Side chain alkylation of toluene with methanol over basic zeolites - novel production route towards styrene?

Styrene is an important monomer for the production of different types of (co-) polymers that are used in, e.g., toys, medical devices, food packaging, paper coatings etc. Styrene is produced with several different industrial processes. In 1998, the production of styrene monomer was approximately 21 million tons that are produced or used by more than 15,000 plants worldwide. Two of the largest production processes are described in Chapter 1 and both have their major drawbacks. These drawbacks have prompted researchers (academic and industrial) to study other styrene synthesis routes. Two possible synthesis routes are introduced in Chapter 1. One of these possibilities is\ud the side chain alkylation of toluene with methanol (MeOH) using basic zeolites. The toluene side chain alkylation reaction with methanol was first discovered by Sidorenko et al. (Dokl. Akad. Nauk. SSSR 1967, 173, 132) in the mid sixties. Since then researchers all over the world have tried to improve the styrene productivity. Major drawbacks are the high methanol conversion to byproducts like CO, H2, and dimethyl ether (DME) and the low yield of styrene. This thesis describes our efforts to understand the fundamentals of the interaction between\ud methanol and the zeolite host and its reaction with toluene

Polystyrene/Graphite Nanocomposites: Effect on Thermal Stability

Nanocomposites consisting of polymer and clay have been shown to exhibit a significant reduction in flammability and an increase in mechanical properties. This work examines the effect of thermal stability and mechanical properties of nanocomposites prepared from potassium graphite and styrene. Synthesis of nanocomposites was accomplished by using potassium graphite (KC8) as the initiator in the polymerization of styrene. A slight increase in thermal stability is observed but mechanical properties are decreased

Linear Chains of Styrene and Methyl-Styrene Molecules and their Heterojunctions on Silicon: Theory and Experiment

We report on the synthesis, STM imaging and theoretical studies of the structure, electronic structure and transport properties of linear chains of styrene and methyl-styrene molecules and their heterojunctions on hydrogen-terminated dimerized silicon (001) surfaces. The theory presented here accounts for the essential features of the experimental STM data including the nature of the corrugation observed along the molecular chains and the pronounced changes in the contrast between the styrene and methyl-styrene parts of the molecular chains that are observed as the applied bias is varied. The observed evolution with applied bias of the STM profiles near the ends of the molecular chains is also explained. Calculations are also presented of electron transport along styrene linear chains adsorbed on the silicon surface at energies in the vicinity of the molecular HOMO and LUMO levels. For short styrene chains this lateral transport is found to be due primarily to direct electron transmission from molecule to molecule rather than through the silicon substrate, especially in the molecular LUMO band. Differences between the calculated position-dependences of the STM current around a junction of styrene and methyl-styrene molecular chains under positive and negative tip bias are related to the nature of lateral electron transmission along the molecular chains and to the formation in the LUMO band of an electronic state localized around the heterojunction.Comment: 17 pages plus 11 figures. To appear in Physical Review

High molar mass segmented macromolecular architectures by nitroxide mediated polymerisation

A straightforward synthetic pathway based on nitroxide mediated polymerisation (NMP) for the synthesis of a variety of high molar mass segmented copolymers comprising both polystyrene (PS) and polyether segments is reported. First, various precursors such as linear or star-shaped polyether macromonomers, containing either a-methylstyrene or styrene functions at one polymer terminus, as well as PS and polyether macroalkoxyamines bearing either 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or N-tert-butyl-1-diethylphosphono-2,2-dimethylpropyl nitroxide (SG1) end-groups, were prepared. In a second step, these prepolymers were used to design different copolymer architectures such as block, graft, star-grafted, toothbrush and palm tree structures, in which PS constituted the backbone and polyether the side chains. Block copolymers were obtained by NMP of styrene initiated with polyether macroalkoxyamines. Copolymerisation of styrene with linear and star-shaped polyether macromonomers by NMP resulted in graft and star-grafted copolymers, respectively. A toothbrush copolymer was produced in a similar way with the exception of the initiator, which was a PS macroalkoxyamine. Likewise, palm tree architectures were obtained by homopolymerising polyether macromonomers initiated by PS macroinitiators. Advanced characterisation of the different polymer structures was performed, including 2D chromatography

