Characterization of polyacrylonitrile,poly(acrylonitrile‐co‐vinyl acetate), and poly(acrylonitrile‐co‐itaconic acid) based activated carbon nanofibers

In this study, three different acrylonitrile (AN)‐based polymers, including polyacrylonitrile (PAN), poly(acrylonitrile‐co‐vinyl acetate) [P(AN‐co‐VAc)], and poly(acrylonitrile‐co‐itaconic acid) [P(AN‐co‐IA)], were used as precursors to synthesize activated carbon nanofibers (ACNFs). An electrospinning method was used to produce nanofibers. Oxidative stabilization, carbonization, and finally, activation through a specific heating regimen were applied to the electrospun fibers to produce ACNFs. Stabilization, carbonization, and activation were carried out at 230, 600, and 750 °C, respectively. Scanning electron microscopy, thermogravimetric analysis (TGA), and porosimetry were used to characterize the fibers in each step. According to the fiber diameter variation measurements, the pore extension procedure overcame the shrinkage of the fibers with copolymer precursors. However, the shrinkage process dominated the scene for the PAN homopolymer, and this led to an increase in the fiber diameter. The 328 m²/g Brunauer–Emmett–Teller surface area for ACNFs with PAN precursor were augmented to 614 and 564 m²/g for P(AN‐co‐VAc) and P(AN‐co‐IA), respectively. The TGA results show that the P(AN‐co‐IA)‐based ACNFs exhibited a higher thermal durability in comparison to the fibers of PAN and P(AN‐co‐VAc). The application of these copolymers instead of AN homopolymer enhanced the thermal stability and increased the surface area of the ACNFs even in low‐temperature carbonization and activation processes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44381.     

Thermal behavior of acrylonitrile carboxylic acid copolymers

Polyacrylonitrile (PAN) and copolymer of acrylonitrile–vinyl acids prepared by solution polymerization technique have been characterized by Differential Scanning Calorimetry (DSC) (under dynamic as well as isothermal conditions), themograviemetric analysis (TGA), and on‐line DSC‐FTIR spectroscopy. The DSC of copolymers was carried out at 5°C/min in nitrogen and air. In nitrogen atmosphere the DSC exotherm show a very sharp peak, whereas, in air atmosphere DSC exotherm is broad, and starts at a much lower temperature compared to what is observed in nitrogen atmosphere. The initiation temperature of PAN homopolymer is higher than that for the copolymers. For instance, the initiation temperature of PAN in air is 244°C, whereas, the onset of exothermic reaction is in the range of 172 to 218°C for acrylonitrile–vinyl acid copolymers. As the vinyl acid content increases the ΔH value reduces. The ΔH value of PAN in air was 7025 J/g, whereas, for P(AN‐AA) with 5.51 mol % of acid it was 3798 J/g. As the content of acrylic acid comonomer is increased to 17.51 mol % the value of ΔH decreases further to 1636 J/g. The same trend was observed with MAA and IA as well. DSC‐FTIR studies depict various chemical changes taking place during heat treatment of these copolymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 685–698, 2003     

Molecular and thermal studies of carbon fiber precursor polymers with low thermal‐oxidative stabilization characteristics

In this investigation, terpolymers, copolymers, and homopolymer of acrylonitrile with dimethylaminopropyl acrylamide (DMAPA), itaconic acid (IA) viz., poly(acrylonitrile‐ran‐3‐dimethylaminopropyl acrylamide‐ran‐itaconic acid) [P(AN‐DMAPP‐IA)], poly(acrylonitrile‐co‐3, dimethylaminopropyl acrylamide) [P(AN‐DMAPP)] were synthesized with varying amounts of comonomers using solution polymerization process. The chemical structure, composition, bonding network were determined employing infrared, 1H and, 13‐carbon nuclear magnetic resonance spectroscopic techniques. Molecular characteristics of as‐synthesized polymers such as different kinds of average molecular weights, molecular weight distribution were estimated applying solution viscometry and size exclusion chromatography. The influence of comonomers (DMPAA, IA) on the thermal stabilization characteristics of acrylonitrile terpolymers in comparison with copolymers and homopolymers of acrylonitrile were studied using differential scanning calorimetry (DSC), hyphenated thermal techniques (thermal gravimetry coupled with differential thermal analyzer).The DSC curves of P(AN‐DMAPP‐IA) exhibit a distinct broader bimodal peaks with thermal exotherm initiating at as low as 165 °C, and followed by two peaks with temperature difference of 42 °C, releasing the evolved heat at a release rate of 0.7–0.11 J g^?1s^?1over 10 min as compared to 1.2, 7.5 J g^?1s^?1 in 4.5, 2 min as observed in P(AN‐DMAPP), polyacrylonitrile, respectively. The thermal stability of P(AN‐DMAPP‐IA) and P(AN‐DMAPP), as evidenced by TGA‐DTA was found to be higher than PAN homopolymers. Specific heat capacity measurements confirmed the DSC results. Bulk densities of P(AN‐DMAPP‐IA) were in the range 0.31–0.35 g/cc. These results confirm the low‐temperature stabilization characteristics and suitability of P(AN‐DMAPP‐IA) as low cost carbon fiber precursor polymers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46381.     

