Novel PPV-based light-emitting polymers containing siloxane moiety

Two PPV-based copolymers consisting siloxane linkage have been synthesized by melt condensation of bisphenol and dianilinodimethylsilane. The rigid PPV segments act as chromosphere and allow fine turning of band gap for blue-light emission, while the flexible siloxane units lead to the effective interruption of conjugation and the enhancement of solubility. The UV-vis absorption, photoluminescent and eletroluminescent properties have been studied.

Correlation Between the Electrical and Optical Properties of an Atmospheric Pressure Plasma During Siloxane Coating Deposition

The effect of varying process parameters on atmospheric plasma characteristics and properties of nanometre thick siloxane coatings is investigated in a reel-to-reel deposition process. Varying plasma operation modes were observed with increasing applied power for helium and helium/oxygen plasmas. The electrical and optical behaviour of the dielectric barrier discharge were determined from current/voltage, emission spectroscopy and time resolved light emission measurements. As applied power increased, multiple discharge events occurred, producing a uniform multi-peak pseudoglow discharge, resulting in an increase in the discharge gas temperature. The effects of different operating modes on coating oxidation and growth rates were examined by injecting hexamethyldisiloxane liquid precursor into the chamber under varying operating conditions. A quenching effect on the plasma was observed, causing a decrease in plasma input power and emission intensity. Siloxane coatings deposited in helium plasmas had a higher organic component and higher growth rates than those deposited in helium/oxygen plasmas.

ORGANOSILICON BIOTECHNOLOGY: A BIO-INSPIRED APPROACH TO THE HYDROLYSIS OF ALKOXYSILANES and THE LIPASE-CATALYZED SYNTHESIS OF SILOXANE-CONTAINING POLYESTERS AND POLYAMIDES

The first part of this thesis studied the capacity of amino acids and enzymes to catalyze the hydrolysis and condensation of tetraethoxysilane and phenyltrimethoxysilane. Selected amino acids were shown to accelerate the hydrolysis and condensation of tetraethoxysilane under ambient temperature, pressure and at neutral pH (pH 7±0.02). The nature of the side chain of the amino acid was important in promoting hydrolysis and condensation. Several proteases were shown to have a capacity to hydrolyze tri- and tet-ra- alkoxysilanes under the same mild reaction conditions. The second part of this thesis employed an immobilized Candida antarctica lipase B (Novozym-435, N435) to produce siloxane-containing polyesters, polyamides, and polyester amides under solvent-free conditions. Enzymatic activity was shown to be temperature dependent, increasing until enzyme denaturation became the dominant pro-cess, which typically occurred between 120-130ᵒC. The residual activity of N435 was, on average, greater than 90%, when used in the synthesis of disiloxane-containing polyesters, regardless of the polymerization temperature except at the very highest temperatures, 140-150ᵒC. A study of the thermal tolerance of N435 determined that, over ten reaction cycles, there was a decrease in the initial rate of polymerization with each consecutive use of the catalyst. No change in the degree of monomer conversion after a 24 hour reaction cycle was found.

Synthesis of pendant epoxy functional polydimethyl siloxane for modification of Diglycidyl Ether of Bis-phenol A

In this study, pendant epoxy functional poly dimethyl siloxanes were synthesized by the hydrosilylation reaction of pendant silyl hydride functional polydimethyl siloxane with allyl glycidyl ether. The hydrosilylation reaction was characterized by spectroscopic techniques. Samples of pendant epoxy functional poly dimethyl siloxanes and pendant silyl hydride functional polydimethyl siloxane were blended with commercial epoxy resin, diglycidyl ether of bis-phenol A, at various ratios using a polyamine as curing agent. The results show that the addition of functionalised poly dimethyl siloxanes increases the flexibility of the cross linked network and also the thermal stability and water resistance

A mechanistic study of cyclic siloxane pyrolyses at low pressures

Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethyl cyclopentasiloxane (D5), and the results interpreted in the context of various kinetic models. In particular, it is shown that the significant pyrolysis products - which include CH3, CH4, C2H2, C2H4, C2H6 and SiO - may be satisfactorily accounted for by radical reactions involving dimethylsiloxane (D1), and estimates are made of the various chain lengths for the proposed reactions based on a range of ambient conditions.

