The percentage of grafting (%) and the efficiency of grafting (%) gradually increased with the concentration of NIPAAm up to 0.5 M, and then decreased at above 0.5 M NIPAAm concentration due to the increase in the homopolymerization of NIPAAm. Both crosslinked chitosan‐g‐NIPAAm and chitosan/PNIPAAm blend reached an equilibrium state within 30 min. The equilibrium water content of all IPN samples dropped sharply at pH > 6 and temperature > 30°C. In the buffer solutions of various pH and temperature, the chitosan/PNIPAAm blend IPN has a somewhat higher swelling than that of the chitosan‐g‐NIPAAm IPN. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1381–1391, 2000     

Interpolymer‐specific interactions and miscibility in poly(styrene‐co‐acrylic acid)/poly(styrene‐co‐N,N‐dimethylacrylamide) blends

The miscibility or complexation of poly(styrene‐co‐acrylic acid) containing 27 mol % of acrylic acid (SAA‐27) and poly(styrene‐co‐N,N‐dimethylacrylamide) containing 17 or 32 mol % of N,N‐dimethylacrylamide (SAD‐17, SAD‐32) or poly(N,N‐dimethylacrylamide) (PDMA) were investigated by different techniques. The differential scanning calorimetry (DSC) analysis showed that a single glass‐transition temperature was observed for all the mixtures prepared from tetrahydrofuran (THF) or butan‐2‐one. This is an evidence of their miscibility or complexation over the entire composition range. As the content of the basic constituent increases as within SAA‐27/SAD‐32 and SAA‐27/PDMA, higher number of specific interpolymer interactins occurred and led to the formation of interpolymer complexes in butan‐2‐one. The qualitative Fourier transform infrared (FTIR) spectroscopy study carried out for SAA‐27/SAD‐17 blends revealed that hydrogen bonding occurred between the hydroxyl groups of SAA‐27 and the carbonyl amide of SAD‐17. Quantitative analysis carried out in the 160–210°C temperature range for the SAA‐27 copolymer and its blends of different ratios using the Painter–Coleman association model led to the estimation of the equilibrium constants K₂, K_A and the enthalpies of hydrogen bond formation. These blends are miscible even at 180°C as confirmed from the negative values of the total free energy of mixing ΔG_M over the entire blend composition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1011–1024, 2007     

Extensive N‐methylation of chitosan: evaluating the effects of the reaction conditions by using response surface methodology

The effects of reaction time, concentration of aqueous sodium hydroxide and molar ratio iodomethane/chitosan on the yield of the reaction of chitosan with iodomethane in N‐methyl‐2‐pyrrolidone (NMP) at 25.0 ± 0.1 °C, as well as on the characteristics of the resulting N,N,N‐trimethylchitosan (TMCh), were evaluated by using full‐factorial 2³ design analysis and response surface methodology. This study also aimed to determine the reaction conditions allowing the production of water‐soluble TMCh presenting a high average degree of quaternization and intrinsic viscosity at high reaction yield. ¹H NMR spectroscopy was employed for structural characterization, including the determination of average degrees of acetylation () and quaternization (), while capillary viscometry was used to determine intrinsic viscosity [η]. The results show that when the extensive N‐methylation is carried out for 24 h in NMP/15% NaOH (w/v) employing a lower excess of iodomethane (CH₃I/Ch = 9), water‐soluble highly substituted ( = 46.0%) TMCh ([η] = 213.0 mL g^?1) can be produced in high yield (81.8%). The highly significant mathematical models resulting from this study describe the dependence of the experimental responses on the reaction conditions and allow the characteristics and properties of the resulting TMCh to be defined by properly choosing the reaction conditions. © 2015 Society of Chemical Industry     

Thermal degradation of Kevlar fiber by high‐resolution thermogravimetry

A novel high‐resolution thermogravimetry (TG) technique in a variable heating rate mode that maximizes resolution and minimizes the time required for TG experiments has been performed for evaluating the thermal degradation and its kinetics of Kevlar fiber in the temperature range ∼ 25–900°C. The degradation of Kevlar in nitrogen or air occurs in one step. The decomposition rate and char yield at 900°C are higher in air than in nitrogen, but the degradation temperature is higher in nitrogen than in air. The initial degradation temperature and maximal degradation rate for Kevlar are 520°C and 8.2%/min in air and 530°C and 3.5%/min in nitrogen. The different techniques for calculating the kinetic parameters are compared. The respective activation energy, order, and natural logarithm of preexponential factor of the degradation of Kevlar are achieved at average values of 133 kJ/mol (or 154 kJ/mol), 0.7 (or 1.1), and 16 min⁻¹ (or 20 min⁻¹) in air (or nitrogen). The technique based on the principle that the maximum weight loss rate is observed at the minimum heating rate gives thermal degradation results that were in excellent agreement with values determined by traditional TG experiments. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 565–571, 1999     

