Optical properties of injection‐molded polystyrene scintillators. II. Distribution of dopants

The distribution of fluorescing dye solutes in scintillating tiles for the Tilecal/Atlas project is assessed, and a link between the homogeneity of the dopant distribution and the optical yield and nonuniformity is established. The effect of the injection‐molding parameters on the dye distribution is also analyzed, as well as the actual dye incorporation into the scintillators. This incorporation has been assessed with a set of experiments performed with laboratory samples with controlled amounts of additives and with samples obtained from injection‐molded scintillators. Differential scanning calorimetry has been used to characterize the raw material and to establish a link between the thermophysical properties and the processing conditions, and it is proven to be a quite appropriate technique. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2714–2718, 2003     

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (C_{tr, PEO‐I} = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and ¹H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

Atom transfer radical polymerization grafting of highly functionalized polystyrene and poly(4‐methylstyrene) macroinitiators with tert‐butyl acrylate

Two monodisperse graft copolymers, poly(4‐methylstyrene)‐graft‐poly(tert‐butyl acrylate) [number‐average molecular weight (M_n) = 37,500, weight‐average molecular weight/number‐average molecular weight (M_w/M_n) = 1.12] and polystyrene‐graft‐poly(tert‐butyl acrylate) (M_n = 72,800, M_w/M_n = 1.12), were prepared by the atom transfer radical polymerization of tert‐butyl acrylate catalyzed with Cu(I) halides. As macroinitiators, poly{(4‐methylstyrene)‐co‐[(4‐bromomethyl)styrene]} and poly{styrene‐co‐[4‐(1‐(2‐bromopropionyloxy)ethyl)styrene]}, carrying 40% of the bromoalkyl functionalities along the chain, were used. The dependencies of molecular parameters on monomer conversion fulfilled the criteria for controlled polymerizations. In contrast, the dependencies of monomer conversion versus time were nonideal; possible causes were examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2930–2936, 2002     

Thermal,mechanical, and morphological characterization studies of poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends with polystyrene and brominated polystyrene

The miscibility of the binary and ternary blends of poly(2,6‐dimethyl‐1,4‐phenylene oxide), brominated polystyrene, and polystyrene was investigated using a differential scanning calorimeter. The morphology of these blends was characterized by scanning electron microscopy. These studies revealed a close relation between the blend structure and its mechanical properties. The compatibilizing effect of poly(2,6‐dimethyl‐1,4‐phenylene oxide) on the miscibility of the polystyrene/brominated polystyrene blends was examined. It was found that poly(2,6‐dimethyl‐1,4‐phenylene oxide), which was miscible with polystyrene and partially miscible with brominated polystyrene, compatibilizes these two immiscible polymers if its contention exceeds 33 wt %. Upon the addition of poly(2,6‐dimethyl‐1,4‐phenylene oxide) to the immiscible blends of polystyrene/brominated polystyrene, we observed a change in the morphology of the mixtures. An improvement in the mechanical properties was noticed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 225–231, 2000     

Facile synthesis and characterization of star‐shaped polystyrene: self‐condensing atom transfer radical copolymerization of N‐[4‐(α‐bromoisobutyryloxy)phenyl]maleimide and styrene

BACKGROUND: Generation of stars around in situ formed cores provides a facile approach to star‐shaped polymers. Therefore the self‐condensing atom transfer radical copolymerization (SCATRCP) of N‐[4‐(α‐bromoisobutyryloxy)phenyl]maleimide (BiBPM) and a large excess of styrene (St) was investigated. RESULTS: BiBPM and St formed a charge transfer complex (CTC), which underwent the SCATRCP, leading to the branched core initiating the atom transfer radical polymerization of St, finally giving star‐shaped polystyrene (PS). Kinetic and structural study showed that a higher dosage of BiBPM resulted in an enhanced polymerization rate, a higher degree of branching and a larger number of short PS arms. Differential scanning calorimetry suggested that the glass transition temperature of the star‐shaped PS decreased with molecular weight. Melt rheometry showed that even a slightly branched architecture of the PS led to a significantly lower viscosity; both the melt flow index and the activation energy increased with the degree of branching. CONCLUSION: Due to the preferential consumption of BiBPM and formation of a CTC, even a very low dosage of BiBPM could lead to star‐shaped PS, which, in comparison with linear analogues, could possess much better melt fluidity. Copyright © 2008 Society of Chemical Industry     

