Memory effect in polymer brushes containing pendant carbazole groups

Poly(9-(2-(4-vinyl(benzyloxy)ethyl)-9H-carbazole)) (PVBEC) brushes, have been successfully prepared on the silicon surfaces via surface-initiated atom transfer radical polymerization (ATRP). Conductance switching at a voltage of about −2.1 V is observed in the memory device based on the PVBEC brushes. The fabricated device shows the good memory characteristics as the ON/OFF current ratio up to 10⁵, and enduring 10⁶ read cycles under −1 V pulse voltages. Compared with those of the conventional Si/PVBEC/Al device fabricated by spin-coating, the switch voltage is lower and the ON/OFF current ratio is higher in the volatile Si-g-PVBEC/Al memory device.     

New insights into structural and electrochemical properties of anisotropic polymer electrolytes

The inter-relationship between the orthogonal alignment of polymer helices and improvement of lithium-transport properties of polymer electrolytes has been determined by scanning electron microscopy, differential-scanning calorimetry and dielectric spectroscopy. It is suggested that ordering of the polymer electrolyte accompanied by increased conduction properties is achieved by mutual coordination of local dipole moments of the polar CH₂-CH₂-O units during casting under a magnetic field.     

Synthesis and characterizations of a polyimide containing a triphenylamine derivative as an interlayer in polymer light-emitting diode

Polyimide containing triphenylamine derivative (TPD-PI) was synthesized to prepare a polymer interlayer having insolubility in common nonpolar solvent for light-emitting polymers. N,N′-diphenyl-N,N′-bis(4-aminophenyl)-1,1-biphenyl-4,4′-diamine, as a new triphenylamine-containing diamine monomer, was synthesized by the palladium-catalyzed amination reaction between 4-nitrodiphenylamine and 4,4′-dibromobiphenyl and subsequent reduction of the nitro-intermediate. The TPD-PI was prepared from the synthesized diamine monomer and 4,4′-(hexafluoropropylidene)-diphthalic anhydride by the standard two-step polymerization method, which involved ring-opening polymerization and subsequent cyclodehydration. The structures and properties of the monomer and the resulting polyimide were characterized with ¹H and ¹³C NMR, elemental analysis, gel permeation chromatography, UV-visible spectroscopy, etc. The TPD-PI is readily soluble in aprotic polar solvents such as N-methyl-2-pyrrolidinone and N,N-dimethylformamide and insoluble in nonpolar solvents such as toluene and xylene. The highest occupied molecular orbital (HOMO) level of the TPD-PI was measured to be 5.5 eV by a photoelectron spectrometer in air, and the band gap was calculated as 3.1 eV from the onset of UV-vis spectrum. The polymer light-emitting diode with the thin TPD-PI layer between a hole injection layer and an emitting polymer layer was fabricated to examine the performance of the polyimide as an polymer interlayer. Although the luminous efficiency of the device is lowered by the introduction of the TPD-PI interlayer, the lifetime of the device is improved.     

Electrical properties of polymer nanocomposites containing rod-like nanofillers

We present an in-depth critical review of major experimental, simulation, and theoretical work in the field of conducting polymer nanocomposites containing rod-like particles such as carbon nanotubes and metal nanowires. These are a versatile class of materials that are of interest for a wide range of applications. Commercialization of various classes of conducting polymer nanocomposites is growing, yet achieving their full technological potential will hinge on the ability to engineer composites with controllable and well-defined properties, as well as aggressive exploration of new application areas. Thus, the focus of this review is to clarify key structure–property relationships, and to discuss the major gaps and greatest opportunities in the field.     

Fluorescence probe for microenvironments: On the fluorescence properties of p-N,N-dialkylaminobenzylidenemalononitrile in polymer matrices

The effect of an alkyl group (R) in a series of poly(alkylmethacrylate) and poly(alkylacrylate) polymers on the fluorescence properties of p-N,N-dialkylaminobenzylidenemalononitrile derivative, 1, has been studied. The fluorescence emission maximum shifts to the blue and the fluorescence quantum yield decreases as the chain length of R increases. These results are interpreted in terms of a model which assumes that the location of 1 is dependent on R and the change in quantum yield reflects the difference in free volume or polymer chain flexibility in various locations in these polymers.     

