Kinetics of the cyclization and isomerization reactions in polyacrylonitrile based carbon fiber precursors during thermal-oxidative stabilization

The kinetics of reactions in polyacrylonitrile (PAN) based carbon fiber (CF) production should be of significance to the guidance of process control, fiber structure formation. PAN precursor fibers were isothermally stabilized at 210, 225, 240, 255, and 270 °C, respectively, for 10 to 100 min in an air oven to study the kinetics of the cyclization and isomerization reactions. The structural evolution of PAN precursor fibers during thermal-oxidative stabilization was characterized by Fourier transform infrared (FTIR) spectroscopy and solid state ¹³C nuclear magnetic resonance (¹³C NMR). The results indicate that the FTIR absorbance of  CN (the resultant of the cyclization) in PAN shows a trend of first increasing and then decreasing. And then the NMR peak assigned to the carbon atoms linking imino groups ( NH ) proves the isomerization of  CN into  NH in pyridone structure. Based upon the FTIR absorbance method, the entire process of the cyclization and isomerization reactions is considered as a consecutive first-order reaction. A kinetic model for the consecutive reaction has been established via the evaluation of the reaction rate constants of two single reactions. According to the model, the simulated kinetic curves of the characteristic groups ( CN,  CN , and  NH ) conform to the FTIR absorbance trends of these groups based on experimental data. This study is expected to furnish in-depth information on the crucial reaction kinetics during stabilization of PAN precursors, which is of advantage to the process optimization of the CF production. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48819.     

Synthesis of fluorinated polypropylene using CuAAC click chemistry

Synthesis of fluorine containing polypropylene (PP F) from chlorinated polypropylene (PP Cl) via Cu(I) catalyzed Huisgen type 1,3-dipolar cycloaddition (CuAAC) and its water repellency properties are demonstrated. Initially, clickable azido-functional polypropylene (PP N₃) and alkyne-functionalized fluorine compound (F Al) are independently prepared by nucleophilic substitution of PP Cl with azidotrimethylsilane-tetrabutylammonium fluoride and esterification reactions of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol with 4-pentyonic acid. The CuAAC reaction between PP N₃ and F Al leads to corresponding PP F under mild conditions. The chemical structures and surface properties of desired PP F are characterized by Fourier transform infrared, ¹H-NMR, differential scanning calorimetry, scanning electron microscopy, atomic force microscope, and contact angle analyses. Based on water contact angle (WCA) measurement, it is found that both PP Cl and PP N₃ films have shown similar hydrophobicity, whereas the WCA of PP F is surprisingly decreased due to the presence of ester and triazole groups coming from F Al compound and the clicked product. This facile modification procedure could be utilized in order to alter the wetting or thermal properties of the commercial polymers for potential applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47072.     

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     

The Conductivity of Poly(o-anisidine), Poly(o-toluidine) and Their Copolymer with Various Inorganic Dopants in the Presence of Electrolyte

ABSTRACT

An attempt has been made to prepare poly(o-anisidine) (POA), poly(o-toluidine) (POT) and copolymer poly(o-anisidine)-co-poly(o-toluidine) (POA-co-POT) thin films dopped by several inorganic salts (sulphates and chlorides) with varying size of cations using aqueous solution of H₂SO₄ as electrolyte. The effect of dopant in the presence of electrolyte is rarely studied in the field of conducting polymers. Various inorganic salts as dopants, namely, K₂SO₄, Na₂SO₄, Li₂SO₄, MgSO₄, KCl, NaCl, LiCl, and MgCl₂ are used at room temperature. The films were electropolymerized in solution containing 0.1 M monomer(s), 1 M H₂SO₄ as electrolyte and 1 M inorganic salt, by applying sequential linear potential scan rate 50 mV/sbetween ? 0.2 to 1.0 V versus Ag/AgCl electrode. The electro-synthesized films were characterized by cyclic voltammetry, UV-visible spectroscopy, and conductivity measurements. It was observed that the UV-visible peaks usually appearing at about 802–826 nm with a shoulder at 410–426 nm shows a shift in presence of doping salt for emeraldine salt (ES) phase of POA, POT, POA-co-POT. In overall study, a significant increase in conductivity is observed for all mentioned dopants and among these K₂SO₄ is found to be the best in sulphate category and KCl in chloride category. The formation of copolymer has been confirmed by differential scanning calorimetry.     

