STYRENE BUTADIENE RUBBER/RECLAIMED RUBBER BLENDS

Cure characteristics and mechanical properties of styrene butadiene rubber reclaimed rubber blends were studied. The blends showed improved processability, as indicated by the minimum torque values. Cure characteristics like minimum torque, (maximum-minimum) torque, cure time and cure rate decreased in the presence of reclaimed rubber. Tensile strength, tear strength, elongation at break were higher for blends. Resilience decreased with reclaim content. Compression set and abrasion loss were higher in the blends.

Diblock and Triblock Copolymers of Styrene and Acetoxymethylstyrene by One-Pot ATRP

We describe the synthesis of diblock and triblock copolymers by sequential atom transfer radical polymerization of styrene and acetoxymethylstyrene. Contrary to the usual block copolymerization involving isolation of the macroinitiator, a convenient one-pot procedure is developed. This is possible because of the preferential polymerization of acetoxymethylstyrene, even in the presence of residual styrene, as inferred from characterization of the intermediate polystyrenes and the block copolymers by size exclusion chromatography, 1H NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and GPEC techniques. The latent acetoxy functionalities in these block copolymers are shown to be easily unmasked to OOH and OBr functionalities, with the potential for block ionomers and dense graft architectures.

Overtone spectra of styrene and polystyrene in the visible and near infrared regions

Vibrational overtone spectra of styrene (liquid) and polystyrene (solid), studied by the laser-induced thermal lens (for ΔV=6) and the conventional near infrared absorption (for ΔV=3–5) techniques, are reported. For polystyrene, the overtone energy-bond length correlation predicts that the aryl CH bonds are ∼0.0005 Å longer than that in benzene, while no such conclusions could be drawn on styrene. Thesp 3 CH overtones in polystyrene are observed on the low energy side of the aryl CH overtones.

Synthesis and Characterization of Novel Ionomers based on Styrene Butadiene Copolymer

Novel thermo-reversible zinc sulphonated ionomers based on styrene butadiene rubber (SBR), and high styrene rubber (HSH) were synthesized by sulphonation followed by neutralization with zinc. The sulphonate content of the ionomer was estimated by using x-ray fluorescence spectroscopy. Presence of sulphonate groups has been confirmed by FTIR and FTNMR spectra. The TGA results show improvement in the thermo~oxidative stability of the modified rubber. Both DSC and DMTA studies show that the incorporation of the ionic groups affect the glass rubber transition of the base polymer. lntroduction ol ionic functionality in to the base material improved the physical properties. Retention of the improved physical properties of the novel ionomers even after three repeated cycles of mixing and molding may be considered as the evidence for the reprocessability of the ionomer. Effect of particulate fillers (HAF black, silica and zinc stearate) on the properties of the zinc sulphonated styrene butadiene rubber ionomer has been evaluated. Incorporation of tillers results in improvement in mechanical properties. Zinc stearate plays the dual role of reinforcement and plasticization. The evaluation of dielectric properties of zinc sulphonated styrene butadiene rubber iorpmers at microwave frequencies reveal that the materials show conductivity at semiconductor level. The real and imaginary parts of the complex permittivity increases with increase in ionic functionality. Use of the 38.5 ZnS-SBR ionomer as a compatibiliser for obtaining the technologically compatible blends from the immiscible SBR/NBR system has been discussed.

Synthesis of multicarboxylic acid appended imidazolium ionic liquids and their application in palladium-catalyzed selective oxidation of styrene

A series of multicarboxylic acid appended imidazolium ionic liquids ( McaILs) with chloride [ Cl](-) or bromide [ Br](-) as anions have been synthesized and characterized. Deprotonation of these ionic acids gives the corresponding zwitterions. Re-protonation of the zwitterions with strong Bronsted acids gives a series of new ionic acid-adducts, many of which remained as room-temperature ionic liquids. A new catalytic system, McaIL/PdCl2 for the selective catalytic oxidation of styrene to acetophenone with hydrogen peroxide as an oxidant has been attempted. In the presence of McaILs, it is found that the quantity of palladium chloride PdCl2 used can be greatly reduced while the activity ( TOF) and selectivity towards acetophenone are enhanced sharply. It is also shown that the catalytic properties of this system could be finely tuned through the molecular design of the McaILs. The best TOF value obtained so far is 146 h(-1) with 100% conversion of styrene at 93% selectivity to acetophenone. In addition, the catalytic activity has been maintained for at least ten catalytic cycles.

Effect of Stretching on the Structure of Cylinder- and Sphere-Forming Styrene-Isoprene-Styrene Block Copolymers

Two styrene-isoprene-styrene block copolymers Vector 4111 and 4113, exhibiting cylindrical (18 wt % PS) and spherical (16 wt % PS) morphology, respectively, have been examined under uniaxial elongation up to 200% strain. On the basis of stress-strain data, mechanical properties are compared for isotropic and oriented polystyrene domains. The structure at various stages of deformation has been determined from SAXS patterns in three planes and two principal deformation directions with respect to orientation. Samples showed a very high degree of hexagonal packing, resulting in an X-ray pattern taken parallel to the cylinder alignment approaching single crystal ordering. Cylinders were aligned with the closest packed planes parallel to film surface. Particular attention has been paid to a lattice deformation process occurring during the first stretching and relaxation cycle. For a copolymer with oriented cylindrical morphology the deformation was affine up to 120% strain. The microdomain spacing was calculated parallel and perpendicular to the stretching direction. The cylindrical microstructure orientation, quantified by Hermans' orientation factor reduced during elongation of oriented polymer, while the elongation of isotropic sample caused an increase of orientation. Deformation of all studied morphologies was reversible.

Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation

Addition of the dithioethers (−)-DIOSR2 (R=Me, iPr) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)2]ClO4 (COD=1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)(DIOSiPr2)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the iPr groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)2Rh(μ-DIOSR2)2(CO)2](ClO4)2. [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65°C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low.

Mononuclear Pt(II) and Pd(II) 1,4-dithiolato complexes. Crystal structures of [Pt((−) DIOS) (PPh3)2] and [Pd(S(CH2) 4S)(Ph2P(CH2) 3PPh2)]. Application in styrene hydroformylation

Addition of 1,4-dithiols to dichloromethane solutions of [PtCl2(P-P)] (P-P = (PPh3)2, Ph2P(CH2)3PPh2, Phd2P(CH2)4PPh2; 1,4-dithiols = HS(CH2)4SH, (−)DIOSH2 (2,3-O-isopropylidene-1,4-dithiol-l-threitol), BINASH2 (1,1′-dinaphthalene-2,2′-dithiol)) in the presence of NEt3 yielded the mononuclear complexes [Pt(1,4-dithiolato)(P-P)]. Related palladium(II) complexes [Pd(dithiolato)(P-P)] (P-P=Ph2P(CH2)3PPh2, Ph2P(CH2)4PPh2; dithiolato = −S(CH2)4S−, (−)-DIOS) were prepared by the same method. The structure of [Pt((−)DIOS)(PPh3)2] and [Pd(S(CH2)4S)(Ph2P(CH2)3PPh2)] complexes was determined by X-ray diffraction methods. Pt—dithiolato—SnC12 systems are active in the hydroformylation of styrene. At 100 atm and 125°C [Pt(dithiolate)(P-P)]/SnCl2 (Pt:Sn = 20) systems provided aldehyde conversion up to 80%.

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd-PSS films were processed using the acid of poly(styrene sulfonate) - H-PSS and neodymium nitrate - Nd(NO(3))(3); the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV-Vis-NIR spectral region presents typical electronic transitions of Nd 3, ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N-O groups in the range of 1400-720 cm(-1), prove the permanence of Nd(NO(3))(x), with x = 1, 2 and/or 3. in the H-PSS matrix. UV-Vis site selective photoluminescence data indicate that the incorporation of Nd 31 introduces a blue shift in PSS emission (325-800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd(3+) reabsorption and energy transfer effects between the PSS matrix and Nd(3+) were also observed. The IR emission of Nd-PSS films at 1076 rim ((4)F(3/2) -> (4)I(11/2)) present constant efficiency, independent on Nd(3+) concentration. The Judd-Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd(3+). Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix. (C) 2008 Elsevier B.V. All rights reserved.

Preparation and characterization of the novels terpolymers of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine impregnated with silver nanoparticles

This paper reports the preparation and characterization of poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} and styrene-divinylbenzene-vinylpiridine filled with nanosilver. Theses materials were synthesized by non aqueous polymerization through a chemical reaction using benzoyl peroxide as the initiator. The nanosilver was obtained from chemical reduction using NaBH(4) as reducing agent and sodium citrate as stabilizer. The nanometric dimension of nanosilver was monitored by UV-visible and confirmed through TEM. The morphology was characterized by SEM and the thermal properties were done by TGA and DSC. The antimicrobial action of the polymers impregnated with nanosilver was evaluated using both microorganisms, Staphylococcus aureus and Escherichia coli. The antimicrobial activity of the poly-{trans-[RuCl(2)(vpy)(4)]-styrene-divinylbenzene} filled with nanosilver was confirmed by the presence of an inhibition halo of the bacterial growth in seeded culture media, but was not confirmed to the styrene-divinylbenzene-vinylpiridine. The present work suggest that trans - [RuCl(2)(vpy)(4)] complex facilitate the release of silver ion from the media.

Synthesis of poly(styrene-co-methyl methacrylate)-based ionomers and their Langmuir and Langmuir-Blodgett (LB) film formation

Poly(styrene-co-methyl methacrylate) (PS-PMMA) ionomers with several degrees of sulfonation were synthesized and characterized by infrared, UV-vis, and NMR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). Stable Langmuir films could be produced with PS-PMMA with 3 and 6 mol % of sulfonation, while PS-PMMA 8% exhibited material loss to the water subphase, probably due to its higher solubility. Surface pressure and surface potential isotherms with PS-PMMA 3% spread onto salt-containing subphases pointed to a film behavior characteristic of the polyelectrolyte effect, where charge repulsion governs the film properties. The Langmuir-Blodgett films of this ionomer were successfully transferred onto various substrates, as confirmed by UV-vis and FTIR spectroscopies. Using cycling voltammetry, we show that LB films from PS-PMMA 3% can be applied in selective sensing of dopamine, even in the presence of interferents such as ascorbic acid.

A GC-FID Method to Determine Styrene in Polystyrene Glasses

The styrene levels of polystyrene (PS) glasses from the most consumed brands of disposable glasses intended for water and coffee in Brazil were determined. A GC-FID method was developed and validated, showing good precision and accuracy. The method was successfully used to determine styrene in 11 PS glass brands. The styrene levels ranged from 1.68 to 43.69 mg/100 g glass, depending on the kind of polymer, thickness, and glass brand. It could be used to control the content of styrene in the polymer. The migration of styrene from the glasses into water and 20 % ethanol was not detected.

NMR study of styrene-butadiene rubber (SBR) and TiO2 nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanocomposites of Styrene-Butadiene Rubber and Synthetic Anatase Obtained by a Colloidal Route and Their Photooxidation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)