Synthesis and characterization of conjugated poly (amino benzyl alcohol) and poly (ethylene glycol) for solid polymer electrolyte

A solid polymer electrolyte chemically bonded to a π-conjugated polymer was prepared for the use as a designed ladder-type structure by the graft copolymerization of poly (aminobenzyl alcohol) (PABA) with poly (ethylene glycol) (PEG). PABA was used as the frame for the ladder and the PEG as the rungs. The expected synergic effect afforded by the introduction of the ionic salts into the crosslinked conjugated polymer and PEG network was investigated as a function of its structure, morphology, and ionic conductivity. The insertion of the ionic salts into the PABA-PEG-PABA network led to the enhancement of the ionic conductivity compared to that of PEG/LiClO₄. The synergic effect may be explained by the more efficient segmental motion of the polymer chains or better ion mobility in the network due to the interrupted crystallization of the PEG chains. The fine tuning of the crosslinked conjugated polymer gel might enable it to show a faster response to electrochemical stimuli.     

Reinforcement of elastomeric poly(dimethylsiloxane) by glassy poly(diphenylsiloxane)

Some novel approaches were taken to provide the improvements in mechanical properties that are almost always necessary to prepare a commercially useful elastomer from poly(dimethylsiloxane) (PDMS) [-Si(CH₃)₂O-]. The reinforcement was provided by poly(diphenylsiloxane) (PDPS) [-Si(C₆H₅)₂O-], a hard glassy polymer, which was introduced into the PDMS by two rather different techniques. In the first, the PDPS was prepared separately by condensation polymerization of diphenylsilanediol and then solution-blended into the PDMS. In the second, it was generated by in situ polymerization of the same monomer absorbed into the PDMS network. The resulting materials were characterized by scanning electron microscopy and by stress-strain isotherms in elongation. At least under some conditions both techniques were found to be successful, leading to increases in ultimate strength by a factor of two or more.     

Adsorption of poly(4-vinylpyridine) onto bentonites

The preparation of new adsorbents based on the coating of a poly(4-vinylpyridine) (P₄VP) polymer onto industrial bentonites was investigated. Two ways of synthesis were investigated, using dibromohexane (DBH) or its absence as a difunctional quaternizing agent in order to fasten the polymer by cross-linking. Several parameters (reagents ratio, type of bentonite, chemical stability in liquid media) were studied. Qualitative (IR and RMN spectroscopies) and quantitative (thermogravimetric) analyses of the samples were carried out.     

新型超支化聚(酰胺-酯)的制备及表征

以二异丙醇胺和六氢化苯二甲酸酐为原料,合成AB_2型单体(DH)。二异丙醇胺过量,利用DH和过量的二异丙醇胺在共沸带水剂二甲苯中进行缩聚反应,合成新型超支化聚(酰胺-酯);同时利用傅立叶红外光谱和化学滴定法对DH和超支化聚(酰胺-酯)进行表征,并对超支化聚(酰胺-酯)的相对分子量分布、溶解性能进行研究。实验结果表明:合成的超支化聚(酰胺-酯)具有较高的分子量,M_n高达42769g/mol,多分散性指数在1．28～1．60之间,呈现很窄的分子量分布;合成的超支化聚(酰胺-酯)具有良好的溶解性能,能溶于醇类、酮类、四氢呋喃等极性溶剂;相对线形高分子,合成的超支化聚(酰胺-酯)具有较低的黏度,体系中含40%的超支化聚(酰胺-酯)仍能全部溶解,且黏度仅为6．61mPa·s。     

Properties of magnetic poly(glycidyl methacrylate) and poly(N-isopropylacrylamide) microspheres

Iron oxide colloids were prepared by coprecipitation of Fe(II) and Fe(III) salts in alkaline media and stabilized by perchloric acid, oleic acid, or poly(acrylic acid). In an attempt to obtain magnetic polymer microspheres differing in size, dispersion polymerization of glycidyl methacrylate (GMA) in ethanol containing HClO₄-stabilized magnetite, dispersion copolymerization of GMA and 2-hydroxyethyl methacrylate (HEMA) in toluene/2-methylpropan-1-ol mixture in the presence of oleic acid-coated magnetite, and inverse suspension copolymerization of N-isopropylacrylamide (NIPAAm) and N,N′-methylenebisacrylamide (MBAAm) in cyclohexane in the presence of poly(acrylic acid)-coated maghemite were compared. The microspheres were characterized by morphology, size, polydispersity, and some magnetic properties.     

