Vinyl Monomer Based Polyperoxides as Potential Initiators for Radical Polymerization: An Exploratory Investigation with Poly(.alpha.-methylstyrene peroxide)

We describe the use of poly(alpha-methylstyrene peroxide) (P alpha MSP), an alternating copolymer of alpha-methylstyrene and oxygen, as initiator for the radical polymerization of vinyl monomers. Thermal decomposition of P alpha MSP in 1,4-dioxane follows first-order kinetics with an activation energy (E(a)) of 34.6 kcal/mol. Polymerization of methyl methacrylate (MMA) and styrene using P alpha MSP as an initiator was carried out in the temperature range 60-90 degrees C. The kinetic order with respect to the initiator and the monomer was close to 0.5 and 1.0, respectively, for both monomers. The E(a) for the polymerization was 20.6 and 22.9 kcal/mol for MMA and styrene, respectively. The efficiency of P alpha MSP was found to be in the range 0.02-0.04. The low efficiency of P alpha MSP was explained in terms of the unimolecular decomposition of the alkoxy radicals which competes with primary radical initiation. The presence of peroxy segments in the main chain of PMMA and polystyrene was confirmed from spectroscopic and DSC studies. R(i)'/2I values for P alpha MSP compared to that of BPO at 80 degrees C indicate that P alpha MSP can be used as an effective high-temperature initiator.

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.

Phase Separation in Binary Nearly-Hard-Sphere Colloids: Evidence for the Depletion Force

A binary aqueous suspension of large (L) and small (S) nearly-hard-sphere colloidal polystyrene spheres is shown to segregate spontaneously into L-rich and S-rich regions for suitable choices of volume fraction and size ratio. This is the first observation of such purely entropic phase separation of chemically identical species in which at least one component remains fluid. Simple theoretical arguments are presented to make this effect plausible.

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.

Synthesis of epoxy-terminated polymers by radical polymerization using alpha-(t-butylperoxymethyl)styrene as chain transfer agent

Epoxy-terminated polystyrene has been synthesized by radical polymerization using alpha-(t-butylperoxymethyl) styrene (TPMS) as the chain transfer agent. The chain transfer constants were found to be 0.66 and 0.80 at 60 and 70 degrees C, respectively. The presence of epoxy end groups was confirmed by functional group modification of epoxide to aldehyde by treatment with BF3.Et(2)O. Thermal stability of TPMS was followed by differential scanning calorimetry and iodimetry. Thermal decomposition of TPMS in toluene follows first order kinetics with an activation energy of 23 kcal/mol. (C) 1996 John Wiley & Sons, Inc.

Some observations on the ignition of composite solid propellants

Heat-up times derived from studies on the ignition characteristics of a few model composite solid propellants, containing polystyrene, carboxy-terminated polybutadiene, plasticised polyvinyl chloride and polyphenol formaldehyde as binders, show that they are directly proportional to the mass of the sample and inversely proportional to the hear flux. Propellant weight-loss prior to ignition and high pressure ignition temperature data on the propellants, ammonium per chlorate, and binders show that the ignition is governed by the gasification of the binder pyrolysis products. The activation energy for the gasification of the pyrolysed polymer products corresponds to their ignition behaviour suggesting that propellant ignition is controlled by the binder.

Lasing in active, sub-mean-free path-sized systems with dense, random, weak scatterers

We report enhanced emission and gain narrowing in Rhodamine 590 perchlorate dye in an aqueous suspension of polystyrene microspheres. A systematic experimental study of the threshold condition for and the gain narrowing of the stimulated emission over a wide range of dye concentrations and scatterer number densities showed several interesting features, even though the transport mean free path far exceeded the system size. The conventional diffusive-reactive approximation to radiative transfer in an inhomogeneously illuminated random amplifying medium, which is valid for a transport mean-free path much smaller than the system size, is clearly inapplicable here. We propose a new probabilistic approach for the present case of dense, random, weak scatterers involving the otherwise rare and ignorable sub-mean-free-path scatterings, now made effective by the high gain in the medium, which is consistent: with experimentally observed features. (C) 1997 Optical Society of America.

On the water-induced critical double point in a polymer solution: the role of isotopic substitution

This paper examines the effect of substitution of water by heavy water in a polymer solution of polystyrene (molecular weight = 13000) and acetone. A critical double point (CDP), at which the upper and the lower partially-miscible regions merge, occurs at nearly the same coordinates as for the system [polystyrene + acetone + water]. The shape of the critical line for [polystyrene + acetone + heavy water] is highly asymmetric. An explanation for the occurrence of the water-induced CDP in [polystyrene + acetone] is advanced in terms of the interplay between contact energy dissimilarity and free-volume disparity of the polymer and the solvent. The question of the possible existence of a one-phase hole in an hourglass phase diagram is addressed in [polystyrene + acetone + water]. Our data exclude such a possibility.