Syntheses of novel chitosan derivative with excellent solubility,anticoagulation, and antibacterial property by chemical modification

The soluble and antibacterial chitosan derivative was prepared on the basis of the regioselective chemical modification. The N‐(2‐phthaloylation) chitosan was obtained via the reaction of chitosan with phthalic anhydride in N,N‐dimethylformamide (DMF) at 130°C, and O‐(3,6‐hydroxyethyl) chitosan was produced using chlorohydrins as grafting agent and hydrazine hydrate as reductant. The structure of hydroxyethyl chitosan (HC) was characterized by X‐ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC) respectively. The solubility, anticoagulation, and antibacterial property were assessed separately. The result shows that amine I of chitosan is replaced and the amide II disappears during chemical modification, and the functional groups of C6‐OH and ‐NH2 are also reacted. The water‐solubility of the novel chitosan derivative was enhanced relatively; it could even slightly soluble in methanol. The results of platelet adhesion and the activated partial thromboplastin times (APTTs) indicate that grafting hydroxyethyl could improve anticoagulation of chitosan. The antibacterial activity of HC against Enterococcus and E. coli had been much better owing to enhancing the degree of protonation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of 2‐ethyl‐4‐methylimidazole derivatives as latent curing agents and their application in curing epoxy resin

Three kinds of 2‐ethyl‐4‐methylimidazole (EMI) derivatives (N‐acetyl EMI, N‐benzoyl EMI, and N‐benzenesulfonyl EMI) were synthesized through the reaction of EMI with acetyl chloride, benzoyl chloride, and benzenesulfonyl chloride, respectively. And the structure was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹H‐nuclear magnetic resonance spectroscopy (¹H NMR) spectra. Furthermore, the synthesized EMI derivatives were applied in diglycidyl ether of bisphenol A epoxy resin (DGEBA) as latent curing agent. Differential scanning calorimeter (DSC) was used to analyze the curing behavior of DGEBA/EMI derivative systems, indicating DGEBA could be efficiently cured by the EMI derivatives at 110～160°C, and the corresponding curing activation energy ranged from 71 to 86 kJ/mol. Viscosity data proves that the storage life of DGEBA with N‐acetyl EMI (NAEMI), N‐benzoyl EMI (NBEMI), and N‐benzenesulfonyl EMI (NBSEMI) at room temperature was 38 d, 50 d, and 80 d, and that at 10°C was 90 d, 115 d, and 170 d, respectively. Besides, thermogravimetry (TG), izod impact strength (IIS), and tensile shear strength (TSS) were tested to characterize the thermal stability and mechanical properties of DGEBA cured by EMI derivatives. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42563.     

Thermal Decomposition Performance of Unsymmetrical Dimethylhydrazine (UDMH) Oxalate

The thermal decomposition behavior of unsymmetrical dimethylhydrazine (UDMH) oxalate was studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TG/DTG), and thermogravimetric analysis combined with infrared spectroscopy (TG‐IR). The endothermic decomposition of UDMH oxalate occurred at temperatures between 180.4 °C and 217.6 °C, the maximum decomposition temperature is 199.2 °C. The kinetic parameters of the decomposition reaction were calculated based on the Kissinger equation. The TG‐IR spectra indicated that the thermal main decomposition products of UDMH oxalate are CO₂,H₂O and NH₃.     