Spectroscopic and electrochemical studies on block‐polymer/PMMA blend based composite polymer electrolytes

Poly(methylmethacrylate)(PMMA)/oxymethylene‐linked polyoxyethylene multi‐block polymer(Om‐POE_n, where n represents number of unit  CH₂CH₂O ) blend based composite electrolyte films containing different lithium salt concentration and nanofillers' content are prepared using solvent evaporation technique. The interaction of polymer–salt complex has been confirmed using FTIR spectral studies. The figuration of CPE was studied by XRD. Ionic conductivity and thermal behavior of the CPEs were studied with various salt concentrations, temperature, and nanofillers' content. The surface structure of the CPE is also investigated using scanning electron microscopy. The high room temperature ionic conductivity, transmittivity in the visible region, and thermal stability make these CPEs potential candidates as solid‐like electrolytes for electrochemical devices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Poly(azomethine-imide)s containing siloxane moities: Optical,thermal, mechanical,and morphological properties

A new series of poly(azomethine-imide)s having siloxane moities in backbone was prepared using different dianhydrides.Thermal, optical, and morphological properties of these polymers were clarified. Also, bulky  CO and  CF₃ group effects and meta or para-substituted aldeyhde effects on the mentioned properties were evaluated. The structural characterization of poly(azomethine-imide)s was carried out using a FT-IR spectroscopy. The optical properties of the polymers were performed via an UV–Vis spectrophotometer. Optical band gap of the poly(imide)s containing azomethine was calculated between 2.20 and 2.33 eV. Thermal behavior of poly(azomethine-imide)s was also studied using TG-DTA, DSC, and DMA techniques. The onset degradation temperature and percentage char values of the polyimides were found in the range from 429 to 545 °C and 22 to 35%, respectively. Thermal stability results demonstrated that benzophenone bearing poly(azomethine-imide)s have higher onset temperature, percentage char, and the glass transition temperature than poly(azomethine-imide)s derived from hexafluoroisopropylidene. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48364.     

Effect of hydrogen‐bonding in the development of high‐affinity metal ion complexants: Polymer‐bound phosphorylated cyclodextrin

In a series of phosphorylated polyols bound to a polystyrene support, the position of the FTIR band assigned to hydrogen bonding between the  OH and phosphoryl oxygen correlates with the affinity of that phosphoryl oxygen for metal ions. Polymer with phosphorylated β‐cyclodextrin (pCD) ligands is now reported as a further test of this correlation. The metal ion affinity is probed with the uranyl ion. pCD is the most red‐shifted of a series of five phosphorylated polyols: the strongest polyol had been phosphorylated pentaerythritol (pPE) with a band at 873 cm⁻¹; pCD has a band at 868 cm⁻¹. Consistent with the FTIR bands, pCD has a significantly higher affinity for the uranyl ion than pPE: the percents complexed from a 10⁻⁴M uranyl solution in a background of 1.0N HNO₃, HCl, and H₂SO₄ are 94.7%, 90.5%, and 93.6%, respectively, for pCD and 68.6%, 52.1%, and 40.1%, respectively, for pPE. This further supports the hypothesis that the strong complexing ability of phosphorylated polyols is due to activation of the phosphoryl oxygen through hydrogen bonding between the PO and the  OH groups within the polyol. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure,electrical and optical properties of (PVA/LiAsF6) polymer composite electrolyte films

In this work, Li⁺ ion conducting polymer composite electrolyte films (PECs) were prepared based on poly (vinyl alcohol) (PVA), lithium hexafluoro arsenate (LiAsF₆), and ceramic filler TiO₂ using solution cast technique. The XRD and FTIR spectra were used to determine the complexation of the PVA polymer with LiAsF₆ salt. The ionic conductivities of the (PVA + LiAsF₆) and (PVA + LiAsF₆ + TiO₂) films have been determined by the A.C. impedance measurements in the temperature range 320–440 K. The maximum conductivity was found to be 5.10 × 10^?4 S cm^?1 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ polymer composite film at 320 K. The calculation of Li⁺ ion transference number was carried out by the combination of A.C. impedance and D.C. polarization methods and is found to be 0.52 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ film. Optical properties such as direct energy gap, indirect energy gap, and optical absorption edge values were investigated in pure PVA and salt complexed PVA films from their optical absorption spectra in the wavelength range of 200–600 nm. The absorption edge was found at 5.76 eV for undoped film, while it is observed at 4.87 and 4.70 eV for 20 and 25 wt% LiAsF₆ doped films, respectively. The direct band gaps for these undoped and salt doped PVA films were found to be 5.40, 5.12, and 4.87 eV, respectively, whereas the indirect band gaps were determined as 4.75, 4.45, and 4.30 eV. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Electrochemical polymerization of poly(o-anisidine) thin films: effect of synthesis temperature studied by cyclic voltammetry

