Diffusion process of amino acids in polymer supports for solid‐phase peptide synthesis as studied by pulsed‐field‐gradient spin‐echo proton nuclear magnetic resonance

The diffusion coefficient (D) values of tert‐butyloxycarbonyl‐glycine, tert‐butyloxycarbonyl‐L ‐tryptophan, tert‐butyloxycarbonyl‐L ‐phenylalanine (Boc‐Phe), and 9‐fluorenylmethoxycarbonyl‐L ‐phenylalanine in Merrifield polystyrene (MPS) gels, poly(ethylene glycol)‐grafted polystyrene (PEG–PS) gels, and crosslinked ethoxylate acrylate (CLEAR) gels, as used in solid‐phase peptide synthesis, were determined by the pulsed‐field‐gradient spin‐echo ¹H‐NMR method. From these experimental results, it was found that the amino acids in MPS gels, PEG–PS gels, and CLEAR gels with N,N‐dimethylformamide‐d₇ (DMF‐d₇) as a solvent had multidiffusion components within a measurement timescale of 10 ms. The D value of Boc‐Phe in polystyrene gels (1% divinylbenzene crosslinked) with tetrahydrofuran‐d₈ was much larger than that in the same gels with DMF‐d₇. Furthermore, the required time in which an amino acid transferred from a reactive site to a reactive site was estimated, within which the solvents and amino acids in the polymer supports diffused in the swollen beads.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 413–421, 2003     

Fabrication of alumina based electrically conductive polymer composites

Novel electrically conductive composites were synthesized by incorporating Cu coated alumina (Cu‐Al₂O₃) powder prepared via electroless plating technique as filler (0–21wt %) into polystyrene‐b‐methylmethacrylate (PS‐b‐PMMA) and polystyrene (PS) matrices. XRD analysis depicted maximum Cu crystallite growth (26.116 nm～ plating time 30 min) onto Al₂O₃ along with a significant change in XRD patterns of composites with Cu‐Al₂O₃ inclusion. SEM–EDX analyses exhibited uniform Cu growth onto Al₂O₃ and confirmed presence of Cu, Al, Pd in Cu‐Al₂O₃, and C, O, Al, Cu, and Pd in PS‐b‐PMMA and PS composites. Increasing filler loadings exhibited increased electrical conductivity (5.55 × 10^?5S/cm for PS‐b‐PMMA; 5.0 × 10^?6S/cm for PS) with increased Young's modulus (1122MPa for PS‐b‐PMMA; 1053.9MPa for PS) and tensile strength (27.998MPa for PS‐b‐PMMA; 30.585MPa for PS) and decreased % elongation. TGA demonstrated increased thermal stability and DTG revealed two‐step degradation in composites while DSC depicted pronounced increment in T_g of Cu‐Al₂O₃/PS‐b‐PMMA with increased filler loading. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42939.     

A nanocomposite of poly(N‐vinylcarbazole) with nanodimensional alumina

A nanocomposite of poly(N‐vinylcarbazole) (PNVC) and Al₂O₃ was prepared by precipitation of a preformed PNVC in a tetrahydrofuran solution onto an aqueous suspension of nanodimensional Al₂O₃. Prolonged extraction of a PNVC–Al₂O₃ composite by benzene failed to extract the loaded PNVC from the Al₂O₃, as shown by Fourier transform infrared studies. Scanning electron microscopy analyses revealed distinct morphological features of the composite, and transmission electron microscopy analyses confirmed that the particle sizes were in the range of 120–240 nm. Thermogravimetric analyses demonstrated the enhanced stability of the nanocomposite relative to the base polymer. Direct current conductivity of the PNVC–Al₂O₃ composites was found to be about 0.14 × 10^?6 S/cm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2233–2237, 2003     

Immobilization of catalase on a novel polymer support,crosslinked polystyrene ethylene glycol acrylate resin: Role of the macromolecular matrix on enzyme activity