Surface modification of siloxane containing polyurethane polymer by dielectric barrier discharge at atmospheric pressure

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

Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel

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

Highly corrosion resistant siloxane-polymethyl methacrylate hybrid coatings

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Aluminoxane-epoxi-siloxane hybrids waveguides

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

Drying study of siloxane-PPG nanocomposites

This is a study of the structural transformations occurring in hybrid siloxane-polypropyleneglycol (PPG) nanocomposites, with different PPG molecular weight, along the drying process. The starting materials are wet gels obtained by the sol-gel procedure using as precursor the 3-(trietoxysilyl)propylisocyanate (IsoTrEOS) and polypropylenglycol bis(2-amino-propyl-ether) (NH2-PPG-NH2). The shrinkage and mass loss measurements were performed using a temperature-controlled chamber at 50 degreesC. The nanostructural evolution of samples during drying was studied in situ by small angle x-ray scattering (SAXS). The experimental results demonstrate that the drying process is highly dependent on the molecular weight of polymer. After the initial drying stage, the progressive emptying of pores leads to the formation of a irregular drying front in gels prepared from PPG of high molecular weight, like 4000 g/mol. As a consequence, an increase of the SAXS intensity due to the increase of electronic density contrast between siloxane clusters and polymeric matrix is observed. For hybrids containing PPG of low molecular weight, the pore emptying process is fast, leading to a regular drying front, without isolated nanopockets of solvents. SAXS intensity curves exhibit a maximum, which was associated to the existence of spatial correlation of the silica clusters embedded in the polymeric matrix. The spatial correlation is preserved during drying. These results also reveal that the structural transformation during drying is governed by capillary forces and depends on the entanglement of polymer chains.

Planar and UV written channel optical waveguides prepared with siloxane poly(oxyethylene)-zirconia organic-inorganic hybrids. Structure and optical properties

Organic-inorganic hybrids were prepared using ureapropyltriethoxysilane, methacryloxypropyltrimethoxysilane and acrylic acid modified zirconium(IV) n-propoxide precursors and were characterized by small angle X-ray scattering, X-ray diffraction and photoluminescence spectroscopy. The results indicate an effective interaction between the zirconium-based nanoparticles and the siliceous nanodomains that induces changes in the hybrids' emission features. Planar waveguides were obtained by spin-coating of the prepared sols on sodalime and silica substrates. Refractive index, thickness, number of propagating modes, and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm by the prism coupling technique. The synergism between the two hybrid precursors resulted in monomode planar waveguides with low losses in the infrared ( from 0.6-1.1 dB cm(-1)) which also support a number of propagating modes in the visible ( losses from 0.4-1.5 dB cm(-1)). Channel waveguides were also obtained by UV photopatterning using amplitude or phase masks and propagating modes were observed at 1550 nm.

Small-angle X-ray scattering study of sol-gel-derived siloxane-PEG and siloxane-PPG hybrid materials

Hybrid organic-inorganic two-phase nanocomposites of siloxane-poly(ethylene glycol) (SiO3/2-PEG) and siloxane-poly(propylene glycol) (SiO3/2-PPG) have been obtained by the sol-gel process. In these composites, nanometric siloxane heterogeneities are embedded in a polymeric matrix with covalent bonds in the interfaces. The structure of these materials was investigated in samples with different molecular weights of the polymer using the smalt-angle X-ray scattering (SAXS) technique. The SAXS spectra exhibit a well-defined peak that was attributed to the existence of a strong spatial correlation of siloxane clusters. LiClO4-doped siloxane-PEG and siloxane-PPG hybrids, which exhibit good ionic conduction properties, have also been studied as a function of the lithium concentration [O]/[Li], O being the oxygens of ether type. SAXS results allowed us to establish a structural model for these materials for different basic compositions and a varying [Li] content. The conclusion is consistent with that deduced from ionic conductivity measurements that exhibit a maximum for [O]/[Li] =15.

Effect of addition of MTES on the structure of siloxane-PPG nanocomposites

Hybrid transparent and flexible siloxane-polypropyleneglycol (PPG) materials with covalent bonds between the inorganic (siloxane) and organic (polymeric) phases were prepared by sol-gel process. In order to improve the quality of the mechanical properties of these materials, different amounts of methyltriethoxysilane (MTES) were added to the initial sol. The effect of MTES addition on the structure of the composites was studied by Small-Angle X-Ray Scattering (SAXS) and Si-29 Nuclear Magnetic Resonance (Si-29 NMR). In absence of MTES, SAXS spectra exhibit a peak that is assigned to spatial correlation due to short range order between the siloxane clusters embedded in the polymeric phase. The experimental results indicate that, for low MTES concentrations ([MTES]/[O] less than or equal to 0.8, O: ether-type oxygen of PPG), the silicon species resulting from hydrolysis and condensation of MTES fill the open spaces between polymeric chains, interacting with the ether-type oxygens. For larger MTES content ([MTES]/[O] greater than or equal to 0.8), the number of free ether-type oxygen sites avalaible for reaction with such silicon species is not large enough. Consequently, a fraction of silicon species resulting from MTES addition graft to siloxane clusters formed by hydrolysis and condensation of the hybrid precursor. For all MTES concentrations the condensation degree of the siloxane phase, determined from Si-29 NMR spectroscopy, is high (> 69%), as expected under neutral pH synthesis conditions.