Functional copolymer of geraniol and acrylonitrile: Synthesis and characterization

The radical copolymerization of acyclic terpene namely geraniol [GER] with acrylonitrile [AN] in DMF at (70 ± 0.1)°C for 1 h, using benzoylperoxide (BPO) as an initiator has been carried out under inert atmosphere of nitrogen. The kinetic expression for reaction is R_p ∝ [BPO]^0.5 [AN]^1.0 [GER]^1.0. The IR spectrum of the copolymer shows bands at 3432 and at 2244 cm^?1 due to ? OH group of GER and ? CN group of AN, respectively. The ¹³C‐NMR spectrum shows peaks at 73–75 δ ppm and 116–120 δ ppm due to ? OH group of GER and ? CN group of AN, respectively. The thermogravimetric analysis and differential scanning calorimetry study shows that copolymer is thermally stable up to 407°C and has glass transition temperatures (T_g) 56°C. The reactivity ratios r₁ (AN) and r₂ (GER) have been calculated as 0.05 and 0.005, respectively. The Alfrey‐Price Q‐e parameter for GER has been calculated as 0.094 and ?2.0, respectively. The molecular weights of the copolymers have been evaluated by gel‐permeation chromatography. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of reaction medium on radical copolymerization of acrylonitrile with vinyl acids

Radical polymerization of acrylonitrile (AN) with methacrylic acid (MAA) and itaconic acid (IA) was carried out in a mixture of dimethylformamide (DMF) and water at 70°C using α, α′‐azobisisobutyronitrile (AIBN) as an initiator. Monomer feed in the polymerization vessel was 98:2 (AN:MAA/IA) in the molar ratio, and the DMF:H₂O ratio was varied between 20:80 and 80:20 (w/w). Copolymers were characterized by FTIR, carbon, hydrogen, nitrogen elemental CHN analysis, ¹H‐ and ¹³C‐NMR, and viscometry. The rate of polymerization (R_p) was found to decrease with an increase in DMF concentration in the reaction medium, that is, in 20% DMF for AN–MAA system, the R_p is 1.23% min⁻¹ in 1 h of polymerization, while in 80% DMF, R_p is reduced to 0.37% min⁻¹. The nature of the vinyl acid also affects the R_p. It has been shown that the rate of polymerization is higher for an AN–MAA system as compared to an AN–IA system (R_p = 1.0% min⁻¹) and the methacrylic or itaconic acid content in the copolymer increases with an increase in the DMF concentration. The MAA content in the poly(AN–MAA) polymer produced in 20% DMF is 3.2 mol %, which increases to 6.1 mol % (calculated through FTIR spectra) when DMF is increased to 80% in the reaction medium. The intrinsic viscosity [η] of the poly(AN–IA) and poly(AN–MAA) copolymers in DMF was found to be in the range of 0.67–2.90 dLg⁻¹ depending on the reaction medium. In determining the intrinsic viscosity, a definite deviation from rectilinearity of the concentration dependence in the high‐dilution region is observed, thereby demonstrating the polyelectrolyte behavior of these polymers. Through FTIR and NMR spectral studies, PAN homopolymer and other copolymers have shown the formation of a small quantity of acrylamide units. In addition copolymer P₁₀, which contains 10.1 mol % IA, has shown anhydride formation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1640–1652, 2001     

Preparation and characterization of acrylonitrile‐ethyl methacrylate copolymers and the effect of LiClO4 salt on electrical properties of copolymer films