Polymeric anodes from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) for 3.5% efficient organic solar cells

We present highly efficient indium tin oxide free polymer solar cells based on poly-(3-hexylthiophene-2,5-diyl) and C₆₁-bis-butric-acid-methyl-ester (P3HT:bisPCBM) comprising a polymeric anode from highly conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) formulations. The film conductivity was optimized by various additives. We found conductivities of almost 600 S/cm upon the addition of dimethylsulfoxide. The wetting properties of different PEDOT:PSS formulations were investigated by contact angle measurements. The optimized high conductivity in combination with the good film forming properties allow for the fabrication of highly efficient organic solar cells with an external power conversion efficiency of 3.5% with PEDOT:PSS as polymeric anode.     

Resistance to nonspecific protein adsorption by poly(vinyl alcohol) thin films adsorbed to a poly(styrene) support matrix studied using surface plasmon resonance.

Thin films of poly(vinyl alcohol) (PVA) polymer were prepared on a flat, nonporous, poly(styrene) support matrix by adsorption from aqueous solution and were characterized in order to investigate the nonspecific adsorption of proteins to a chromatographically relevant surface. The integrity and surface coverage of the PVA thin films were established by surface analysis and atomic force microscopy imaging. The adsorption of the PVA polymers to the poly(styrene) substrate and the nonspecific adsorption of proteins to the PVA-coated surface were monitored using surface plasmon resonance. PVA was strongly bound to the poly(styrene) surface, but the surface density of the adsorbed PVA polymers was affected substantially by the concentration, molecular weight, and degree of hydrolysis of PVA polymers used. There was evidence of increasing degrees of unfolding of the PVA polymer onto the poly(styrene) surface as the concentration of the the PVA coating solution increased. Complete PVA coverage of the poly(styrene) surface was observed at PVA concentrations of 0.1 mg/mL or greater but with significant influence of both molecular weight and degree of hydrolysis of the PVA polymers. Resistance of the PVA-coated poly(styrene) surface to the nonspecific adsorption of human serum albumin (HSA) correlated with the degree of surface coverage of the PVA. The use of anti-HSA as a probe for adsorbed HSA suggested that HSA was displacing PVA from the poly(styrene) surface at the lower PVA surface coverage. A complete barrier to nonspecific protein adsorption was observed with a PVA coating solution concentration of greater than 0.1 mg/ mL with a degree of hydrolysis of <88%.     

MFC-structured biodegradable poly(l-lactide)/poly(butylene adipate-co-terephatalate) blends with improved mechanical and barrier properties

Both polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable polymers. They are thermoplastics which can be processed using conventional polymer processing methods. In this study, microfibrillar-reinforced composites (MFC) based on PLA/PBAT (PLA/Ecoflex^®) blends in different weight ratios were prepared under industry-relevant conditions by melt extrusion followed by continuous cold drawing of the extrudates. Strip-like specimens (films) and plates (laminates) of the drawn blends were prepared by compression molding (CM) at processing temperature above the melting temperature (T _m) of PBAT, but below T _m of PLA. SEM and WAXS observations show that the extruded blend components are isotropic, but become highly oriented after drawing, and they are converted into MFC-structured polymer–polymer composites after CM. An effect of PLA microfibrils on the non-isothermal crystallization of the Ecoflex during cooling from the melt, associated with the formation of crystalline regions of the matrix around the fibrils, was observed. Depending on the blend composition, the compression-molded samples possess a 3- to 7-time higher tensile strength as well as a 15–30 higher modulus than the neat Ecoflex. In addition, the MFC-structured plates exhibited superior barrier properties compared to the neat Ecoflex, e.g., the oxygen permeability decreased by up to 5 times.     

The reaction between poly(dichlorophosphazene) and epoxide compounds using Friedel-Crafts catalysts

The reaction between poly(dichlorophosphazene) and epichlorohydrin was carried out in tetrachloroethane using various Friedel-Crafts type catalysts. It was found that ferric chloride, FeCl₃, is the most suitable catalyst to transfer chlorine from poly(dichlorophosphazene) to CH in epoxide compounds. The molecular weight of the prepared product had decreased in comparison with that of poly(dichlorophosphazene); however, the products having the highest molecular weight were prepared with epifluorohydrin or 1,2-epoxy-3,3,3,-trichloropropane.     

Influence of poly(ethylene glycol) block length on the adsorption of thermoresponsive copolymers onto gold surfaces

The adsorption of a series of four poly(N-isopropylacrylamide)-based copolymers composed of a hydrophilic block of methoxy poly(ethylene glycol) (MPEG) with a variable length and a PNIPAAM block of fixed size (MPEG _n -b-PNIPAAM₇₁) onto flat and spherical citrate-coated gold surfaces has been investigated. The adsorption onto planar surfaces was studied by means of the quartz crystal microbalance with dissipation monitoring, whereas polymer adsorption onto gold nanoparticles was examined using dynamic light scattering and visible spectroscopy. Experiments were performed with two different concentrations of polymer in bulk solution, namely 0.05 and 0.0005 wt%. The influence of the MPEG length on the thickness of the adsorbed layer on the nanoparticles, and the adsorbed mass onto the planar surfaces were recorded at different temperatures.     