Crosslinked polystyrene ethylene glycol acrylate resin (CLPSER) was developed for the immobilization of the enzyme catalase by the introduction of a crosslinker, O,O′‐bis(2‐acrylamidopropyl) poly(ethylene glycol)₁₉₀₀, to styrene. The crosslinker was prepared by the treatment of acryloyl chloride with O,O′‐bis(2‐aminopropyl) poly(ethylene glycol)₁₉₀₀ in the presence of diisopropylethylamine. The resin was characterized with IR and ¹³C‐NMR spectroscopy. The catalytic activity of the catalase‐immobilized system of CLPSER was compared with divinylbenzene‐crosslinked polystyrene, ethylene glycol dimethacrylate crosslinked polystyrene, and 1,4‐butanediol dimethacrylate crosslinked polystyrene systems. Crosslink levels of 2, 8, and 20 mol % were evaluated. Among these crosslinked systems, the 2 mol % system was found to be most suitable to support catalytic activity. When a long flexible hydrophilic poly(ethylene glycol) crosslink, introduced between the polystyrene (PS) backbone and functional groups was used for immobilization, the extent of coupling and enzyme activity increased. Depending on the nature of the support, the catalytic activity of the system varied. The hydrophilic CLPSER support was most efficient for immobilization compared to the other PS‐based supports. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 8–19, 2005     

Ultraviolet‐ray treatment of polysulfone membranes on the O2/N2 and CO2/CH4 separation performance

UV irradiation on polysulfone (PSF) membranes was studied to improve their gas‐separation properties. Membranes with 19–25% PSF contents were prepared by the phase‐inversion method, and the membrane surface was modified with UV rays with a wavelength of 312 nm and a power of 360 µw/cm². Measurements of gas permeation were conducted with pure carbon dioxide (CO₂), methane (CH₄), oxygen (O₂), and nitrogen (N₂) gases under 3–8 bar pressure at 25°C. Fourier transform infrared spectrometry revealed that the polar functional groups of hydroxyl and carbonyl were introduced by UV irradiation. The water contact angle of the treated membrane was reduced from 70–75° to 10–12° after 12 h of UV exposure. Scanning electron microscopy observation showed that the dense skin layer increased as the polymer concentration increased. After UV treatment, the permeation of O₂ decreased from 0.4–3.4 to 0.2–2.3 m³ m^?2 h^?1 bar^?1, whereas that of N₂, CO₂, and CH₄ increased for all of the pressures used from 0.1–1.7 m³ m^?2 h^?1 bar^?1 to about 0.1–3.4 m³ m^?2 h^?1 bar^?1; this depended on the applied pressure and the PSF content. As a result, the selectivity ratio of O₂/N₂ decreased from 1.9–7.8 to 0.6–1.5, whereas that of CO₂/CH₄ increased from 0.9–2.6 to 1.1–6.1. Moreover, the O₂/N₂ and CO₂/CH₄ of the untreated and the treated membranes decreased with increasing pressure and increased with increasing polymer concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42074.     

Polyaniline‐functionalized magnetic mesoporous nanocomposite: A smart material for the immobilization of lipase

Magnetically separable mesoporous silica nanocomposites with polyoaniline functionalization (Pani‐MS@Fe₃O₄) were synthesized for the immobilization of lipase via electrostatic adsorption. The as‐prepared Pani‐MS@Fe₃O₄ nanocomposites as well as immobilized lipase were characterized by FTIR, XRD, HRTEM, FESEM, BET, and TGA techniques. The BET surface area was calculated to be 779.27 m²/g, 425 m²/g, and 230.45 m²/g for magnetic mesoporous nanoparticle (MS@Fe₃O₄), Pani‐MS@Fe₃O₄ nanocomposite, and lipase immobilized Pani‐MS@Fe₃O₄ nanocomposite respectively. The comparison experiments verified that the immobilized lipase exhibited slightly higher optimal pH and temperature value with a wider pH‐activity and temperature stability in comparison with the free lipase. From Michaelis–Menten kinetic study, the lower K_m value (0.25 mM) and higher V_max value (0.0341 mM/min) for the immobilized lipase revealed the higher affinity of immobilized lipase toward the substrate. Further, reusability studies of the immobilized lipase indicated that up to 70% of the original activity was retained after having been recycled seven times. POLYM. COMPOS. 37:1152–1160, 2016. © 2014 Society of Plastics Engineers     