Copolymers of poly(acrylonitrile‐co‐ethyl methacrylate), P(AN‐EMA), with three different EMA content and parent homopolymers were synthesized by emulsion polymerization. The chemical composition of copolymers were identified by FTIR, ¹H‐NMR and ¹³C‐NMR spectroscopy. The thermal properties of copolymers were modified by changing the EMA content in copolymer compositions. Various amounts of LiClO₄ salt loaded (PAN‐co‐PEMA) copolymer films were prepared by solution casting. The dielectric properties of these films at different temperatures and frequencies were investigated. It was found that the dielectric constant and ac‐conductivity of copolymer films were strongly influenced by the salt amounts and EMA content in copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of poly(hydroxamic acid)–poly(amidoxime) chelating ligands from polymer‐grafted acacia cellulose

Graft copolymerization of methyl acrylate (MA) and acrylonitrile (AN) onto acacia cellulose was carried out using free radical initiating process in which ceric ammonium nitrate (CAN) was used as an initiator. The optimum grafting yield was determined by the certain amount of acacia cellulose (AGU), mineral acid (H₂SO₄), CAN, MA, and AN at 0.062, 0.120, 0.016, 0.397, and 0.550 mol L^?1, respectively. The poly(methyl acrylate‐co‐acrylonitrile)‐grafted acacia cellulose was obtained at 55°C after 2‐h stirring, and purified acrylic polymer‐grafted cellulose was characterized by FTIR and TG analysis. Therein, the ester and nitrile functional groups of the grafted copolymers were reacted with hydroxylamine solution for conversion into the hydroxamic acid and amidoxime ligands. The chelating behavior of the prepared ligands toward some metal ions was investigated using batch technique. The metal ions sorption capacities of the ligands were pH dependent, and the sorption capacity toward the metal ions was in the following order: Zn²⁺ > Fe³⁺ > Cr³⁺ > Cu²⁺ > Ni²⁺. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fe‐mediated ICAR ATRP of styrene and acrylonitrile in polyethylene glycol

In this contribution, random copolymers of p(styrene‐co‐acrylonitrile) via initiators for continuous activator regeneration (ICAR) in atom transfer radical polymerization (ATRP) (ICAR ATRP) of styrene and acrylonitrile (SAN) were synthesized at 90°C in low molecular weight polyethylene glycol (PEG‐400) using CCl₄ as initiator, FeCl₃·6H₂O as catalyst, succinic acid as ligand and thermal radical initiator azobisisobutyronitrile (AIBN) as thermal free radical initiator. In this system, well‐defined copolymer of SAN was achieved. The kinetics results showed that the copolymerization rate obeyed first‐order kinetics model with respect to the monomer concentration, and a linear increase of the molecular weights with the increasing of monomer conversion with narrow molecular weight distribution was observed in the range of 1.1–1.5. The conversion decreased with increasing the amount of FeCl₃·6H₂O and increased with increasing the molar ratio of [St]₀/[AN]₀/[CCl₄]₀ and temperature. AIBN has a profound effect on the polymerization. The activation energy was 55.67 kJ mol^?1. The living character of copolymerization was confirmed by chain extension experiment. The resultant random copolymer was characterized by ¹H‐NMR and GPC. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40135.     

Structures and properties of thermoregulated acrylonitrile–methyl acrylate sheet containing microphase change materials

A series of melt processable poly(acrylonitrile–methyl acrylate) copolymers with a feeding ratio of 85/15 mol% (abbreviated as 85/15 AN/MA below) containing 0–25 wt% of microencapsulated phase change materials (micro‐PCMs) were synthesized by aqueous precipitation polymerization. The number average sequence lengths (NASLs) and tacticity of 85/15 AN/MA were determined using ¹³C‐NMR. The results showed that the NASL of contiguous AN sequences is 10.00 and the tacticity is atactic with approximately 51% m and 49% r diads (the relative orientation of two adjacent cyanogroup). 85/15 AN/MA containing various contents of micro‐PCMs were processed into sheets in melt condition at 210°C and 20 MPa. The structures and properties of the copolymers and sheets containing micro‐PCMs were studied by using Fourier transform infrared spectroscopy, nuclear magnetic resonance (¹H‐NMR), scanning electron microscopy, differential scanning calorimetry, gel permeation chromatography, X‐ray diffraction, and dynamic mechanical analysis. The composition of AN/MA copolymer agreed well with its monomer feed ratio. The melting enthalpy of the sheets containing 25 wt% of micro‐PCMs was approximately 25 J/g, which increased steadily as the micro‐PCMs content increased. The modulus of the sheets decreased with the micro‐PCMs content increased. The glass transition temperature (T_g) of the sheets was in the range of 79.7–81.7°C, which also increased with the micro‐PCMs content increasing. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Block copolymers of acrylonitrile and poly(dimethylsiloxane)s