Modelling of gas transport properties of polymer electrolytes containing various amounts of water

Gas transport properties of three different PEO-based polymer electrolytes containing PEO sulfonic acid dianions, cations and 90 or 35 or 0 wt% of water are studied by atomistic molecular modelling. The gas molecules studied are H₂, O₂, CO₂ and CH₄. The pair correlation functions are calculated to see the distribution of the gas molecules in the systems. The diffusion coefficients of the gas molecules are calculated and found to be dependent of the amount and distribution of the water in the system and of the size of the penetrant. The motion of the gas molecules is explored in each system. The amount and distribution of water has a strong effect on the motion of the gas molecules. The ionic copenetrants seem not to have any direct influence on the diffusion of the gas molecules in the polyelectrolyte materials. However, ions have an effect on the distribution of the water in the polyelectrolyte materials.     

Solvent size effect on the static and dynamic properties of polymer chains in athermal solvents

The static and dynamic properties of polymer chains in athermal solvents with different sizes are studied by molecular dynamics method. With increasing solvent size, the radius of gyration and the diffusion coefficient of the polymer decay fast until a critical solvent size is reached. For the polymer diffusion coefficients, this decay only depends on the solvent size; while for the radius of gyration of polymers, this decay depends on both solvent size and the length of the polymers. The increase of solvent size also makes the polymer tend to be thicker ellipsoid until a critical solvent size is reached. The static scaling exponent of the polymer also shows the solvent size dependence. Moreover, four regions are identified where the polymers show different dynamic behaviors according to the dynamic structure factors of the polymer.     

Effect of sample size on solvent extraction for detecting cocontinuity in polymer blends

The effect of sample size on the results of solvent extraction measurements for detecting cocontinuity in polymer blends was investigated. Poly(ethylene oxide)/polystyrene (PEO/PS) blend samples of several thicknesses were analyzed by removing the PEO phase using water extraction. The experimental degree of continuity was shown to have a linear dependence on the reciprocal of sample thickness. A model is proposed to explain this dependence and to allow the bulk or true degree of continuity to be determined. Measurement of the bulk degree of continuity is useful for understanding properties of cocontinuous polymer blends such as electrical conductivity, impact strength, or tensile strength.     

Recent advances in polymer reaction engineering: Modeling and control of polymer properties

Complex reaction kinetics and mechanisms, physical changes and transport effects, non-ideal mixing, and strong process nonlinearity characterize polymerization processes. Polymer reaction engineering is a discipline that deals with various problems concerning the fundamental nature of chemical and physical phenomena in polymerization processes. Mathematical modeling is a powerful tool for the development of process understanding and advanced reactor technology in the polymer industry. This review discusses recent developments in modeling techniques for the calculation of polymer properties including molecular weight distribution, copolymer composition distribution, sequence length distribution and long chain branching. The application of process models to the design of model-based reactor optimizations and controls is also discussed with some examples. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

含氮磷高分子肥料的制备和结构研究

水溶性合成高分子聚合物能被微生物分解,是一种优良的土壤改良剂,并对土壤营养元素有良好的吸附作用,可减少元素流失,提高肥效。合成了一种营养元素高分子缓释化肥,将含氮磷的降解水溶性高分子材料引入到化肥领域,并通过实验研究不同的反应工艺条件对高分子肥料结构和含氮磷肥效的影响。     

Photochromic nanocomposite films of mononitrosyl complexes embedded in polymer matrices

New photochromic nanocomposite films based on mononitrosyl ruthenium complex [RuCl(NO)py₄]²⁺ have been synthesized by dispersion in polymer matrices. Infrared study under irradiation reveals that the composites present very high population of metastable state (≈45%). Nanoparticles of molecular complex stabilized in different matrices have been observed by transmission electron microscopy.     