A water‐dispersible conducting nanocomposite from suspension polymerisation of thiophene in presence of N‐vinylcarbazole

The polymerisation of a mixture of thiophene and N‐vinylcarbazole was achieved in aqueous suspension in the presence of nanodimensional alumina and FeCl₃ as oxidant. The resultant composite was found to contain both polythiophene (PTP) and poly(N‐vinylcarbazole) (PNVC) components even after reflux in benzene, which would remove any PNVC homopolymer. The presence of the individual polymer components was endorsed by FTIR spectroscopic analyses. Thermogravimetric analyses showed that the overall stabilities of the composite and the corresponding homopolymers were in the order: PTP–Al₂O₃ > PTP > PTP–PNVC–Al₂O₃ > PNVC. Differential thermal analyses studies showed the manifestation of two different exotherms corresponding to the presence of two different polymeric constituents in the PTP–PNVC–Al₂O₃ composite. Differential scanning calorimetry studies revealed two glass‐transition temperatures (T_g) suggesting the presence of two polymeric moieties in the PTP–PNVC composite. Scanning electron micrographs of the PTP–Al₂O₃ and PTP–PNVC–Al₂O₃ composites showed distinctive morphological patterns. Transmission electron microscopic images of the composite revealed that the average particle size varied between 20 and 80 nm. DC conductivities of the composites were of the order of 10^?6 S cm^?1. Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of novel core‐shell magnetic nanogels based on 2‐acrylamido‐2‐methylpropane sulfonic acid in aqueous media

Ultrafine well‐dispersed Fe₃O₄ magnetic nanoparticles were directly prepared in aqueous solution using controlled coprecipitation method. The synthesis of Fe₃O₄/poly (2‐acrylamido‐2‐methylpropane sulfonic acid) (PAMPS), Fe₃O₄/poly (acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AM‐co‐AMPS) and Fe₃O₄/poly (acrylic acid‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AA‐co‐AMPS) ‐core/shell nanogels are reported. The nanogels were prepared via crosslinking copolymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid, acrylamide and acrylic acid monomers in the presence of Fe₃O₄ nanoparticles, N,N′‐methylenebisacrylamide (MBA) as a crosslinker, N,N,N′,N′‐tetramethylethylenediamine (TEMED) and potassium peroxydisulfate (KPS) as redox initiator system. The results of FTIR and ¹H‐NMR spectra indicated that the compositions of the prepared nanogels are consistent with the designed structure. X‐ray powder diffraction (XRD) and transmission electron microscope (TEM) measurements were used to determine the size of both magnetite and stabilized polymer coated magnetite nanoparticles. The data showed that the mean particle size of synthesized magnetite (Fe₃O₄) nanoparticles was about 10 nm. The diameter of the stabilized polymer coated Fe₃O₄ nanogels ranged from 50 to 250 nm based on polymer type. TEM micrographs proved that nanogels possess the spherical morphology before and after swelling. These nanogels exhibited pH‐induced phase transition due to protonation of AMPS copolymer chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication of oriented electrospun cellulose nanocrystals–polystyrene composite fibers on a rotating drum