The chemical redox system of ceric ammonium nitrate(Ce⁴⁺) and poly(dimethylsiloxane)s (PDMS) with monohydroxy (MH), dihydroxy (DH), and diamine(DA) chain ends was used to polymerize acrylonitrile (AN) to produce monohydroxy poly(dimethylsiloxane)s‐b‐polyacrylonitrile (MH.PDMS‐b‐PAN), dihydroxy poly(dimethylsiloxane)s‐b‐polyacrylonitrile (DH.PDMS‐b‐PAN), and α, ω‐diamine poly(dimethylsiloxane)s‐b‐polyacrylonitrile (DA.PDMS‐b‐PAN) block copolymers. The concentration, reaction time, and the type of poly(dimethylsiloxane) affect the yield and the molecular weight of the copolymers. The ratio of AN/ceric salt/PDMS has remarkably affects the properties of formed copolymers. DH.PDMS‐b‐PAN copolymers were also prepared by electroinduced polymerization in the presence of catalytic amount of Ce⁴⁺ in a divided electrochemical cell where Ce³⁺ is readily oxidized into Ce⁴⁺ at the anode. The products were characterized by Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, DSC, and their surface properties were investigated through contact‐angle measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Phase‐transfer catalysis: Free‐radical polymerization of acrylonitrile using potassium peroxomonosulphate– tetrabutyl phosphonium chloride catalyst system: A kinetic study

This article presents the systematic study of kinetics and mechanism of phase‐transfer‐catalyzed free‐radical polymerization of acrylonitrile (AN) and water‐soluble initiator potassium peroxomonosulphate (PMS) coupled with tetrabutyl phosphonium chloride (TBPC) in ethyl acetate/water biphase system in the temperature range 45–55°C at fixed pH and ionic strength. The rate of polymerization increases with an increase in concentrations of AN, PMS, and phase transfer catalyst, PTC. It was observed that R_p is proportional to [AN]^1.5, [KHSO5₅⁻]^0.5, and [TBPC]^0.5. A suitable kinetic scheme has been proposed to account for the experimental observations and its significance was discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1564–1571, 2000     

Synthesis of polyamidoxime chelating ligand from polymer‐grafted corn‐cob cellulose for metal extraction

A conventional free‐radical initiating process was used to prepare graft copolymers from acrylonitrile (AN) with corn‐cob cellulose with ceric ammonium nitrate (CAN) as an initiator. The optimum grafting was achieved with corn‐cob cellulose (anhydroglucose unit, AGU), mineral acid (H₂SO₄), CAN, and AN at concentrations of 0.133, 0.081, 0.0145, and 1.056 mol/L, respectively. Furthermore, the nitrile functional groups of the grafted copolymers were converted to amidoxime ligands with hydroxylamine under basic conditions of pH 11 with 4 h of stirring at 70°C. The purified acrylic polymer‐grafted cellulose and polyamidoxime ligand were characterized by Fourier transform infrared spectroscopy and field emission scanning electron microscopy analysis. The ligand showed an excellent copper binding capacity (4.14 mmol/g) with a faster rate of adsorption (average exchange rate = 7 min), and it showed a good adsorption capacity for other metal ions as well. The metal‐ion adsorption capacities of the ligand were pH‐dependent in the following order: Cu²⁺ > Co²⁺ > Mn²⁺ > Cr³⁺ > Fe³⁺ > Zn²⁺ > Ni²⁺. The metal‐ion removal efficiency was very high; up to 99% was removed from the aqueous media at a low concentration. These new polymeric chelating ligands could be used to remove aforementioned toxic metal ions from industrial wastewater. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40833.     