The effect of temperature on the electrochemical synthesis of poly(o-anisidine) (POA) thin films has been investigated. The POA films were synthesized electrochemically under cyclic voltammetric conditions in aqueous solutions of H₂SO₄ at various temperatures between -6°C and 40°C. These films were characterized by cyclic voltammetry (CV), UV–visible spectroscopy and scanning electron microscopy (SEM). It has been found that the rate of polymer formation depends on the synthesis temperature and is highest at 15°C. The optical absorption spectra indicate a major peak at about 800nm and a shoulder at about 440nm independent of the synthesis temperature. The peak at about 800nm corresponds to the presence of the emeraldine salt phase of POA, while the latter may be attributed to the formation of radical cations. The absorbance and width of the peak at about 800nm is observed to increase at low synthesis temperatures. The POA film synthesized at 15°C shows predominant formation of the emeraldine salt phase of POA. The surface morphology as revealed by SEM, is observed to depend on the synthesis temperature, and is caused by different rates of polymer formation at different temperatures. © 1998 SCI.     

Spectral characterization of lysozyme adsorption on dye-affinity beads

Cibacron Blue F3GA-attached magnetic poly(2-hydroxyethyl methacrylate) [mPHEMA] beads were prepared by suspension polymerization of HEMA in the presence of magnetite (Fe₃O₄) nanopowder. Average diameter size of the mPHEMA beads was 150–200 μm. The characteristic functional groups of Cibacron Blue F3GA-attached mPHEMA beads were analyzed by Fourier transform infrared spectrometer (FTIR) and Raman scattering spectrometer. The lysozyme adsorption and desorption characteristics of Cibacron Blue F3GA-attached mPHEMA beads were also investigated using FTIR and Raman spectroscopic techniques. When the Raman spectrum of lysozyme adsorbed mPHEMA is evaluated characteristic Amide-I band appears at 1657 cm⁻¹. The intensity of this band decreases in the spectrum of lysozyme desorbed mPHEMA sample. When the characteristic bands of lysozyme adsorbed and desorbed mPHEMA samples are compared, the band intensities of desorbed sample are lower than those of lysozyme adsorbed sample except for the band appearing at 656 cm⁻¹ (Tyr vC S). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrochemical synthesis of sulfonated polypyrrole in FSO3H/acetonitrile solution

The incorporation of SO₃^? groups into a polypyrrole backbone was successfully carried out using FSO₃H/acetonitrile medium. The degree of sulfonation (sulfonation or sulfur‐to‐nitrogen ratio) of polymer was controlled by varying FSO₃H concentration while the film was being electrodeposited. The cyclic voltammograms of the electrodeposited films were taken between ?1.00 and +2.00 V (versus Ag/AgCl) in blank solution. A substantial effect on the electrical conductivity was observed upon the incorporation of SO₃^? groups in the polypyrrole polymeric chain. The elemental analysis results of the freshly prepared and reduced films give independent evidence that the SO₃^? groups are covalently bound to the structure. FTIR, UV‐Vis, spectroscopy and SEM techniques were used to characterize the electrosynthesized polypyrrole films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 526–533, 2004     

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     

Mid‐Infrared Monitoring of Gas‐Liquid Reactions in Vitamin D Analogue Synthesis with a Novel Fiber Optical Diamond ATR Sensor