Nitrobenzene (CNC-1), trifluoromethyl benzene (CNC-2) modified and polystyrene-grafted (CNC-g) cellulose nanocrystals in polystyrene (PS)-N,N dimethylformamide (DMF) solutions were electrospun and collected as stretched and aligned fibers on a rotating drum. Scanning electron microscope pictures showed significant alignment in the case of unmodified and nitrobenzene-modified CNC-1/PS nanocomposite fibers once the linear speed of rotor reached to 15 m s⁻¹. Fiber diameter decrease was more strong with rotor speed increase in the case of trifluoromethyl benzene modified (CNC-2) and polystyrene-grafted (CNC-g) cellulose nanocrystals/PS systems. Dynamic mechanical analysis including storage and elastic modulus of electrospun-oriented fibers were performed on surface-modified and polymer-grafted CNC/PS samples. According to α transition peak, the increase in the glass-transition temperature with filler concentration was the highest in polymer-grafted CNC-g/PS composite fibers. It was due to the interpenetration of grafted polymer brushes and free polymer chains in continuous phase and resulted in restrictions of motions of polymer chains in the PS matrix. The elastic moduli of nitrobenzene (CNC-1) and trifluoromethyl benzene (CNC-2)-modified CNC-filled PS composite fibers agreed well with percolation model, which indicates the CNC–CNC interactions and network formation with an increase in concentration. Magnitude of the elastic modulus of polymer grafted CNC-g at 0.33 vol % in PS was significantly higher than the prediction from percolation theory. It was due the immobilized polymer chains around CNC-g particles. However, grafted polymer chains, at higher CNC concentrations acted like stickers among CNC particles and caused CNC agglomerates with entrapped free polystyrene from the matrix, thus caused a decrease in the elastic modulus. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48942.     

Viscosity of polystyrene solutions expanded with carbon dioxide

The viscosity of solutions of polystyrene (PS) in decahydronaphthalene (DHN) was measured in the presence of carbon dioxide (CO₂) with a moving‐piston viscometer. The effects of the CO₂ pressure (0–21 MPa), polymer concentration (1–15 wt %), temperature (306–423 K), and polymer molecular weight (126 and 412 kDa) on the viscosity were investigated. In the absence of CO₂, the increase in the viscosity with increasing polymer concentration was approximately exponential in concentration and was well described by the Martin equation. All the data fell on a single line when the relative viscosity was plotted against cM^0.50 (where c is the concentration of the polymer in solution and M is the molecular weight of the polymer). The viscosity of the polymer solution decreased with increasing CO₂ pressure under otherwise constant conditions. For a given CO₂ pressure, the viscosity reduction was greatest when the relative viscosity was high in the absence of CO₂, that is, for high‐molecular‐weight polymer, high polymer concentrations, and low temperatures. Reductions in the relative viscosity of almost 2 orders of magnitude were observed in some cases. The viscosity of solutions of PS in DHN also was measured in the presence of sulfur hexafluoride (SF₆). At a given pressure, SF₆ was about as effective as CO₂ in reducing the solution viscosity. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 540–549, 2006     

Synthesis,characterization, thermal stability,conductivity, and band gap of a new aromatic polyether containing an azomethine as a side

In this study, the oxidative polycondensation reaction conditions of 4‐[(4‐methylphenyl)iminomethyl]phenol (4‐MPIMP) were studied by using oxidants such as air O₂, H₂O₂, and NaOCl in an aqueous alkaline medium between 50 and 90°C. The structures of the synthesized monomer and polymer were confirmed by FTIR, UV–vis, ¹H–¹³C‐NMR, and elemental analysis. The characterization was made by TGA‐DTA, size exclusion chromatography (SEC), and solubility tests. At the optimum reaction conditions, the yield of poly‐4‐[(4‐methylphenyl)iminomethyl]phenol (P‐4‐MPIMP) was found to be 28% for air O₂ oxidant, 42% for H₂O₂ oxidant, and 62% for NaOCl oxidant. According to the SEC analysis, the number–average molecular weight (M_n), weight–average molecular weight (M_w), and polydispersity index values of P‐4‐MPIMP were found to be 4400 g mol^?1, 5100 g mol^?1, and 1.159, using H₂O₂, and 4650 g mol^?1, 5200 g mol^?1, and 1.118, using air O₂, and 5100 g mol^?1, 5900 g mol^?1, and 1.157, using NaOCl, respectively. According to TG analysis, the weight losses of 4‐MPIMP and P‐4‐MPIMP were found to be 85.37% and 72.19% at 1000°C, respectively. P‐4‐MPIMP showed higher stability against thermal decomposition. Also, electrical conductivity of the P‐4‐MPIMP was measured, showing that the polymer is a typical semiconductor. The highest occupied molecular orbital and the lowest unoccupied molecular orbital energy levels and electrochemical energy gaps (E) of 4‐MPIMP and P‐4‐MPIMP were found to be ?5.76, ?5.19; ?3.00, ?3.24; 2.76 and 1.95 eV, respectively. According to UV–vis measurements, optical band gaps (E_g) of 4‐MPIMP and P‐4‐MPIMP were found to be 3.34 and 2.82 eV, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Molecular design,synthesis, and electro‐optic properties of novel Y‐type polyesters with high thermal stability of second harmonic generation