Synthesis of block copolymers with thermodynamically compatible chain segments: di‐ and triblock copolymers of polystyrene and poly(2,6‐dimethyl‐1,4‐phenylene oxide)

Mono‐ and bifunctional poly(phenylene oxide) (PPO) macroinitiators for atom transfer radical polymerization (ATRP) were prepared by esterification of mono‐ and bishydroxy telechelic PPO with 2‐bromoisobutyryl bromide. The macroinitiators were used for ATRP of styrene to give block copolymers with PPO and polystyrene (PS) segments, namely PPO‐block‐PS and PS‐block‐PPO‐block‐PS. Various ligands were studied in combination with CuBr as ATRP catalysts. Kinetic investigations revealed controlled polymerization processes for certain ligands and temperature ranges. Thermal analysis of the block copolymers by means of DSC revealed only one glass transition temperature as a result of the compatibility of the PS and PPO chain segments and the formation of a single phase; this glass transition temperature can be adjusted over a wide temperature range (ca 100–199 °C), depending on the composition of the block copolymer. Copyright © 2005 Society of Chemical Industry     

Optical properties of modified epoxy resin with various oxime derivatives in the UV‐VIS spectral region

Optical absorbance measurements have been performed on the epoxy resin and the composites prepared by its modification with two different oxime derivatives (benzaldoxime and 2‐furaldoxime) in the wavelength interval of 190–680 nm by unpolarized light. Using the experimental absorbance data, dielectric constant and refractive index dispersion have been determined by means of standard oscillator fit procedure. Moreover, based on the dispersion analysis, direct and indirect band gap energies of the samples have been calculated. It is found that direct band energy for epoxy is nearly 3.49 eV, while its value for the oxime derivatives has been increased up to the 4.15 eV. Another important result to be pointed out is that the absorbance for the 2‐furaldoxime doped resin has been greatly increased in a respectively, narrow interval (～ 30 nm wide) in the UV region, while in the case for the benzaldoxime doped sample, a decreasing has been observed in the absorbance at the same region. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of novel polystyrene‐block‐polyurethane‐block‐polystyrene tri‐block copolymers through atom transfer radical polymerization

Background: Radical polymerization is used widely to polymerize more than 70% of vinyl monomers in industry, but the control over molecular weight and end group of the resulting polymers is always a challenging task with this method. To prepare polymers with desired molecular weight and end groups, many controlled radical polymerization (CRP) ideas have been proposed over the last decade. Atom transfer radical polymerization (ATRP) is one of the successful CRP techniques. Using ATRP, there is no report on the synthesis of polystyrene‐block‐polyurethane‐block‐polystyrene (PSt‐b‐PU‐b‐PSt) tri‐block copolymers. Hence this paper describes the method of synthesizing these tri‐block copolymers. To accomplish this, first telechelic bromo‐terminated polyurethane was synthesized and used further to synthesize PSt‐b‐PU‐b‐PSt tri‐block copolymers using CuBr as a catalyst and N,N,N,N″,N″‐pentamethyldiethylenetriamine as a complexing agent. Results: The ‘living’ nature of the initiating system was confirmed by linear increase of number‐average molecular weight and conversion with time. A semi‐logarithmic kinetics plot shows that the concentration of propagating radical is steady. The results from nuclear magnetic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry show that the novel PSt‐b‐PU‐b‐PSt tri‐block copolymers were formed through the ATRP mechanism. Conclusion: For the first time, PSt‐b‐PU‐b‐PSt tri‐block copolymers were synthesized through ATRP. The advantage of this method is that the controlled incorporation of polystyrene block in polyurethane can be achieved by simply changing the polymerization time. Copyright © 2007 Society of Chemical Industry     

Structure and mechanical properties of uniaxially oriented films of syndiotactic polystyrene and poly(2,6‐dimethyl‐1,4‐phenylene oxide) blends

