Calcium phosphate incorporated poly(ethylene oxide)‐based nanocomposite electrolytes for lithium batteries. I. Ionic conductivity and positron annihilation lifetime spectroscopy studies

Nanocomposite polymer electrolytes (NCPEs) composed of poly(ethylene oxide), calcium phosphate [Ca₃(PO₄)₂], and lithium perchlorate (LiClO₄)/lithium bis(trifluoromethane sulfonyl)imide [LiN(CF₃SO₂)₂ or LiTFSI] in various proportions were prepared by a hot‐press method. The membranes were characterized by scanning electron microscopy, differential scanning calorimetry, thermogravimetry–differential thermal analysis, ionic conductivity testing, and transference number studies. The free volume of the membranes was probed by positron annihilation lifetime spectroscopy at 30°C, and the results supported the ionic conductivity data. The NCPEs with LiClO₄ exhibited higher ionic conductivities than the NCPE with LiTFSI as a salt. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Enhancement of thermal stability associated with the chemical treatment of bacterial (Gluconacetobacter xylinus) cellulose

Bacterial cellulose produced by Gluconacetobacter xylinus was treated with sodium carbonate (Na₂CO₃) and sodium hydroxide (NaOH) to remove entrapped noncellulosic materials. Fourier transform infrared (FTIR) spectroscopy has been used to investigate the effect of alkali on the chemical structure of bacterial cellulose. The changes in the crystalline nature of these membranes were analyzed using X‐ray diffraction (XRD) technique. The morphology and the removal of noncellulosic impurities followed by alkali treatment were studied using scanning electron microscopy (SEM) and energy dispersive X‐ray spectrometry (EDS). The enhanced thermal stability of bacterial cellulose was evident from thermogravimetric analysis (TGA). Further, the alkali treatments resulted in relatively pure form of cellulose, which finds application in various spheres. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Microwave‐assisted synthesis of new optically active poly(ester‐imide)s containing N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine moieties

Pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) (1) was reacted with L‐phenylalanine (2) in a mixture of acetic acid and pyridine (3 : 2) and the resulting imide‐acid [N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid] (4) was obtained in quantitative yield. The compound (4) was converted to the N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid chloride (5) by reaction with thionyl chloride. A new facile and rapid polycondensation reaction of this diacid chloride (5) with several aromatic diols such as phenol phthalein (6a), bisphenol‐A (6b), 4,4′‐hydroquinone (6c), 1,8‐dihydroxyanthraquinone (6d), 4,4‐dihydroxy biphenyl (6e), and 2,4‐dihydroxyacetophenone (6f) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o‐cresol. The polymerization reactions proceeded rapidly and are completed within 20 min, producing a series of optically active poly(ester‐imide)s with good yield and moderate inherent viscosity of 0.10–0.26 dL/g. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐imide)s are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2211–2216, 2002     

Value‐added derivatives of soda lignin from alfa grass (Stipa tenacissima). I. Modification and characterization

Alfa grass (Stipa tenacissima) is the only raw material for manufacturing paper pulp in Algeria, Tunisia, and Morocco. Soda lignin (SL) is obtained from black liquor (BL), a byproduct of manufacturing paper from alfa grass. This work was aimed at modifying SL and using it as a polymer lubricant. Modified SL was obtained in two steps: the precipitation of BL at pH 4 with sulfuric acid (2N) followed by the modification of SL by esterification using stearic anhydride (SA) dissolved in dioxane at 50°C for 8 h. The effects of different contents of SA on the hydrophobic properties and heat stability of modified SL were evaluated with contact angle analysis and thermogravimetric analysis. A commercial stearate used in plastic processing was chosen as the reference. Its thermal properties were ascertained with thermogravimetry, and its behavior was similar to that of the modified lignins. A structural comparison study was performed with Fourier transform infrared (FTIR) spectroscopy and solid‐state ¹³C‐NMR. The FTIR and ¹³C‐NMR results showed that there were significant differences between the main structures of SL samples reacted with 10, 30, or 100% (w/w) SA. The main part of the work consisted of modifying SL, evaluating the properties of the obtained products with respect to their use as lubricants, and comparing them to industrial lubricants. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of novel poly(amide imide)s based on bis(p‐amidobenzoic acid)‐n‐trimellitylimido‐L‐leucine