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene was prepared and condensed with terephthaloyl chloride, adipoyl chloride, and sebacoyl chloride to yield novel Y‐type polyesters containing NLO‐chromophore dioxynitrostilbenyl groups, which constituted parts of the polymer backbone. Polymers were found soluble in common organic solvents such as acetone and N,N‐dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis with glass‐transition temperatures obtained from differential scanning calorimetry in the range 110–152 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at a 1064 cm^?1 fundamental wavelength were around 3.51 × 10^?8 esu. The dipole alignment exhibited high thermal stability even at 10 °C higher than the glass‐transition temperature, and there was no SHG decay below 120 °C for one of these polymers due to the partial main‐chain character of polymer structure, which was acceptable for NLO device applications. Copyright © 2005 Society of Chemical Industry     

Poly(styrene–divinyl benzene)‐immobilized Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene: Efficient catalyst for the photocatalytic degradation of xylenol orange

A polymer‐supported Fe(III) complex of 1,3‐bis(benzimidazolyl)benzene [PS–Fe(III)BBZNH] was used in the photodegradation of xylenol orange (XO) dye with H₂O₂ under UV irradiation. The catalyst was synthesized and characterized by elemental analysis, and Fourier transform infrared, far‐infrared, and UV–visible–diffuse reflectance spectroscopy, Scanning electron microscopy, Brunauer–Emmett–Teller surface area measurements, thermogravimetric analysis, and magnetic measurements. An octahedral coordination around Fe(III) was confirmed by electronic spectral data, and a decrease in the intensity of the ν_CH2Cl peak in PS–Fe(III)BBZNH was observed compared to the polymer support; this indicated the binding of the ligand to the support. An array of experiments were carried out to assess the influence of various reaction parameters on its photocatalytic performance to ensure maximum dye degradation. The maximum photocatalytic activity was observed at pH 8 with 125 mg of catalyst, 300 ppm of XO, and 200 ppm of H₂O₂ with complete mineralization after 90 min, as confirmed by chemical oxygen demand measurements. Furthermore, the reactions were repeated under sunlight and under dark conditions to check the photocatalytic efficiency of PS–Fe(III)BBZNH. It displayed better catalytic performance compared than the unsupported complex, PS–Cu(II)BBZNH [Cu(II) complex of 1,3‐bis(benzimidazolyl)benzene], and PS–VO(IV)BBZNH [VO(IV) complex of 1,3‐bis(benzimidazolyl)benzene]. PS–Fe(III)BBZNH could be recycled for up to seven runs. A tentative mechanism involving ·OH radical was proposed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46480.     

Characterization and transport properties of a novel aliphatic polyamide with an ethyl branch

The CO₂ gas and water vapor transport properties of a novel aliphatic polyamide with an ethyl branch were investigated. The polymer was characterized with density measurements, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction analyses, and the amorphous and glassy nature of the polymer at the ambient temperature were confirmed. The CO₂ sorption isotherm of the polymer appeared to obey the dual‐mode sorption isotherm, which was characteristic of the glassy state. The water vapor sorption below a relative humidity of 0.4 or 0.5 was explained in terms of the Brunauer–Emmett–Teller sorption mechanism, whereas that at a high relative humidity demonstrated a dissolution type of water vapor into the polyamide. The permeability coefficients of He, CO₂, O₂, and N₂ gases through the membrane were as follows: P(He) > P(CO₂) > P(O₂) > P(N₂). The novel polyamide membrane was more permeable to CO₂, O₂, and N₂ gases than nylon 6 and nylon 66 membranes, containing a crystalline and hydrogen‐bonding nature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1955–1960, 2005     