Synthesis and solution properties of a new pH-responsive polymer containing amino acid residues

The amine salt, N,N-diallyl-N-carboethoxymethylammonium chloride was cyclopolymerized in water using ammonium persulfate as an initiator to afford a cationic polyelectrolyte which on acidic hydrolysis of the pendant ester groups gave the corresponding cationic acid salt (CAS). The CAS was converted into an anionic polyelectrolyte (APE) and polybetaine (PB). The solution properties of the APE having two basic functionalities were investigated in detail by potentiometric and viscometric techniques. Basicity constants of the amine as well as the carboxylate groups in APE are ‘apparent’ and as such follow the modified Henderson-Hasselbalch equation; as the degree of protonation (α) of the whole macromolecule increases, the protonation of the amine nitrogens and carboxylate groups becomes increasingly more difficult and easier, respectively. While the APE, PB and CAS were found to be soluble in salt-free water, the corresponding PB and CAS of the SO₂ copolymers of the amine salt 1 were found to be insoluble in water.     

一种高分子两性含氟表面活性剂的合成及其溶液性质

以甲基丙烯酸三氟乙酯(TFEMA)、丙烯酸(AA)、氯丙烯(AC)、三甲胺(TMA)为原料,合成了一种高分子两性含氟表面活性剂,通过红外光谱对该表面活性剂进行了结构表征.测试了该两性含氟表面活性剂的溶液性质,结果表明,该表面活性剂水溶液的等电点为pH 4.5～7.5、cmc为4.0×10-2g/L、γcmc为59.1 mN/m、泡沫稳定性为0.89.两性含氟表面活性剂含强碱性N原子,pH对表面活性剂的临界胶束浓度有一定影响,但对泡沫性能影响不大.     

Self-association and microenvironment of random amphiphilic copolymers of sodium N-acryloyl-l-valinate and N-dodecylacrylamide in aqueous solution

The present paper reports on the syntheses and association behavior of two random copolymers of sodium N-acryloyl-l-valinate and N-dodecylacrylamide in buffered (pH 8.0) aqueous solution containing 0.1 M NaCl. Surface tension and viscosity results showed pronounced amphiphilic nature of the copolymers in aqueous solution at pH 8.0. Steady-state fluorescence studies using pyrene and N-phenyl-1-naphthylamine as probe molecules suggested microdomain formation through interpolymer association above a critical concentration called ‘critical aggregation concentration’ (CAC) as low as ca. 10⁻³ g L⁻¹. The local polarity of the hydrophobic domain formed in aqueous solution was estimated from steady-state fluorescence spectra of pyrene. The microviscosity of the domains was evaluated using 1,6-diphenyl-1,3,5-hexatriene as a fluorescent probe using steady-sate fluorescence depolarization and time-resolved fluorescence method. Dynamic light scattering technique was performed over a wide range of concentration to determine hydrodynamic size of the aggregates. It was observed that both copolymers retain rather open conformation in dilute solutions having polymer concentrations less than CAC. However, with increase in concentration the intermolecular association becomes favorable towards the formation of more compact aggregates. The transmission electron microscopic images of both copolymers at a concentration above CAC revealed spherical aggregates of uniform diameter (∼50 nm).     

A quantum-chemical study on the boron centers in nonaqueous electrolyte solutions and polymer electrolytes

Quantum-chemical calculations were performed to study the effect of Lewis acid centers introduced to liquid or polymer electrolytes as boric acid esters. Particular attention has been paid to the modeling of solvent effects on ion–ion and anion-acid center interactions. Calculated complexation energies for lithium salts and polymerizable boric acid esters with diols in different solvents were analyzed and related to available conductivity data.     

Electrochemical synthesis,characterization and capacitive properties of novel thiophene based conjugated polymer

In this paper, a novel thiophene based monomer, 1-(pyren-1-yl)-2,5-di(thiophen-2-yl)-1H-pyrrole, PThP, was synthesized and characterized by ¹H NMR and ¹³C NMR spectroscopic methods. The electrochemical behavior and electropolymerization of this novel monomer were performed on pencil graphite electrode (PGE) by cyclic voltammetry. The effect of solvent, dopant, scan number and scan rate on the electropolymerization and properties of the conjugated polymer films were investigated. The capacitive properties of the poly(PThP) films were tested by electrochemical impedance spectroscopy (EIS). The highest specific capacitance value was calculated for the conjugated polymer modified PGE that was obtained in 0.1 M tetrabutylammonium perchlorate/dichloromethane solution for 30 cycles at 25 mV/s scan rate as 25.45 mF cm⁻². The surface morphologies of the conjugated polymer modified electrodes were determined by scanning electron microscopy (SEM).     