The thermo–oxidative degradation of acrylonitrile–butadiene–styrene copolymers during processing as studied by chemiluminescence

The glow curve obtained upon processing acrylonitrile–butadiene–styrene copolymers (ABS), through various machines, reaches a peak at 180°C. The proper assignment of that peak has required the study of the chemiluminescence (CL) shown by related polymers such as: polybutadiene (PB), styrene–acrylonitrile copolymer (SAN), and polyacrylonitrile (PAN). Three hydroperoxide types associated with the structural units, that is, 1, 2, and cis- and trans-1,4, exhibiting CL peaks at 180, 240, and 340°C, respectively, have been identified in the PB sample. The activation energy (E_a), recorded for the hydroperoxides thermal decomposition, was 15.0 ± 1.0, 17.85 ± 0.9, 20.7 ± 0.8 kcal/mol. PAN shows a CL peak at 180°C. Its occurance is related to the color developed during the thermal treatment. That PAN peak has been attributed to the hydroperoxides generated on the acrylonitrile units neighboring the azomethinic structures. The corresponding E_a is 23.3 ± 1.0 kcal/mol. The same peak (having an identical position and E_a) has been identified with processed ABS and SAN copolymers. As is evident by CL studies, the processing induced oxidation mainly occurs within the SAN phase of the ABS copolymers, though it was also noted within 1,2 units of the PB phase.     

Molecular design and stabilization mechanism of acrylonitrile bipolymer

In order to replace terpolymer with bipolymer, a bifunctional comonomer 3‐aminocarbonyl‐3‐butenoic acid methyl ester (ABM) was synthesized for preparing poly(acrylonitrile‐co‐3‐aminocarbonyl‐3‐butenoic acid methyl ester) [P(AN‐co‐ABM)] bipolymers as carbon fiber precursor. The structure and stabilization of P(AN‐co‐ABM) bipolymers were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, and differential scanning calorimetry. The monomer reactivity ratios were calculated by the Fineman‐Ross and Kelen‐Tüdõs methods, and the results show that ABM displays higher reactivity than acrylonitrile. Two parameters E_s = A_1618cm^‐1/A_2244cm^‐1 and SI = (I₀ ‐ I_s)/I₀ were defined to evaluate the extent of stabilization, and the activation energy (E_a) of the stabilization reactions were calculated by Kissinger and Ozawa methods. The results show that the P(AN‐co‐ABM) bipolymers exhibit significantly improved stabilization performance when compared with polyacrylonitrile (PAN) homopolymer, such as lower cyclization temperature, lower E_a, and larger extent of stabilization under the same conditions. Simultaneously, the rheological analysis shows that P(AN‐co‐ABM) possesses better spinnability than PAN. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of the potential of polymeric carriers based on chitosan‐grafted‐polyacrylonitrile in the formulation of drug delivery systems

Graft copolymerization of chitosan with acrylonitrile (AN) was carried out by free radical polymerization using KMnO₄ and oxalic acid as a combined redox initiator system. Graft copolymerization was confirmed by Fourier transform infrared spectra (FTIR), proton nuclear magnetic resonance spectra (¹H‐NMR), thermal gravimetric analysis (TGA) measurements, and wide angle X‐ray diffraction (WAXD). In addition, further modification of the cyano groups of the grafted copolymers was performed by partial hydrolysis into carboxylic function groups with various extents. The extent of hydrolysis was monitored using FTIR spectroscopy. The potential of the hydrolyzed and unhydrolyzed grafted copolymers as polymeric carriers for drug delivery systems was extensively studied by preparation of tablets incorporated with methyl orange (MO) as a drug model. In vitro drug release was carried out in simulated gastric and intestinal conditions. The effects of grafting percentage (GP) and the extent of hydrolysis on the release kinetics were evaluated. Release continued up to 24 h for both hydrolyzed and unhydrolysed chitosan‐g‐PAN copolymers. The nature of drug transport through the polymer matrices was studied by comparing with power law or Kormeyer‐Peppas equation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of electrorheological active ionomers from poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine)

In this study, synthesis, characterization, partial hydrolysis, and salt formation of poly(2‐hydroxyethyl methacrylate)‐co‐poly(4‐vinyl pyridine), (poly(HEMA)‐co‐poly‐(4‐VP)) copolymers were investigated. The copolymers were synthesized by free radical polymerization using K₂S₂O₈ as an initiator. By varying the monomer/initiator ratio, chain lengths of the copolymers were changed. The copolymers were characterized by gel permeation chromatography (GPC), viscosity measurements, ¹H and ¹³C NMR and FTIR spectroscopies, elemental analysis, and end group analysis methods. The copolymers were partially hydrolyzed by p‐toluene sulfonic acid monohydrate (PTSA·H₂O) and washed with LiOH_(aq) solution to prepare electrorheological (ER) active ionomers, poly(Li‐HEMA)‐co‐poly(4‐VP). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3540–3548, 2006     