Structural effect of emulsifiers on the emulsion stability of a water/benzene mixture

Core–shell‐type microspheres with microphase‐separated shells of polystyrene (PS) and poly(ethylene glycol) (PEG) (microsphere_block: molar ratio: PS/PEG 49.1/45.9 mol %; M_w: PS chain: 1.07 × 10⁴, PEG chain 1.0 × 10⁴; the ratio of arm numbers of PEG to PS: 1.0; microsphere_graft: molar ratio: PS/PEG 33.8/55.9 mol %; M_w: PS chain: 1.54 × 10⁴, PEG chain 1.0 × 10⁴, the ratio of arm numbers of PEG to PS: 2.55) were synthesized by crosslinking of spherical domains of poly(2‐hydroxyethyl methacrylate) (PHEMA) and poly(4‐vinyl pyridine) (P4VP) of the microphase‐separated films of poly(ethylene glycol)‐block‐poly(2‐hydroxyethyl methacrylate)‐block‐polystyrene triblock terpolymer (M_n: 2.18 × 10⁴; molar ratio: PS 49.1 mol %, PHEMA 5.0 mol %, PEG 45.9 mol %) and polystyrene‐block‐[poly(4‐vinyl pyridine)‐graft‐poly(ethylene glycol)] block–graft copolymer (M_n: 4.56 × 10⁴; molar ratio: PS 33.8 mol %, P4VP 10.3 mol %, PEG 55.9 mol %; branch number of PEG: 2.55), respectively. The structures of microphase‐separated films were investigated by transmission electron microscopy and small‐angle X‐ray scattering. The effects of the arm number ratio of PS to PEG and the total arm number on the stability of the water/benzene emulsion were investigated. The emulsion stability of oil in water was improved by using the microsphere synthesized with the microsphere_graft. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 321–331, 2004     

Kinetic study on the poly(methyl methacrylate) seeded soapless emulsion polymerization of styrene. III. Seeds with crosslinking

In this work, a seeded soapless emulsion polymerization was carried out with crosslinking (XL) poly(methyl methacrylate) (PMMA) as seeds, styrene as monomer, and potassium persulfate (K₂S₂O₈) as initiator to synthesize the PMMA XL–PS composite latex, which we knew as the latex interpenetrating polymer network (IPN). The morphology of the latex IPN was observed by transmission electron microscopy (TEM). It showed a core–shell structure. The kinetic data from the early stages of the reaction of seeded soapless emulsion polymerization showed that the square root of polymer yield (W_p)^1/2 was proportional to the reaction time. The reaction rate decreased with the increase of crosslinking density of PMMA seeds. The core–shell model proposed in our previous work^1–2 was modified to predict the conversion of polymerization over the entire course of the synthesis of PMMA (XL)–PS composite latex. Our modified core–shell kinetic model fitted well with the experimental data. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:425–438, 1997     

Polystyrene composites of single‐walled carbon nanotubes‐graft‐polystyrene

Single‐walled carbon nanotubes (SWCNTs) dispersed in N‐methylpyrrolidone (NMP) were functionalized by addition of polystyryl radicals from 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐ended polystyrene (SWCNT‐g‐PS). The amount of polystyrene grafted to the nanotubes was in the range 20‐25 wt% irrespective of polystyrene number‐average molecular weight ranging from 2270 to 49 500 g mol^?1. In Raman spectra the ratios of D‐band to G‐band intensity were similar for all of the polystyrene‐grafted samples and for the starting SWCNTs. Numerous near‐infrared electronic transitions of the SWCNTs were retained after polymer grafting. Transmission electron microscopy images showed bundles of SWCNT‐g‐PS of various diameters with some of the polystyrene clumped on the bundle surfaces. Composites of SWCNT‐g‐PS in a commercial‐grade polystyrene were prepared by precipitation of mixtures of the components from NMP into water, i.e. the coagulation method of preparation. Electrical conductivities of the composites were about 10^?15 S cm^?1 and showed no percolation threshold with increasing SWCNT content. The glass transition temperature (T_g) of the composites increased at low filler loadings and remained constant with further nanotube addition irrespective of the length and number of grafted polystyrene chains. The change of heat capacity (ΔC_p) at T_g decreased with increasing amount of SWCNT‐g‐PS of 2850 g mol^?1, but ΔC_p changed very little with the amount of SWCNT‐g‐PS of higher molecular weight. The expected monotonic decrease in ΔC_p coupled with the plateau behavior of T_g suggests there is a limit to the amount that T_g of the matrix polymer can increase with increasing amount of nanotube filler. Copyright © 2012 Society of Chemical Industry     

