The performance of poly(styrene)-block-poly(2-vinyl pyridine)-block- poly(styrene) triblock copolymers as pH-driven actuators

Poly(styrene)-block-poly(2-vinyl pyridine)-block-poly(styrene) (PS-b-P2VP-b-PS) triblock copolymers were synthesised by anionic polymerisation. Thick films were cast from solution and their structure analysed by small angle X-ray scattering (SAXS). Longer annealing times led to more ordered structures whereas short evaporation times effectively "lock" the polymer chains in a disordered state by vitrification. Well-ordered structures not only provide an isotropic network, which reduces localised stress within the material, but are also essential for fundamental studies of soft matter because their activity on the molecular scale must be analysed and understood prior to their use in technological applications. Well-characterised PS-b-P2VP-b-PS materials have been coupled to a pH-oscillating reaction and their potential application as responsive actuators is discussed. This journal is © The Royal Society of Chemistry.

Effect of II‐VI Semiconductor Nanomaterials and Electron Irradiation on Polystyrene (PS) & Poly(ethylene‐co‐vinyl acetate) (EVA)

Organic-inorganic nanocomposites combine unique properties of both the constituents in one material. Among this group of materials, clay based as well as ZnO, TiO2 nanocomposites have been found to have diverse applications. Optoelectronic devices require polymerinorganic systems to meet certain desired properties. Dielectric properties of conventional polymers like poly(ethylene-co-vinyl acetate) (EVA) and polystyrene (PS) may also be tailor tuned with the incorporation of inorganic fillers in very small amounts. Electrical conductivity and surface resistivity of polymer matrices are found to improve with inorganic nanofillers. II-VI semiconductors and their nano materials have attracted material scientists because of their unique optical properties of photoluminescence, UV photodetection and light induced conductivity. Cadmium selenide (CdSe), zinc selenide (ZnSe) and zinc oxide (ZnO) are some of the most promising members of the IIVI semiconductor family, used in light-emitting diodes, nanosensors, non-linear optical (NLO) absorption etc. EVA and PS materials were selected as the matrices in the present study because they are commercially used polymers and have not been the subject of research for opto-electronic properties with semiconductor nanomaterials

A poly(D,L-lactide) resin for the preparation of tissue engineering scaffolds by stereolithography

Porous polylactide constructs were prepared by stereolithography, for the first time without the use of reactive diluents. Star-shaped poly(D,L-lactide) oligomers with 2, 3 and 6 arms were synthesised, end-functionalised with methacryloyl chloride and photocrosslinked in the presence of ethyl lactate as a non-reactive diluent. The molecular weights of the arms of the macromers were 0.2, 0.6, 1.1 and 5 kg/mol, allowing variation of the crosslink density of the resulting networks. Networks prepared from macromers of which the molecular weight per arm was 0.6 kg/mol or higher had good mechanical properties, similar to linear high molecular weight poly(D,L-lactide). A resin based on a 2-armed poly(D,L-lactide) macromer with a molecular weight of 0.6 kg/mol per arm (75 wt%), ethyl lactate (19 wt%), photo-initiator (6 wt%), inhibitor and dye was prepared. Using this resin, films and computer-designed porous constructs were accurately fabricated by stereolithography. Pre-osteoblasts showed good adherence to these photocrosslinked networks. The proliferation rate on these materials was comparable to that on high molecular weight poly(D,L-lactide) and tissue culture polystyrene.

High-Pressure Kinetics of Vinyl Polyperoxides

This is the first report on studies carried out in detail on high-pressure oxygen copolymerization (> 50 psi) of the vinyl monomers styrene and alpha-methylstyrene (AMS). The saturation pressure of oxygen for AMS oxidation, hitherto obscure, is found to be 300 psi. Whereas the ease of oxidation is more favorable for styrene, the rate and yield of polyperoxide formation are higher for AMS. This is explained on the basis of the reactivity of the corresponding alkyl and peroxy radicals. Below 50 degrees C, degradation of the poly(styrene peroxide) formed is about 2.5 times less than that observed above 50 degrees C, so much so that it gives a break in the rate curve, and thereafter the rate is lowered. Normal free radical kinetics is followed before the break point, after which the monomer and initiator exponents become unusually high. This is interpreted on the basis of chain transfer to the degradation products. The low molecular weight of polyperoxides has been attributed to the (i) low reactivity of RO(2)(.) toward the monomer, (ii) chain transfer to degradation products, (iii) facile cleavage of O-O bond, followed by unzipping to nonradical products, and (iv) higher stability of the reinitiating radicals. At lower temperatures, (i) predominates, whereas at higher temperatures, chiefly (ii)-(iv) are the case.

A novel (main chain) (side chain) polymeric peroxide: Synthesis and initiating characteristics of poly(alpha-(tert-butylperoxymethyl)styrene peroxide)

A novel (main chain)-(side chain) vinyl polyperoxide, poly(alpha-(tert-butylperoxymethyl)styrene peroxide) (MCSCPP), an alternating copolymer of alpha-(tert-butylperoxymethyl)styrene (TPMS) and oxygen, has been synthesized by the oxidative polymerization of TPMS. The MCSCPP was characterized by H-1 NMR, C-13 NMR, IR, DSC, EI-MS, and GC-MS studies. The overall activation energy (E(a)) for the degradation of MCSCPP was found to be 27 kcal/mol. Formaldehyde and alpha-(tert-butylperoxy)acetophenone (TPAP) were identified as the primary degradation products of MCSCPP; TPAP was found to undergo further degradation. The side chain peroxy groups were found to be thermally more stable than those in the main chain. Polymerization of styrene in the presence of MCSCPP as initiator, at 80 degrees C, follows classical kinetics. The presence of peroxy segments in the polystyrene chain was confirmed by both H-1 NMR and thermal decomposition studies. Interestingly, unlike other vinyl polyperoxides, the MCSCPP initiator shows an increase in molecular weight with conversion.