N‐Trimellitylimido‐L ‐leucine was reacted with thionyl chloride, and N‐trimellitylimido‐L ‐leucine diacid chloride was obtained in a quantitative yield. The reaction of this diacid chloride with p‐aminobenzoic acid was performed in dry tetrahydrofuran, and bis(p‐amidobenzoic acid)‐N‐trimellitylimido‐L ‐leucine (5) was obtained as a novel optically active aromatic imide–amide diacid monomer in a high yield. The direct polycondensation reaction of the monomer imide–amide diacid 5 with 4,4′‐diaminodiphenylsulfone, 4,4′‐diaminodiphenylether, 1,4‐phenylenediamine, 1,3‐phenylenediamine, 2,4‐diaminotoluene, and benzidine (4,4′‐diaminobiphenyl) was carried out in a medium consisting of triphenyl phosphite, N‐methyl‐2‐pyrolidone, pyridine, and calcium chloride. The resulting novel poly(amide imide)s (PAIs), with inherent viscosities of 0.22–0.52 dL g^?1, were obtained in high yields, were optically active, and had moderate thermal stability. All of the compounds were fully characterized with IR spectroscopy, elemental analyses, and specific rotation. Some structural characterization and physical properties of these new optically active PAIs are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 35–43, 2002; DOI 10.1002/app.10181     

Thermal behavior of some homogeneously polymethyl methacrylate (PMMA)‐grafted high α‐cellulose products

The graft copolymerization of methyl methacrylate (MMA) onto high α‐cellulose was carried out homogeneously in an N,N‐dimethyl acetamide/lithium chloride solvent system by using benzoyl peroxide as radical initiator. The rate of grafting was evaluated as a function of concentrations of initiator and monomer, reaction time, and temperature. The grafted products were characterized with the help of infrared spectroscopy, whereas the thermal decomposition of optimum PMMA‐grafted high α‐cellulose was studied using TGA, DTG, and DTA techniques at two heating rates, 10 and 20°C/min, in nitrogen atmosphere in the range of room temperature to 650°C. Three major decomposition steps were identified and the relative thermal stabilities of the PMMA‐grafted high α‐cellulose products were assessed. The kinetic parameters for the three decomposition steps were estimated with the help of two well‐known methods. The thermal stability of the grafted products decreased with the increase of graft yield (GY). Crystallinity or peak intensity of wide‐angle X‐ray diffraction patterns decreased with the increase of GY. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3471–3478, 2004     

Anhydride production as an additional mechanism of poly(3‐hydroxybutyrate) pyrolysis

Anhydrides production is newly proposed as an additional pyrolysis mechanism of a biopolymer, poly(3‐hydroxybutyrate) (PHB). In spite of many suggestions of multiple degradation mechanisms, simple random chain scission by β‐elimination has been accepted as an exclusive mechanism of the thermal degradation of PHB. However, a wide range of activation energy value of the degradation and the deviation from the random chain scission statistics have suggested the presence of other kinds of mechanism out of the random scission. To confirm other mechanisms out of the random scission, minor pyrolyzates from PHB were characterized with ¹H/¹³C‐NMR, Fourier transform infrared spectroscopy, and fast atom bombardment mass spectrometry. As a result, crotonic anhydride and its oligomers were detected as minor products from condensation reactions between carboxyl groups. The anhydrides production must be one reaction out of the conforming process to the random degradation statistics and contribute to the complexity of PHB pyrolysis. An expected thermal degradation pathway of PHB was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microwave‐assisted and classical heating polycondensation reaction of bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine with diisocyanates as a new method for preparation of optically active poly(amide imide)s