A novel mid‐infrared optical sensor enabling in situ ATR measurements was applied to investigate several steps of a vitamin D analogue synthesis. The probe based on silver halide fibers coupled to a diamond prism was connected to a conventional FTIR spectrometer with internal MCT detector. All steps of the reaction were monitored by real‐time in situ FTIR measurements. The steps carried out were the dissolution of SO₂ in a CH₂Cl₂/CH₃OH solvent mixture as well as the addition of SO₂ to a vitamin D analogue, the subsequent ozonation of the double bond in the SO₂ addition product, and the following reduction of the formed hydroperoxide with triphenylphosphine. The dissolving process of SO₂ and the addition of SO₂ to the vitamin D analogue were monitored by changing the characteristic ν_as(SO₂) and ν_s(SO₂) modes of dissolved and incorporated SO₂. It was found that during ozonation of the SO₂ addition product the formation of hydroperoxide is accompanied by the simultaneous formation of the corresponding aldehyde identified by the typical ν(C=O) band at 1720 cm^–1. Extended ozone exposure favors the formation of the corresponding acid detected by an additional carbonyl band at lower wavenumbers. During the reaction with triphenylphosphine the increasing intensity of the aldehyde band and the appearance of the ν(P=O) mode of the formed triphenylphosphine oxide indicate the progressive reduction of hydroperoxide. The hydroperoxide band disappears completely during the reaction whereas the ν_as(SO₂) band remains unaffected.     

Soluble semi-conductive chelate polymers containing Cr(III) in the backbone: Synthesis, characterization, optical, electrochemical, and electrical properties

Soluble kinds of coordination polymers containing Cr(III) ion in the backbone were synthesized. Structures of the polymers were characterized by FT-IR, UV-vis, ¹H and ¹³C NMR, and size exclusion chromatography (SEC). Thermal degradation data were obtained by TG-DTA and DSC techniques. Cyclic voltammetry (CV) measurements were carried out and the HOMO-LUMO energy levels and electrochemical band gaps were calculated. Additionally, the optical band gaps (E_g) were determined by using UV-vis spectra of the materials. Electrical conductivity measurements of doped (with iodine) and undoped polymers related to temperature were carried out by four-point probe technique using a Keithley 2400 electrometer. Measurements were made by using the polymeric films deposited on ITO glass plate by dip-coating method. Also, absorption spectra of doped polymeric films were recorded by a single beam spectrophotometer showing that doping procedure causes shifting in absorption spectra. Their abilities of processing in gas sensors were also discussed. According to obtained results the synthesized chelate polymers are semi-conductors having polyconjugated structures. Also, P-2 is the most electro-conductive polymer among the synthesized, while P-1 is the most thermally stable one.     

The effect of copolymer composition on the surface properties of perfluoroalkylethyl acrylates

The surface properties of two perfluoroalkylethyl acrylic copolymers—aqueous, Zonyl^®329 and solvent‐based, Zonyl^®225—were studied. Zonyl^®329 is a water‐based dispersion and Zonyl^®225 a solvent‐based copolymer solution; both polymers have the same perfluoroalkyethyl side chains [F(CF₂)_nCH₂CH₂? ] but have different comonomer compositions. Thin films, prepared by dip coating onto mica and quartz, with and without annealing, were characterized by contact angle and by X‐ray photoelectron spectroscopy (XPS). The contact angle measurements showed little variation with polymer and with substrate, consistent with the supposition that the perfluoroalkylethyl chains aggregate on the surface and thus dominate surface properties, irrespective of the composition of the rest of the polymer. XPS revealed only small variations in surface chemistry for studied films. Annealed films showed improved segregation for solvent‐based Zonyl^®225, which has both hydrocarbon alkyl and perfluoroalkylethyl side chains; the presence of hydrocarbon alkyl chains enables the perfluoroalkylethyl chains to reorganize after annealing. Depending on the external conditions, this thermal treatment can enable more perfluoroalkylethyl chains to reach the film surface (solid/air interface), leading to a reduction in the dispersive‐dominant surface and enhancement in perfluoroalkylethyl segregation. This suggested that perfluoroalkylethyl side chains dominate the surface properties, which are thus not dependent on substrate, backbone composition, or formulation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Viscosity temperature relationship for dilute solutions of poly[2,2′-(alkylene-arylene)-5,5′-bibenzimidazolyl]

Various copolymers having benzimidazole rings along with alkylene and arylene groups in the backbone were prepared from 3,3′-diaminobenzidine tetrahydrochloride dihydrate and dicarboxylic acids in polyphosphoric acid. The viscosities of these polymers in concentrated sulphuric acid (98%) have been determined at 30, 40 and 50°C. There is no systematic variation in the value of K′ (Huggins constant) with temperature. Values of Q and A in the expression η = A exp(Q/RT) were obtained for these polymer samples in H₂SO₄. On the basis of the ‘A’ values, it has been concluded that most of these polymers were stiff chains with the exception of those containing cis-vinylene groups in the backbone.     