Lens epithelial cell response to atmospheric pressure plasma modified poly(methylmethacrylate) surfaces

Selective control of cellular response to polymeric biomaterials is an important consideration for many ocular implant applications. In particular, there is often a need to have one surface of an ophthalmic implant capable of promoting cell attachment while the other needs to be resistant to this effect. In this study, an atmospheric pressure dielectric barrier discharge (DBD) has been used to modify the surface region of poly(methyl methacrylate) (PMMA), a well established ocular biomaterial, with the aim of promoting a controlled response to human lens epithelial cells (LEC) cultured thereon. The DBD plasma discharge environment has also been employed to chemically graft a layer of poly(ethylene glycol) methyl ether methacrylate (PEGMA) onto the PMMA and the response to LEC likewise determined. Two different molecular weights of PEGMA, namely 1000 and 2000 MW were used in these experiments. The LEC response to DBD treated polystyrene (PS) samples has also been examined as a positive control and to help to further elucidate the nature of the modified surfaces. The LEC adhered and proliferated readily on the DBD treated PMMA and PS surfaces when compared to the pristine polymer samples which showed little or no cell response. The PMMA and PS surfaces that had been DBD grafted with the PEGMA₁₀₀₀ layer were found to have some adhered cells. However, on closer inspection, these cells were clearly on the verge of detaching. In the case of the PEGMA₂₀₀₀ grafted surfaces no cells were observed indicating that the higher molecular weight PEGMA has been able to attain a surface conformation that is capable of resisting cell attachment in vitro.     

Release dynamics of tetracycline from a loaded semi-interpenetrating polymeric material of polyvinyl alcohol and poly(acrylamide-co-styrene)

A semi-interpenetrating polymer network (IPN) of polyvinyl alcohol (PVA) and poly(acrylamide-co-styrene) (PAMS) was prepared and its potential for controlled release of tetracycline was assessed. The IPN was characterized by IR spectral analysis and network parameters such as the average molecular weight between crosslinks (M_{_c}), crosslink density (q) and number of elastically effective chains (V_{_e}) were evaluated. The influence of various experimental conditions such as different percent loadings, composition of the IPNs, thickness of the loaded device, pH and nature of the release medium were investigated on the release profiles of the drug. Various kinetic constants such as the diffusional exponent (n), diffusion constant (D) and penetration velocity (v) were evaluated for different release processes and based on the dynamic release data, an analysis of transport mechanisms of tetracycline was made using Fick's equations.     

Spectroscopic study of poly(3-alkylthiophenes) electrochemically synthesized in different conditions

In this work, poly(3-alkylthiophenes) films were synthesized electrochemically in acetonitrile with LiClO₄ or Et₄NBF₄ at 5 or 18 °C. The films were deposited on platinum plates, and the polymer as-prepared was referred to as-oxidized. The as-reduced polymer was obtained by subjecting the as-oxidized product to ?1.70 V for 1 min. These various products were characterized by cyclic voltammetry, reflectance UV–Vis and Raman spectroscopy, and the results were used to estimate the ionization potential (I _P), electron affinity (E.A.) and energy gap (E _g) parameters. This study was possible because the Raman spectra demonstrated three structures (aromatic, radical cation and dication segments) which formed the P3MT and P3OT polymer chains.     

单分散聚甲基丙烯酸乙酯的制备与性能研究

活性阴离子聚合为聚合物分子设计和合成提供了一种有效方法.以1,1二苯基己基锂(DPHLi)为引发剂,添加LiClO4络合剂,采用活性阴离子聚合体系制备了单分散聚甲基丙烯酸乙酯(PEMA).考察了聚合温度、引发剂、添加剂等工艺参数对聚合反应的影响规律,并研究了不同pH值聚甲基丙烯酸乙酯的降解性能.     

Synthesis and photoelectric property of poly (3-octylthiophene)/titanium dioxide nano-composite material

A conducting polymer composite, poly (3-octylthiophene)/titanium dioxide nano-composite was first synthesized through the ultrasonic method. The results from X-ray diffraction, X-ray photoelectron spectroscopy and infrared spectroscopy show that there is chemical interaction in the composite, which indicates that TiO₂ was successfully coated by poly (3-octylthiophene) molecules. The energy gap of the poly (3-octylthiophene)/titanium dioxide composite is lower to 0.65 eV; and it also shows that the optical performance of the new material is far superior than POT or TiO₂ separately, by Ultraviolet–visible spectra and fluorescence spectroscopy.     