A new class of optically active poly(amide imide)s were synthesized via direct polycondensation reaction of diisocyanates with a chiral diacid monomer. The step‐growth polymerization reactions of monomer bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine (BPABTL) (5) as a diacid monomer with 4,4′‐methylene bis(4‐phenylisocyanate) (MDI) (6) was performed under microwave irradiation, solution polymerization under gradual heating and reflux condition in the presence of pyridine (Py), dibuthyltin dilurate (DBTDL), and triethylamine (TEA) as a catalyst and without a catalyst, respectively. The optimized polymerization conditions according to solvent and catalyst for each method were performed with tolylene‐2,4‐diisocyanate (TDI) (7), hexamethylene diisocyanate (HDI) (8), and isophorone diisocyanate (IPDI) (9) to produce optically active poly(amide imide)s by the diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.09–1.10 dL/g. These polymers are optically active, thermally stable, and soluble in amide type solvents. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation, and thermal analyses methods. Some structural characterization and physical properties of this new optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1647–1659, 2004     

Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) with high molecular weight poly(lactic acid) blends determined by thermal analysis

An important strategy used in the polymer industry in recent years is blending two bio‐based polymers to attain desirable properties similar to traditional thermoplastics, thus increasing the application potential for bio‐based and bio‐degradable polymers. Miscibility of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) with poly(L ‐lactic acid) (PLA) were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Three different grades of commercially available PLAs and one type of PHBV were blended in different ratios of 50/50, 60/40, 70/30, and 80/20 (PHBV/PLA) using a micro‐compounder at 175°C. The DSC and TGA analysis showed the blends were immiscible due to different stereo configuration of PLA polymer and two distinct melting temperatures. However, some compatibility between PHBV and PLA polymers was observed due to decreases in PLA's glass transition temperatures. Additionally, the blends do not show clear separation by SEM analysis, as observed in the thermal analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. III. Elongational rheology

The elongational rheology of solutions of cellulose in the ionic liquid solvent 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) was measured at 80, 90, and 100°C; 8, 10, and 12 wt% cellulose; Hencky strains 5, 6, 7; and strain rates from 1 to 100 s^?1. Master curves were generated by shifting the elongational viscosity curves with respect to temperature and Hencky strain. Also, general master curves were generated by simultaneously shifting with respect to both temperatures and Hencky strain. From the Arrhenius plots of the temperature shift factors, the activation energy for elongational flow was determined. The elongational rheology of these solutions was elongational strain rate thinning similar to that of their shear behavior and polymer melts and they were also strain hardening. Both effects and the viscosity increased with cellulose concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. I. Shear rheology

In this article, shear rheology of solutions of different concentrations obtained by dissolution of cellulose in the ionic liquid (IL) solvent 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) was studied by measuring the complex viscosity and dynamic moduli at different temperatures. The obtained viscosity curves were compared with those of lyocell solutions and melt blowing grade polypropylene melts of different melt flow rates (MFR). Master curves were generated for complex viscosity and dynamic moduli by using Carreau and Cross viscosity models to fit experimental data. From the Arrhenius plots of the shift factors with respect to temperature, the activation energies for shear flow were determined. These varied between 18.99 and 24.09 kCal/mol, and were compared with values for lyocell solutions and different polymeric melts, such as polyolefins, polystyrene, and polycarbonate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

Thermal decomposition behavior of carbon‐nanotube‐reinforced poly(ethylene 2,6‐naphthalate) nanocomposites