Preparation of vinyl amine‐co‐vinyl alcohol/polysulfone composite membranes and their carbon dioxide facilitated transport properties

A vinyl amine–vinyl alcohol copolymer (VAm–VOH) was synthesized through free‐radical polymerization, basic hydrolysis in methanol, acidic hydrolysis in water, and an anion‐exchange process. In the copolymer, the primary amino groups on the VAm segment acted as the carrier for CO₂‐facilitated transport, and the vinyl alcohol segment was used to reduce the crystallinity and increase the gas permeance. VAm–VOH/polysulfone (PS) composite membranes for CO₂ separation were prepared with the VAm–VOH copolymer as a selective layer and PS ultrafiltration membrane as a support. The membrane gas permselectivity was investigated with CO₂, N₂, and CH₄ pure gases and their binary mixtures. The results show that the CO₂ transport obeyed the facilitated transport mechanism, whereas N₂ and CH₄ followed the solution–diffusion mechanism. The increase in the VAm fraction in the copolymer resulted in a carrier content increase, a crystallinity increase, and intermolecular hydrogen‐bond formation. Because of these factors, the CO₂ permeance and CO₂/N₂ selectivity had maxima with the VAm fraction. At an optimum applied pressure of 0.14 MPa and at an optimum VAm fraction of 54.8%, the highest CO₂ permeance of 189.4 GPU [1 GPU = 1 × 10^?6 cm³(STP) cm^?2 s^?1 cmHg^?1] and a CO₂/N₂ selectivity of 58.9 were obtained for the CO₂/N₂ mixture. The heat treatment was used to improve the CO₂/N₂ selectivity. At an applied pressure of 0.8–0.92 MPa, the membrane heat‐treated under 100°C possessed a CO₂ permeance of 82 GPU and a CO₂/N₂ selectivity of 60.4, whereas the non‐heat‐treated membrane exhibited a CO₂ permeance of 111 GPU and a CO₂/N₂ selectivity of 45. After heat treatment, the CO₂/N₂ selectivity increased obviously, whereas the CO₂ permeance decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40043.     

Analyses of structurally modified quasi‐solid‐state electrolytes using electrochemical impedance spectroscopy for dye‐sensitized solar cells

Electrochemical properties of structurally modified quasi‐solid‐state electrolytes were examined using porous substrates (PSs). The PS was prepared into two categories by a phase inversion method with a brominated poly(phenylene oxide) (BPPO): the sponge and finger types. Effects of the humidification and cosolvent compositions on the morphology of the PS were analyzed by scanning electron microscopy. In all cases of the PSs, a higher V_OC was observed of about 0.1 V than that of a liquid electrolyte owing to a suppressed back electron charge transfer. In addition, the PS prepared by the polymer solution of 1 : 4 : 1 (BPPO : N‐methyl‐2‐pyrrolidone : butyl alcohol) with the humidification process showed better photovoltaic properties in terms of the current density and conversion efficiency owing to the appropriate combinations of pore size, tortuosity, and interconnectivity. Effects of the pore structures were intensively examined using electrochemical impedance spectroscopy. The impedance results revealed that large pores at the surface layers are advantageous for a lower R_S and R_TiO2. Meanwhile, the straight inner structure is beneficial for the facile I^?/I₃^? diffusion, thus lowering R_Pt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39739.