A new crystal morphology of straight-stalk dendrites in blends of poly(butylene adipate) with amorphous poly(vinyl acetate)

Discontinuity in crystallization rates and a new and unusual morphology consisting of thickened straight-stalks crystal lamellae with also straight branches radiating out from a common nucleus were observed in blends of poly(vinyl acetate) (PVAc) with poly(1,4-butylene adipate) (PBA). The discontinuity in the crystal growth and mechanisms of straight-dendrite morphology of the PVAc/PBA blends were analyzed using polarized-light optical microscopy (POM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD). The discontinuity in crystallization rate and dendritic morphology occurred only at or near PVAc/PBA 10/90 blend composition upon crystallization at high-temperature regimes of T_c = 30-33 °C. By comparison, when crystallized at the same temperatures, PVAc/PBA blends of amorphous polymer loading greater than 15% or the neat PBA (amorphous polymer loading = 0) developed no dendrites but only typical Maltese-cross spherulites. Mechanism of straight dendrites in the blends is preliminarily expounded. Detailed interpretation requires further analyses.     

Chemical synthesis of hydroxyapatite/poly(ε-caprolactone) composites

Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂)—biodegradable polymer composites as bone replacement scaffolds were synthesized by a colloidal non-aqueous precipitation technique at room temperature. The starting materials used for synthesizing hydroxyapatite (HA) were Ca(NO₃)₂·4H₂O and H₃PO₄ with a Ca/P ratio of 1.67 while poly(ε-caprolactone) (PCL) was used as the biodegradable polymer. The composites were prepared containing up to 34.5 wt.% HA and PCL polymer without any evidence of phase separation. This paper describes, the synthesis and structure of the HA/PCL composites. In addition, the pH changes during precipitation, the yield of the chemical reaction, and the possible existence of any bond between the ceramic and the polymer including the microstructure of the composites were studied. Finally, the mechanical and thermal properties of the composites were investigated. The results of these studies are described and discussed.     

Atmospheric pressure plasma liquid deposition of copper nanoparticles on poly(4-vinylpyridine)-grafted-poly(tetrafluoroethylene) surface and their autocatalytic properties

We demonstrate catalyst-free electroless deposition of copper on a poly(4-vynylpyrridine)-grafted-poly(tetrafluoroethylene) surface. The principle of this process relies on deposition of an organo-copper(II) precursor film on the functionalized polymer surface and on subsequent plasma-assisted reduction of the copper ion to form nanoparticles. A polymer surface densely and homogeneously seeded with copper nanoparticles enable to initiate autocatalytic electroless deposition of copper layer without need for any prior sensitizing the surface with conventionally used SnCl₂ and Pd species.     

Structural and magnetodielectric properties of poly(vinylidene-fluoride)-[0.8(Bi0.5Na0.5)TiO3-0.2CoFe2O4] polymer composite films

Composite thick films of xPoly(vinylidene-fluoride)-(1−x)[0.8(Bi_0.5Na_0.5)TiO₃-0.2CoFe₂O₄] with x = 0.1, 0.2, 0.3 and 0.4 were synthesized by hot press method. X-ray diffraction pattern of the composite films indicate the existence of distinct peaks of poly(vinylidene-fluoride), (Bi_0.5Na_0.5)TiO₃ and CoFe₂O₄ phases. The value of dielectric loss and saturation magnetization of polymer composite films decrease with increase in poly(vinylidene-fluoride) content. The magnetodielectric effect of the polymer composite films was found to improve with increasing poly(vinylidene-fluoride) content. The linear fitting of Δε ∼ γM² gives the value of magnetoelectric interaction coefficient (γ) of polymer composite films.     

Synthesis and photoelectric property of poly(3-octylthiophene)/ferric oxide complexes

Ferric oxide was prepared by the supercritical fluid drying (SCFD) method. A conducting polymer composite, poly(3-octylthiophene)/ferric oxide (POT/Fe₂O₃) was first synthesized through the chemical method. X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), and Infrared spectroscopy (IR) show that there is a chemical interaction in the composite, which indicates that Fe₂O₃ was successfully coated by poly(3-octylthiophene) molecules. The energy gap of the poly(3-octylthiophene)/ferric oxide composite is lower at 0.448 eV, which also shows that the optical performance of the new material is far superior to POT or Fe₂O₃ separately, by Ultraviolet–Visible spectra (UV–Vis) and fluorescence spectroscopy (PL). Solar cell was sensitized by POT/Fe₂O₃. A solar-to-electric energy conversion efficiency of 0.258% was attained with the system.