Polymer nanocomposites based on poly (ethylene 2,6‐naphthalate) (PEN) and carbon nanotubes (CNTs) were prepared by direct melt blending with a twin‐screw extruder. Dynamic thermogravimetric analysis was conducted on the PEN/CNT nanocomposites to clarify the effect of CNTs on the thermal decomposition behavior of the polymer nanocomposites. The thermal decomposition kinetics of the PEN/CNT nanocomposites was strongly dependent on the CNT content, the heating rate, and the gas atmosphere. On the basis of the thermal decomposition kinetic analysis, the variation of the activation energy for thermal decomposition revealed that a very small quantity of CNTs substantially improved the thermal stability and thermal decomposition of the PEN/CNT nanocomposites. Morphological observations demonstrated the formation of interconnected or network‐like structures of CNTs in the PEN matrix. The unique character of the CNTs introduced into the PEN matrix, such as the physical barrier effect of CNTs during thermal decomposition and the formation of interconnected or network‐like structures of CNTs, resulted in the enhancement of the thermal stability of the PEN/CNT nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Multicarboxylic aromatic acid core initiator for the synthesis of star‐shaped poly(ϵ‐caprolactone) with carboxyl end groups

We successfully carried out the ring‐opening polymerization of ?‐caprolactone with 1,3,5‐benzenetricarboxylic acid and 1,2,4,5‐benzenetetracarboxylic acid as the core initiators at 225°C in bulk, and three‐armed and four‐armed star poly(?‐caprolactone)s [poly(?‐CL)s] with carboxyl end groups were obtained. No transesterification, which would have led to a decrease in the molecular weight of poly(?‐CL), was found. The effects of the polymerization conditions on the polymerization are discussed; the poly(?‐CL)s were characterized by ¹H‐NMR, gel permeation chromatography, and thermogravimetric analysis in detail. A mechanism of alkyl–oxygen bond scission by the nucleophilic attack of the carboxyl anions via hydrogen proton transfer is presented for this system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3713–3717, 2006     

Modified solution technique for preparing poly(3,4‐ethylenedioxythiophene) and a Poly(3,4‐ethylenedioxythiophene)/silver nanocomposite: Optical and thermal behavior

In this study, we prepared poly(3,4‐ethylenedioxythiophene) (PEDOT) via the chemical oxidation of the 3,4‐ethylenedioxythiophene monomer in a system consisting of miscible binary organic solvents, that is, acetonitrile (CH₃CN) and chloroform (CHCl₃). This successful technique was then used to synthesize a poly(3,4‐ethylenedioxythiophene) (PEDOT)/silver (Ag) nanocomposite as well. In this facile and efficient technique, a higher solubility of the oxidizing reagent, which originated from a relative enhancement in the polarity of the reaction medium, led to significant changes in the optical and thermal behaviors of the resulting products. To investigate the degree of validity of the technique applied, a pure sample of PEDOT (PEDOT I) was also synthesized with CHCl₃ alone, and this was then compared with a sample prepared in CH₃CN/CHCl₃ binary solvents (PEDOT II). To prepare the PEDOT/Ag nanocomposite, first the PEDOT synthesized in binary solvents was thoroughly dissolved in a dimethyl sulfoxide solvent. Next, Ag nanopowder was uniformly dispersed in the previous solution of PEDOT with sonication. The PEDOT/Ag nanocomposite was then precipitated through the addition of a methanol nonsolvent. The approximate size of nano‐Ag within the polymer matrix was found to be about 40 nm. Scanning electron microscopy images of the pure PEDOT II and PEDOT/Ag nanocomposite exhibited an agglomerated sponge and nanospherical homogeneity, respectively. In comparison with PEDOT I, considerable redshifts in the ultraviolet–visible absorption spectra of the pure PEDOT II and PEDOT/Ag nanocomposite were observed. In addition, the thermostability order was found to be PEDOT/Ag > PEDOT II > PEDOT I at all temperatures above 300°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2707–2712, 2013     

Synthesis,characterization, thermal stability,and compatibility properties of poly(vinyl p‐nitrobenzal acetal)‐g‐polyglycidylazides