Effect of cupric ion on thermal degradation of chitosan

The thermal degradation of chitosan and chitosan–cupric ion compounds in nitrogen was studied by thermogravimetry analysis and differential thermal analysis (DTA) in the temperature range 30–600°C. The effect of cupric ion on the thermal degradation behaviors of chitosan was discussed. Fourier transform-infrared (FTIR) and X-ray diffractogram (XRD) analysis were utilized to determine the micro-structure of chitosan–cupric ion compounds. The results show that FTIR absorbance bands of  N H,  C N ,  C O C etc. groups of chitosan are shifted, and XRD peaks of chitosan located at 11.3, 17.8, and 22.8° are gradually absent with increasing weight fraction of cupric ion mixed in chitosan, which show that there are coordinating bonds between chitosan and cupric ion. The results of thermal analysis indicate that the thermal degradation of chitosan and chitosan–cupric ion compounds in nitrogen is a two-stage reaction. The first stage is the deacetylation of the main chain and the cleavage of glycosidic linkages of chitosan, and the second stage is the thermal destruction of pyranose ring of chitosan and the decomposition of residual carbon, in which both are exothermic. The effect of cupric ion on the thermal degradation of chitosan is significant. In the thermal degradation of chitosan–cupric ion compounds, the temperature of initial weight loss (T_st), the temperature of maximal weight loss rate (T_max), that is, the peak temperature on the DTG curve, and the peak temperature (T_p) on the DTA curve decrease, and the reaction activation energy (E_a) varies with increasing weight fraction of cupric ion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

N,N′‐Pentamethylenethiuram disulfide‐ and N,N′‐pentamethylenethiuram hexasulfide‐accelerated sulfur vulcanization. I. Interaction of curatives in the absence of rubber

N,N′‐pentamethylenethiuram disulfide (CPTD), CPTD/sulfur, and N,N′‐pentamethylenethiuram hexasulfide (CPTP6) were heated in a DSC at a programmed heating rate and isothermally at 140°C. Residual reactants and reaction products were analyzed by HPLC at various temperatures or reaction times. CPTD rapidly formed N,N′‐pentamethylenethiuram monosulfide (CPTM) and N,N′‐pentamethylenethiuram polysulfides (CPTP) of different sulfur rank, CPTP of higher sulfur rank forming sequentially, as reported earlier for tetramethylthiuram disulfide (TMTD). As with TMTD, the high concentration of the accelerator monosulfide that develops is attributed to an exchange between CPTD and sulfenyl radicals, produced on homolysis of CPTD. However, a different mechanism for CPTP formation to that suggested for TMTD is proposed. It is suggested that disulfenyl radicals, resulting from CPTM formation, exchange with CPTD and/or CPTP already formed, to give CPTP of higher sulfur rank. CPTD/sulfur and CPTP6 very rapidly form a similar product spectrum with CPTP of sulfur rank 1–14 being detectable. Unlike with TMTD/sulfur, polysulfides of high sulfur rank did not form sequentially when sulfur was present, CPTP of all sulfur rank being detected after 30 s. It is proposed that sulfur adds directly to thiuram sulfenyl radicals. Recombination with sulfenyl radicals, which would be the most plentiful in the system, would result in highly sulfurated unstable CPTP. CPTP of higher sulfur rank are less stable than are disulfides as persulfenyl radicals are stabilized by cyclization, and the rapid random dissociation of the highly sulfurated CPTP, followed by the rapid random recombination of the radicals, would result in the observed product spectrum. CPTP is thermally less stable than is TMTD and at 140°C decomposed rapidly to N,N′‐pentamethylenethiourea (CPTU), sulfur, and CS₂. At 120°C, little degradation was observed. The zinc complex, zinc bis(pentamethylenedithiocarbamate), did not form at vulcanization temperatures, although limited formation was observed above 170°C. ZnO inhibits degradation of CPTD to CPTU. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2718–2731, 2000     

Synthesis and evaluation of trimethylolpropane triacrylate crosslinked superabsorbent polymers for conserving water and fertilizers

A series of superabsorbent polymers (SAP) were synthesized by free radical thermal copolymerization of acrylic acid and N‐isopropyl acrylamide monomers using trimethylolpropane triacrylate as crosslinker. They were characterized by FT‐IR and thermal stability (TGA/DTG), and evaluated for their water and fertilizer uptake and release characteristics under different crosslinker levels, temperature, pressure, and pH. The observed maximum absorption of water by the SAP was 1130 g/g of polymer. The release was modeled which showed a non‐Fickian mechanism. The water uptake of SAP was correlated with the average molecular weight between the crosslinks and crosslink density. Analysis of the weight loss data from TG in air revealed a zero order kinetics for the initial degradation step with an activation energy (AE) of 70.8 kJ/mol. The AEs for water uptake and release for thermal degradation were also determined through Arrhenius plots. The results inferred that the synthesized SAP can be exploited for commercial agricultural applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013