The structure and mechanical properties of highly oriented films of a miscible blend of syndiotactic polystyrene and poly(2,6‐dimethylphenylene‐1,4‐oxide) (sPS/PPO) were studied in the composition range of sPS/PPO = 10/0 to 5/5. The oriented films were prepared by stretching the amorphous films of the blends. Wide‐angle X‐ray diffraction and polarized FTIR spectroscopy were used to analyze the amount of mesophase and molecular orientation. Drawing of the amorphous films of sPS and sPS/PPO blend induced a highly oriented mesophase. The mesophase content increases with increasing draw ratio and becomes nearly constant above a draw ratio of 3. Under the same draw ratio, the mesophase content decreases with increasing PPO content. The orientation function in the mesophase is as high as 0.95–0.99 irrespective of the composition and draw ratio. On the other hand, the orientation of molecular chains in the amorphous phase and mesophase increases with increasing draw ratio, and it decreases with increasing PPO content. The drawn films of pure sPS show high strength and high modulus in the drawing direction, but exhibit low strength in the direction perpendicular to the drawing. In the case of sPS/PPO = 7/3 blend, however, the ultimate strength in the perpendicular direction was dramatically improved compared with that of pure sPS and the ultimate strength in the parallel direction was similar to that for the oriented pure sPS. The improved mechanical properties in the sPS/PPO blends were discussed in relation to the structural characteristics of the sPS/PPO blend system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:2789–2797, 2004     

Emulsion polymerization of styrene with Iso‐octyl‐3‐mercaptopropionate as chain transfer agent

Four batch and unseeded emulsion polymerizations of styrene were investigated, which included isooctyl 3‐mercaptopropionate (iOMP) as chain transfer agent (CTA). This compound was analyzed by ¹³C NMR and GC/MS, resulting in a mixture of over 10 isomers. Because of different reactivities of the CTA isomers, the produced polystyrenes presented broad and bimodal molecular weight distributions (MWDs). A mathematical model was adjusted to the measurements, and the measured MWDs were adequately predicted when assuming the CTA as a binary mixture of high but different reactivities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,structural and spectral properties of an ionic polyacetylene: Poly[N‐(5‐nitro‐2‐furanmethylene)‐2‐ethynylpyridinium bromide]

A new ionic polyacetylene was prepared by the activation polymerization of 2‐ethynylpyridine with 2‐(bromomethyl)‐5‐nitrofuran in high yield without any additional initiator or catalyst. This polymerization proceeded well in a homogeneous manner to give a high yield of the polymer (92%). The activated acetylenic triple bond of N‐(5‐nitro‐2‐furanmethylene)‐2‐ethynylpyridinium bromide, formed in the first quaternerization process, was found to be susceptible to linear polymerization. This polymer was completely soluble in such polar organic solvents as dimethylformamide, dimethyl sulfoxide, and N,N‐dimethylacetamide. The inherent viscosities of the resulting polymers were in the range 0.12–0.19 dL/g, and X‐ray diffraction analysis data indicated that this polymer was mostly amorphous. The polymer structure was characterized by various instrumental methods to have a polyacetylene backbone structure with the designed substituent. The photoluminescence peak was observed at 593 nm; this corresponded to a photon energy of 2.09 eV. The polymer exhibited irreversible electrochemical behaviors between the doping and undoping peaks. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of tailor‐made polystyrene nanocomposite with mixed clay‐anchored and free chains via atom transfer radical polymerization

Tailor‐made polystyrene nanocomposite with mixed free and clay‐attached polystyrene chains was synthesized using atom transfer radical polymerization. Vinylbenzyl trimethylammonium chloride having a double bond, which could be incorporated into polystyrene chains by a grafting through process, was used as a nanoclay modifier. Conversion and molecular weight evaluation was carried out using gas chromatography and gel permeation chromatography, respectively. The thermogravimetric analysis results confirmed the elevated thermal stability of the nanocomposites in comparison with the neat polystyrene sample. Additionally, the T_g increases by clay loading was confirmed by differential scanning calorimetry (DSC). The difference in the degradation temperature of C? Br bond in attached and free polystyrene chains was well revealed in DSC thermograms. Finally, a lower clay loading resulted in an exfoliated structure as proved by X‐ray diffraction and transmission electron microscopy results. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

High Nd3+→Yb3+ energy transfer efficiency in tungsten‐tellurite glass: A promising converter for solar cells

This work reports on the energy transfer efficiency for Nd³⁺/Yb³⁺ co‐doped tellurite glasses (80TO₂‐20WO₃, in mol%,). The correlation between Yb³⁺ ion concentration and the downconversion mechanism was investigated using optical and thermal lens spectroscopies, which enabled investigation of the radiative and nonradiative processes, respectively, involved in energy transfer from neodymium to ytterbium. The Nd³⁺ near‐infrared fluorescence disappeared almost entirely when the maximum concentration of Yb³⁺ ions (4 mol%) was doped into the host. In contrast, there was a corresponding increase in the ytterbium emission at around 980 nm. When ytterbium was added, there was also a simultaneous reduction in the amount of heat generated by the sample due to a reduction in the nonradiative decay rate, corroborating the suspected high energy transfer efficiency of Nd³⁺→Yb³⁺. The results indicate that tungsten‐tellurite glasses may be of potential use in solar cells for matching the solar emission spectrum to the semiconductor cell.     