Ionic interactions and transport mechanism in polyurethane electrolytes

Alternating current (AC) impedance, Fourier transform (FT)–Raman, and Fourier transform infrared (FTIR) have been conducted on solutions of poly(ethylene oxide)_(MW=1000)–urethane electrolytes commingled with LiCF₃SO₃ as the function of temperature and salt concentration. From the analysis of the Vs(SO₃) vibration, the ionic concentration of salt in various chemical environments can be calculated approximately. The spectroscopic evidence was found for the redissociated ion pairs, and ionic congeries increased with increasing temperature. AC impedance measurements is used to calculate the ionic diffusion coefficient (D_i). Investigated the various concentrations (from O/Li = 4 ～ 20) at the different temperature (40 ～ 120°C), We found that the calculated values (D_i) with the Nernst–Einstein equation are higher than the direct measurement. The discrepancy increases with the increase of temperature. A good correlation between the conductivity and the ionic redissociation is determined from the Vs(SO₃) vibration band. The fraction of the “free” ion significantly corresponds to the revised Nernst–Einstein equation by using the Nernst–Einstein relation and compared with those direct measurement. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 785–790, 2002     

Thermally induced crystallization and enzymatic degradation studies of poly (L‐lactic acid) films

Poly(L ‐lactic acid) (PLLA) films with different crystallinities were prepared by solvent casting and subsequently annealed at various temperatures (T_a) (80–110°C). The effects of crystallinity on enzymatic degradation of PLLA films were examined in the presence of proteinase K at 37°C by means of weight loss, DSC, FTIR spectroscopy, and optical microscopy. DSC and the absorbance ratio of 921 and 956 cm^?1 (A₉₂₁/A₉₅₆) were used to evaluate crystallinity changes during thermally induced crystallization and enzymatic hydrolysis. The highest percentage of weight loss was observed for the film with the lowest initial crystallinity and the lowest percentage of weight loss was observed for the film with highest crystallinity. FTIR investigation of degraded films showed a band at 922 cm^?1 and no band at 908 cm^?1 suggested that all degraded samples form α crystals. The rate of degradation was found to depend on the initial crystallinity of PLLA film and shown that enzymatic degradation kinetics followed first‐order kinetics for a given enzyme concentration. DSC crystallinity and IR absorbance ratio, A₉₂₁/A₉₅₆ ratio, showed no significant changes with degradation time for annealed PLLA films whereas as‐cast PLLA film showed an increase in crystallinity with degradation; this revealed that degradation takes place predominantly in the free amorphous region of annealed PLLA films without changing long range and short range order © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Efficient and Highly Chemoselective Direct Reductive Amination of Aldehydes using the System Silane/Oxorhenium Complexes

This work reports a novel method for direct reductive amination of aldehydes with silanes catalyzed by several high‐valent oxorhenium(V) and oxorhenium(VII) complexes. The catalytic system PhSiH₃/ReIO₂(PPh₃)₂ (2.5 mol%) was very efficient for the synthesis of secondary amines and highly chemoselective, tolerating a wide range of functional groups such as  NO₂,  CF₃,  SO₂R,  CO₂R,  F,  Cl,  Br,  I,  CN,  OH,  OCH₃,  SCH₃,  NCOR, and double bonds. This novel method was also employed in the synthesis of tertiary amines with moderate yields.     

Single Step Synthesis of Nitro‐Functionalized Hydroxyl‐Terminated Polybutadiene

The paper reports the energization of Hydroxyl‐Terminated Polybutadiene (HTPB) by functionalizing explosophore  NO₂ over the HTPB backbone, resulting in the formation of conjugated nitro‐alkene derivative of HTPB. A convenient, inexpensive and efficient “one pot” procedure of synthesizing Nitro‐Functionalized Hydroxyl‐Terminated Polybutadiene (Nitro‐HTPB) is reported. The reaction was carried out with sodium nitrite and iodine. To retain the unique physico‐chemical properties of HTPB, functionalization by  NO₂ group was restricted to 10 to 15 % of double bonds. The Nitro‐HTPB was characterized by FTIR, ¹H NMR, VPO, DSC, TGA etc. The polymer has shown good thermal stability for practical applications. The kinetic parameters for the decomposition of Nitro‐HTPB at 150–300 °C were obtained from non‐isothermal DSC data.