Correlated conformation and charge transport in multiwall carbon nanotube-conducting polymer nanocomposites

The strikingly different charge transport behaviours in nanocomposites of multiwall carbon nanotubes (MWNTs) and conducting polymer polyethylenedioxythiophene-polystyrene-sulfonic-acid (PEDOT-PSS) at low temperatures are explained by probing their conformational properties using small-angle x-ray scattering (SAXS). The SAXS studies indicate the assembly of elongated PEDOT-PSS globules on the walls of nanotubes, coating them partially, thereby limiting the interaction between the nanotubes in the polymer matrix. This results in a charge transport governed mainly by small polarons in the conducting polymer despite the presence of metallic MWNTs. At T > 4 K, hopping of the charge carriers following one-dimensional variable range hopping is evident which also gives rise to a positive magnetoresistance (MR) with an enhanced localization length (similar to 5 nm) due to the presence of MWNTs. However, at T < 4 K, the observation of an unconventional positive temperature coefficient of resistivity is attributed to small polaron tunnelling. The exceptionally large negative MR observed in this temperature regime is conjectured to be due to the presence of quasi-1D MWNTs that can aid in lowering the tunnelling barrier across the nanotube-polymer boundary resulting in large delocalization.

SEC-MALDI-TOF mass spectral characterization of a hyperbranched polyether prepared via melt transetherification

An AB(2) monomer, 1-(2-hydroxyethoxy)-3,5-bis-(methoxymethyl)-2,4,6-trimethylbenzene, was synthesized from mesitol and melt-polycondensed in the presence of an acid catalyst via a transetherification process at 145-150 degreesC to yield a soluble, moderately high molecular weight hyperbranched polyether. The degree of branching in the polymer was calculated to be 0.78 by a comparison of its NMR spectrum with that of an appropriately designed model compound. The weight-average molecular weight of the hyperbranched polymer was determined to be 64,600 (weight-average molecular weight/number-average molecular weight = 5.2) by size exclusion chromatography (SEC) in CHCl3, with polystyrene standards. The origin of the broad molecular weight distribution, which could either be intrinsic to such hyperbranched structures or be due to structural heterogeneity, was further probed by the fractionation of the samples by SEC and by the subjection of each fraction to matrix-assisted laser desorption/ionization time-of-flight mass spectral analysis. The mass spectral analysis suggested the presence of two primary types of species: one corresponding to the simple branched structure and the other to macrocyclics. Interestingly, from the relative intensities of the two peaks, it was apparent that cyclization became favorable at higher conversions in the melt transetherification process. (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.

Threshold-like features in the magnetic response of iron-filled multi-walled carbon nanotube and polymer composite

The magnetic properties of iron-filled multi-walled carbon nanotubes dispersed in polystyrene (Fe-MWNT/PS) have been investigated as a function of Fe-MWNT concentration (0.1-15 wt%) from 300 to 10 K. Electron microscopy studies indicate that Fe nanorods (aspect ratio similar to 5) remain trapped at various lengths of MWNT and are thus, prevented from oxidation as well as aggregation. The magnetization versus applied field (M-H loop) data of 0.1 wt% of Fe-MWNTs in PS show an anomalous narrowing at low temperatures which is due to the significant contribution from shape anisotropy of Fe nanorods. The remanence shows a threshold feature at 1 wt%. The enhanced coercivity shows a maximum at 1 wt% due to the dominant dipolar interactions among Fe nanorods. Also the squareness ratio shows a maximum at 1 wt%.

Ultrasonic degradation of butadiene, styrene and their copolymers

Ultrasonic degradation of commercially important polymers, styrene-butadiene (SBR) rubber, acrylonitrile-butadiene (NBR) rubber, styrene-acrylonitrile (SAN), polybutadiene rubber and polystyrene were investigated. The molecular weight distributions were measured using gel permeation chromatography (GPC). A model based on continuous distribution kinetics approach was used to study the time evolution of molecular weight distribution for these polymers during degradation. The effect of solvent properties and ultrasound intensity on the degradation of SBR rubber was investigated using different pure solvents and mixed solvents of varying volatility and different ultrasonic intensities. (C) 2011 Elsevier B.V. All rights reserved.

High emission currents and low threshold fields in multi-wall carbon nanotube-polymer composites in the vertical configuration

In this work, we present field emission characteristics of multi-wall carbon nanotube (MWCNT)-polystyrene composites at various weight fractions along the cross-section of sample. Scanning electron microscope images in cross-sectional view reveal that MWCNTs are homogeneously distributed across the thickness and the density of protruding tubes can be scaled with weight fraction of the composite film. Field emission from composites has been observed to vary considerably with density of MWCNTs in the polymer matrix. High current density of 100 mA/cm(2) was achieved at a field of 2.2 V/lm for 0.15 weight fraction. The field emission is observed to follow the Fowler-Nordheim tunneling mechanism, however, electrostatic screening is observed to play a role in limiting the current density at higher weight fractions. (C) 2012 American Institute of Physics. [doi:10.1063/1.3685754]

Electron field emission from reduced graphene oxide on polymer film

Field emission of reduced graphene oxide coated on polystyrene film is studied in both parallel and perpendicular configurations. Low turn-on field of 0.6 V/lm and high emission current density of 200 mA/cm(2) are observed in perpendicular configuration (along the cross section), whereas a turn-on field of 6 V/lm and current density of 20 mu A/cm(2) are obtained in parallel configuration (top surface). The emission characteristics follow Fowler-Nordheim (FN) tunneling and the values of enhancement factor estimated from FN plots are 5818 (perpendicular) and 741 (parallel). Furthermore, stability and repeatability of the field emission characteristics in perpendicular configuration are presented. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4788738]