Energy‐transfer method to study vapor‐induced latex film formation

Nonradiative energy transfer method was used to study latex film formation induced by organic solvent vapor. Seven different films with the same latex content were prepared separately from poly(methyl methacrylate) (PMMA) particles and exposed to ethyl benzene, toluene, chloroform, dichloromethane, tetrahydrofuran, and acetone vapor in seven different experiments. Energy‐transfer experiments were carried out between PMMA‐bound naphthalene (N) and pyrene (P) during vapor‐induced film formation. Latex films were prepared from equal amounts of N‐ and P‐labeled latex particles, and steady state spectra of N and P were monitored during film formation. It was observed that the P to N intensity ratio, I_P/I_N, increased as the vapor exposure time increased. The Prager–Tirrell (PT) model was employed to obtain back‐and‐forth frequencies, ν, of the reptating PMMA chains during latex film formation induced by solvent vapor. ν values were obtained and found to be correlated with the solubility parameter, δ. Polymer interdiffusion obeyed the t^1/2 law during film formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 632–645, 2002; DOI 10.1002/app.10346     

Synthesis and characterization of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers by atom‐transfer radical polymerization

Well‐defined polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐PS triblock copolymers were synthesized by atom‐transfer radical polymerization (ATRP), using C—X‐end‐group PEO as macroinitiators. The triblock copolymers were characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The experimental results showed that the polymerization was controlled/living. It was found that when the number‐average molecular weight of the macroinititors increased from 2000 to 10,000, the molecular weight distribution of the triblock copolymers decreased roughly from 1.49 to 1.07 and the rate of polymerization became much slower. The possible polymerization mechanism is discussed. According to the Cu content measured with atomic absorption spectrometry, the removal of catalysts, with CHCl₃ as the solvent and kaolin as the in situ absorption agent, was effective. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2882–2888, 2000     

Solubility of polystyrene with various molecular weights in subcritical 1,1,1,2‐tetrafluoroethane: experiment and modified model

The solubility of polystyrene with molecular weight of 100 000 and 260 000 g mol^?1 was measured at temperatures from 313 to 333 K and at pressures from 5.0 to 13.0 MPa in subcritical 1,1,1,2‐tetrafluoroethane (R134a). The effects of pressure, temperature and molecular weight on the solubility of polystyrene were investigated. Meanwhile, the solubility of polystyrene was correlated using six density‐based semi‐empirical models (Chrastil, A‐L, K‐J, S‐S, M‐S‐T and Bartle). The M‐S‐T model was used to verify the self‐consistency of the experimental data, and the enthalpy values of polystyrene, including ΔH_total, ΔH_sub and ΔH_sol, were estimated through the Chrastil and Bartle models. In addition, a modified M‐S‐T model was proposed through a detailed study of semi‐empirical model formulas and verified by the solubility of polystyrene in subcritical R134a and 38 other solid solutes in supercritical carbon dioxide and subcritical R134a. © 2018 Society of Chemical Industry     

Photo‐oxidation of polystyrene/clay nanocomposites under accelerated UV exposure: Effect on the structure and molecular weight

The present work investigates the effects of photo‐oxidation under accelerated UV conditions on the structure, the molecular weight and the morphology of polystyrene (PS)/organophilic montmorillonite (OMMT) at various clay contents: 2.5, 5, and 7 wt %. Fourier transform infrared spectroscopy, viscosimetry and scanning electron microscopy were used to evaluate the extent of degradation of nanocomposite samples in comparison with neat PS, up to 216 h of exposure. The study has shown that the formation rates of both carbonyl and hydroperoxide groups increase with exposure time, being much higher for PS/OMMT nanocomposites. Moreover, it is also observed that all samples exhibit a large increase in the scission index, however less pronounced for neat PS. These results clearly indicate the formation of low molecular weight products that could arise from chain scission. Further, the photo‐oxidation rate seems to be more affected by the presence of clay, which acts as a catalyst, rather than by the variation of clay contents. Finally, the degraded materials exhibit eroded surface. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009