Synthesis and properties of a new AB-cross-linked copolymer membrane system

The alcohol permeability and permselectivity properties as well as the morphology of membranes made of a newly developed AB-cross-linked copolymer system composed of elastomeric and glassy components were investigated. The copolymer was synthesized by a hydrosilylation reaction between poly(styrene-stat-isoprenes) (Mn from 40,000 to 100,000 g/mol) with high content in unsaturated side groups (≈ 60% of entire isoprene content) and polyhydrogen polysiloxanes with varying SiH content (0.75 10.7 mol %) and molecular mass, Mn, from 2,500 to 36,000 g/mol. A two-track approach was taken to determine the morphology of the copolymer system. The first employed the usual polymer characterization methods such as electron microscopy, DSC, IR spectroscopy, the density gradient method, and mechanical measurements. For the second approach, different copolymer permeability models were tested so as to give an insight into the copolymer morphology. As a final step, the permeability and permselectivity properties were correlated with the morphological structure of the copolymer system. It was observed that the respective continuous microphase dominated the copolymer's physical properties, as, e.g., permeability, permselectivity, and mechanical properties. The microphase inversion in the copolymer system was proved by the permeability/permselectivity as well as by the mechanical measurements

Structure and dielectric properties of electroactive tetraaniline grafted non-polar elastomers

Intrinsic modification of polybutadiene and block copolymer styrene–butadiene–styrene with the electrically conducting emeraldine salt of tetraaniline (TANI) via a three-step grafting method, is reported in this work. Whilst the TANI oligomer grafted at a similar rate to both polybutadiene and styrene–butadiene–styrene under the same conditions, the resulting elastomers exhibited vastly different properties. 1 mol% TANI-PB exhibited an increased relative permittivity of 5.9, and a high strain at break of 156%, whilst 25 mol% TANI-SBS demonstrated a relative permittivity of 6.2 and a strain at break of 186%. The difference in the behaviour of the two polymers was due to the compatibilisation of TANI by styrene in SBS through π-π stacking, which prevented the formation of a conducting TANI network in SBS at. Without the styrene group, TANI-PB formed a phase separated structure with high levels of TANI grafting. Overall, it was concluded that the polymer chain structure, the morphology of the modified elastomers, and the degree of grafting of TANI, had the greatest effect on the mechanical and dielectric properties of the resultant elastomers. This work paves the way for an alternative approach to the extrinsic incorporation of conducting groups into unsaturated elastomers, and demonstrates dielectric elastomers with enhanced electrical properties for use in actuation devices and energy harvesting applications

Synthesis of polymer encapsulated nano-clay hybrid via miniemulsion

Issued as final reportNational Science Foundation (U.S.

Flavoprotein monooxygenases for oxidative biocatalysis: recombinant expression in microbial hosts and applications

External flavoprotein monooxygenases comprise a group of flavin-dependent oxidoreductases that catalyze the insertion of one atom of molecular oxygen into an organic substrate and the second atom is reduced to water. These enzymes are involved in a great number of metabolic pathways both in prokaryotes and eukaryotes. Flavoprotein monooxygenases have attracted the attention of researchers for several decades and the advent of recombinant DNA technology caused a great progress in the field. These enzymes are subjected to detailed biochemical and structural characterization and some of them are also regarded as appealing oxidative biocatalysts for the production of fine chemicals and valuable intermediates toward active pharmaceutical ingredients due to their high chemo-, stereo-, and regioselectivity. Here, we review the most representative reactions catalyzed both in vivo and in vitro by prototype flavoprotein monooxygenases, highlighting the strategies employed to produce them recombinantly, to enhance the yield of soluble proteins, and to improve cofactor regeneration in order to obtain versatile biocatalysts. Although we describe the most outstanding features of flavoprotein monooxygenases, we mainly focus on enzymes that were cloned, expressed and used for biocatalysis during the last yearsFil: Ceccoli, Romina Denis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; ArgentinaFil: Bianchi, Dario Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; ArgentinaFil: Rial, Daniela Veronica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Biología Molecular y Celular de Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Biología Molecular y Celular de Rosario; Argentin