A series of energetic polymers, poly(vinyl p‐nitrobenzal acetal)‐g‐polyglycidylazides (PVPNB‐g‐GAPs), are obtained via cross‐linking reactions of poly(vinyl p‐nitrobenzal acetal) (PVPNB) with four different molecular weights polyglycidylazides (GAPs) using toluene diisocyanate as cross‐linking agent. The structures of the energetic polymers are characterized by ultraviolet visible spectra (UV‐Vis), attenuated total reflectance‐Fourier transform‐infrared spectroscopy (ATR‐FT‐IR), ¹H nuclear magnetic resonance spectrometry (¹H NMR), and ¹³C nuclear magnetic resonance spectrometry (¹³C NMR). Differential scanning calorimetry (DSC) is applied to evaluate the glass‐transition temperature of the polymers. DSC traces illustrate that PVPNB‐g?2^#GAP, PVPNB‐g?3^#GAP, and PVPNB‐g?4^#GAP have two distinct glass‐transition temperatures, whereas PVPNB‐g?1^#GAP has one. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) are used to evaluate the thermal decomposition behavior of the four polymers and their compatibility with the main energetic components of TNT‐based melt‐cast explosives, such as cyclotetramethylene tetranitramine (HMX), cyclotrimethylene‐trinitramine (RDX), triaminotrinitrobenzene (TATB), and 2,4,6‐trinitrotoluene (TNT). The DTA and TGA curves obtained indicate that the polymers have excellent resistance to thermal decomposition up to 200°C. PVPNB‐g?4^#GAP also exhibits good compatibility and could be safely used with TNT, HMX, and TATB but not with RDX. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42126.     

Investigation of the thermostability of poly(ethylene terephthalate)–hemp fiber composites: Extending natural fiber reinforcements to high‐melting thermoplastics

The thermal stability of poly(ethylene terephthalate) reinforced with 1, 5, 10, 15, and 20% hemp fibers was investigated with the aim of extending the applications of biocomposites to high‐melting thermoplastics. The material was injection‐molded following compounding with a torque‐based Rheomix at 240, 250, and 260°C. A combination of thermogravimetric methods at 5, 10, and 20°C/min, Liu and Yu's collecting temperature method, and Friedman's kinetic method were used for testing and analysis. A significant thermostability for all formulations was observed below 300°C; this demonstrated their potential for successful melt processing. Moreover, two degradation steps were observed in the temperature ranges 313–390 and 390–490°C. The associated apparent activation energies within the temperature ranges were determined as 150–262 and 182–242 kJ/mol, respectively. We found that the thermostability was significantly affected by the heating rates; however, the effect of the temperature of the mixing chamber was negligible. These findings suggest that the successful melt processing of high‐melting thermoplastics reinforced with natural fibers is possible with limited fiber thermodegradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42500.     

Synthesis and characterization of polyamides and poly(amide‐imide)s derived from 2,6‐bis(3‐aminophenoxy)benzonitrile or 2,6‐bis(4‐aminophenoxy)benzonitrile

A series of polyamides and poly(amide‐imide)s was prepared by direct polycondensation of ether and nitrile group containing aromatic diamines with aromatic dicarboxylic acids and bis(carboxyphthalimide)s respectively in N‐methyl 2‐pyrrolidone (NMP) using triphenyl phosphite and pyridine as condensing agents. New diamines, such as 2,6‐bis(4‐aminophenoxy)benzonitrile and 2,6‐bis(3‐aminophenoxy)benzonitrile, were prepared from 2,6‐dichlorobenzonitrile with 4‐aminophenol and 3‐aminophenol, respectively, in NMP using potassium carbonate. Bis(carboxyphthalimide)s were prepared from the reaction of trimellitic anhydride with various aromatic diamines in N,N′‐dimethyl formamide. The inherent viscosities of the resulting polymers were in the range of 0.27 to 0.93 dl g^?1 in NMP and the glass transition temperatures were between 175 and 298 °C. All polymers were soluble in dipolar aprotic solvents such as dimethylsulfoxide, dimethylacetamide and NMP. All polymers were stable up to 350 °C with a char yield of above 40 % at 900 °C in nitrogen atmosphere. All polymers were found to be amorphous except the polyamide derived from isophthalic acid and the poly(amide‐imide)s derived from diaminodiphenylether and diaminobenzophenone based bis(carboxyphthalimide)s. Copyright © 2004 Society of Chemical Industry