Charge transfer copolymerization and properties of isopropyl methacrylate with acrylonitrile and methacrylonitrile

Isopropyl methacrylate (IPMA) with Acrylonitrile (AN) and Methacrylonitrile (MAN) copolymers of different copositions were prepared at 60°C and 80°C, respectively, using a mixture of n-Butylamine (nBA) and carbon tetrachloride (CCl₄) in dimethyl sulphoxide (DMSO) as a charge transfer (CT) initiator. The percentage composition of the copolymers was established by elemental analysis. The copolymerization reactivity ratios were computed by the Kelen–Tudos method. In both the systems, IPMA was found to be more reactive; the copolymers sequence was random in nature. The copolymers were characterized by IR, ¹H-NMR, ¹³C-NMR spectroscopy and intrinsic viscosity measurements in dimethyl formamide (DMF) at 30±0.1°C. The thermal behavior of the AN-IPMA copolymers was studied by thermogravimetry (TG) in air. The thermal stability increased, with increasing AN content in the copolymer chain. The solubility parameter of AN-IPMA copolymer was evaluated by studying the intrinsic viscosity in different solvents. The solubility parameter of the copolymer was found to be 9.7 (cal/cc)^1/2.     

Preparation of hydrolysis of poly(acrylonitrile‐co‐methyl acrylate) membranes via thermally induced phase separation: Effects of hydrolysis conditions and additives

In this work, melt processable poly(acrylonitrile‐co‐methyl acrylate) [(P(AN‐MA)] was hydrolyzed first and then formed into microporous membrane via thermally induced phase separation. In order to optimize the hydrolysis condition and fabricate hydrophilic PAN‐based membranes, a series of hydrolysis experiments were performed to indicate the influence of hydrolysis temperature, alkaline species and time. The structure and properties of hydrolyzed P(AN‐MA) [H‐P(AN‐MA)] membranes were also investigated. It was found that with the increase of hydrolysis temperature, pure water flux (PWF) increased first and then decreased. When the hydrolysis temperature increased to 30 °C, the PWF of the H‐P(AN‐MA) membrane was up to the maximum of 6712.7 L/m² h, which increased by 1661.6 L/m² h, compared with the P(AN‐MA) membranes. When 1 wt % sodium dodecyl sulfate (SDS) was incorporated into the diluents, the PWF increased dramatically, especially in high hydrolysis temperature. When the hydrolysis temperature was up to 70 °C, the PWF of H‐P(AN‐MA) membranes containing 1 wt % SDS increased by 2.3 times compared to the sample without SDS under the same condition. With 2 wt % amino functionalized multi‐walled carbon nanotubes (MWCNTs‐NH₂) employed as the additive, the tensile strength was up to 4.55 MPa. When 1 wt % SDS and 0.5 wt % MWCNTs‐NH₂ were mixed together, the bovine serum albumin rejection increased from 31.2% to 40.9%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46380.     

Synthesis and characterization of electrically conducting copolymer of aniline and o‐bromoaniline using methane sulfonic acid as dopant

Polyaniline (PAN), poly(o‐bromoaniline) (POBA), and poly(aniline‐co‐o‐bromoaniline) (PABA) were synthesized by oxidative coupling. These polymers are protonated by 10–20% methane sulfonic acid (MSA) and 1M HCl. The new polymer bases have greater solubility than that of PAN in common polar organic solvents; PAN–MSA was observed to be the most thermally stable of these polymers. POBA is associated with residual quinoid diimine units as illustrated in the IR and UV‐vis spectra, after reduction with hydrazine dihydrochloride. Both the doping agents cause a downward shift of the quinoid absorption in the IR spectra. MSA‐ and HCl‐doped PAN and PABA polymers exhibit a coil‐like conformation in DMSO, whereas only MSA‐doped PAN and PABA show an “expanded coil‐like” conformation in m‐cresol with a “free carrier tail” above 800 nm in their electronic spectra. XPS spectra indicated the presence of covalent bromine in the POBA and PABA polymers. Bromine retention was greater in the homopolymer as evidenced by the IR studies after aging at 350°C. Compared to HCl, MSA is found to be a more effective dopant, enhancing the conductivity of the copolymers by 10²–10³ times in magnitude. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2662–2669, 2002