Glass transitions and interactions in polymer blends containing poly(4-hydroxystyrene) brominated

The miscibility and interactions of binary blends of poly(4-hydroxystyrene) brominated (P4HSBR) with poly(?-caprolactone) (PCL), poly(vinyl acetate) (PVA) and poly(vinyl methylether) (PVME) are investigated by means of differential scanning calorimetry (DSC). Glass transition temperatures, T_gs, are used to assess the miscibility of these systems. All of them were found to be miscible over the whole composition range. T_gs of the blends are lower than Fox predictions, in contrast to the results previously obtained for systems involving poly(4-hydroxystyrene) (P4HS). The melting of PCL in the blends was studied. From the melting temperature depression of PCL in the blends the polymer-polymer interaction parameter was obtained and compared with the ones obtained for P4HS/PCL and poly(4-hydroxystyrene-co-methoxystyrene) (P4HSM)/PCL systems. The best interactions are achieved in P4HS/PCL and the bromination or methoxylation of the P4HS worsen the interactions with the PCL. The presence of a cusp in the T_g-composition curve was analysed in terms of the Kovacs' theory in systems with P4HS and P4HSBR.     

Direct measurement of polymer segment orientation and distortion in shear: semi-dilute solution behavior

The shear induced backbone segment orientation and deformation of the polymeric chromophore diacetylene 4-butoxycarbonylmethylurethane (4BCMU) in semi-dilute solution has been measured with an extended dichroism technique. At low shear rates the random coil, visco-elastic polymer shows orientation in the flow direction. At higher shear rates a reduction in the average conjugation length is observed with an increase in the number of segments orienting perpendicular to the flow direction. Novel behavior, which is not consistent with standard models, is observed for this visco-elastic polymer at high shear rates. The results presented are discussed in view of prior experimental and theoretical work.     

A review on synthesis and properties of polymer functionalized graphene

This review highlights the functionalization chemistry of graphene with polymers by both covalent and non-covalent approaches. Due to the strong cohesive interactions graphene platelets agglomerate, causing difficulty to attain its optimum properties. The covalent functionalization is illuminated both from ‘grafting to’ and ‘grafting from’ techniques discussing the merits and demerits of the processes. The controlled free radical polymerization techniques used for this purpose e.g. ATRP, SET–LRP and RAFT etc. are discussed along with the conventional free radical polymerization. We have also noted the various approaches used in non-covalent functionalization e.g. π–π, H-bonding and hydrophobic interactions. These functionalized graphenes show good and stable dispersion facilitating composite formation with commodity plastics enhancing it's mechanical, thermal and conductivity properties. The optoelectronic properties of these functionalized graphene are interesting to fabricate sensors, photovoltaics, supercapacitors etc. A short account of the properties of these modified graphenes is also embodied with an emphasis on different area where future developments are expected.     

Manufacture and properties of a structural synthetic polymer fiber‐containing nanoclay for concrete reinforcement

This study established the optimum conditions for structural synthetic polymer fiber manufacture to make a fiber having excellent tensile strength. Two polypropylene resins, differing in their melt indices, and four different draw ratio values were investigated, that is, 6, 7, 8, and 9, to establish which had the greatest influence on tensile strength. The tensile strength and the modulus of elasticity were measured for the manufactured fibers. In addition, nanoclay was added to polypropylene and polyolefin fibers to improve the mechanical properties of fiber‐reinforced cementitious composites. The optimum mixing ratio and draw ratio of the synthetic polymer fibers were established prior to nanoclay addition. Fiber mixing ratios (polypropylene:polyethylene) of 100:0, 90:10, and 85:15, a draw ratio of 8, and nanoclay additions of 1, 3, and 5 wt% were studied. The modulus of elasticity improved with nanoclay addition, while the tensile strength remained almost unchanged, except in the case of 100% polypropylene with 5 wt% nanoclay. POLYM. COMPOS., 34:1698–1709, 2013. © 2013 Society of Plastics Engineers