Photoinitiating capabilities of vinyl polyperoxides and metamorphosis of block-into-block copolymer

This article describes the first comprehensive study on the use of a vinyl polyperoxide, namely poly(styrene peroxide) (PSP), an equimolar alternating copolymer of oxygen and styrene, as a photoinitiator for free radical polymerization of vinyl monomers like styrene. The molecular weight, yield, structure and thermal stability of polystyrene (PS) thus obtained are compared with PS made using a simple peroxide like di-t-butyl peroxide. Interestingly, the PS prepared using PSP contained PSP segments attached to its backbone preferably at the chain ends. This PSP-PS-PSP was further used as a thermal macroinitiator for the preparation of another block copolymer PS-b-PMMA by reacting PSP-PS-PSP with methyl methacrylate (MMA). The mechanism of block copolymerization has been discussed. (C) 1996 John Wiley & Sons, Inc.

Electrochemical co-deposition of bimetallic Pt-Ru nanoclusters dispersed on poly(3,4-ethylenedioxythiophene) and electrocatalytic behavior for methanol oxidation

Nanoclusters of bimetallic Pt-Ru are electrochemically deposited on conductive polymer, poly(3,4-ethylenedioxythiophene)(PEDOT), which is also electrochemically deposited on a carbon paper substrate. The bimetallic deposition is carried out in an acidic electrolyte consisting of chloroplatinic acid and ruthenium chloride at 0.0 V versus saturated calomel electrode (SCE) on PEDOT coated carbon paper. A thin layer PEDOT on a carbon paper substrate facilitates the formation of uniform, well-dispersed, nano clusters of Pt-Ru of mean diameter of 123 nm, which consist of nanosize particles. In the absence of PEDOT, the size of the clusters is about 251 nm, which are unevenly distributed on carbon paper substrate. Cyclic voltammetry studies suggest that peak currents of methanol oxidation are several times greater on PtRu-PEDOT electrode than on Pt-Ru electrode in the absence of PEDOT. (C) 2011 Elsevier B.V. All rights reserved.

Kinetics of thermal degradation of vinyl polyperoxides in solution

The thermal degradation of vinyl polyperoxides, poly(styrene peroxide, (PSP), poly(alpha-methylstyrene peroxide) (PAMSP) and poly(alpha-phenylstyrene pet-oxide) (PAPSP), was carried out at different temperatures in toluene. The time evolution of molecular weight distributions (MWDs) was determined by gel permeation chromatography (GPC). A continuous distribution model was used to evaluate the random chain degradation rate coefficients. The activation energies, determined from the temperature dependence of the rate coefficients, suggest that thermal degradation of polyperoxides is controlled by the dissociation of the O-O bonds in the backbone of the polymer chain. Among the three polyperoxides investigated, the thermal stability is the highest for PAPSP and the lowest for PAMSP. (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis, properties, and comparative analyses on the chain flexibility of an ultrastable vinyl polyperoxide

The most stable vinyl polyperoxide, namely, poly(indene peroxide) (PINDP), an alternating copolymer of indene and oxygen, was synthesized by the oxidative polymerization of indene. It was characterized by H-1-NMR and C-13-NMR, Fourier transform infrared, differential scanning calorimetry, direct pyrolysis mass spectrometry, and gas chromatography mass spectrometry studies. The overall activation energy for the degradation and the glass-transition temperature of PINDP were 47 kcal/mol and 327 K respectively, which were very high compared to those of other vinyl polyperoxides. (C) 2002 Wiley Periodicals, Inc.

A new polymeric flame retardant additive for vinyl polymers

Diethyl allyl phosphate (DEAP) monomer has been synthesized, and characterized, using H-1 NMR and direct ionization mass spectrometric (DI-MS) techniques. It was free-radically polymerized to yield the poly(diethyl allyl phosphate) (PDEAP). The direct pyrolysis-mass spectrometric (DP-MS) analysis of the PDEAP revealed that it undergoes thermal degradation to yield mainly the monomer. Utility of PDEAP as a potent flame-retardant additive in polystyrene (PS) and poly(methyl methacrylate) (PMMA) has also been established.

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Synthesis of novel star-like hyperbranched polymers with poly(amido amine) core and poly(L-lysine) shell

Hyperbranched poly(amido amine)s containing vinyl and hydroxyl groups were successfully synthesized via Michael addition polymerization of triacrylamide (TT) and 3-amino-1,2-propanediol (APD) with equal molar ratio in feed. H-1, C-13 and HSQC NMR techniques were used to clarify the structure of hyperbranched polymers and polymerization mechanism.

Facile synthesis of poly(o-phenylenediamine) microfibrils using cupric sulfate as the oxidant

A rapid, templateless, surfactantless approach is proposed to prepare microfibrils by simply mixing of aqueous cupric sulfate and o-phenylenediamine (oPD) solutions at room temperature. The as-prepared poly(o-phenylenediamine) (PoPD) microfibrils have been characterized by optical microscope, transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis) and X-ray diffraction (XRD).

Phase Behavior and self-assembly of poly[N-vinylformamide-co-(acrylic acid)] copolymers under highly acidic conditions

Copolymers of N-vinylformamide and acrylic acid were synthesized by conventional aqueous free-radical polymerization. The phase behavior of the copolymer solutions was investigated through the addition of hydrochloric acid and the variation of the temperature. With a moderate content of N-vinylformamide, the copolymers showed complex phase behaviors. Under low-acidity conditions, a suspending liquid was formed, whereas under high-acidity conditions, the random copolymers could assemble into round nanoparticles with a broad particle size distribution.