Novos monômeros obtidos a partir do metacrilato de glicidila, bisfenol A e 4, 4 isopropilidenodicicloexanol : síntese, caracterização estrutural e propriedades de compósitos para utilização em resinas de restauração dental

Nowadays, composite resins are the direct restorative materials more important in dental clinical performance, due to their versatility and aesthetic excellence. Bis-GMA (2,2-bis[4(2-hydroxy-3-metacryloxypropoxy)phenil]propane) is the base monomer more frequently used in restorative composite resins. However, this monomer presents some disadvantages, such as high viscosity and two aromatic rings in its structure that can promote allergic reactions to the humans. In this work, the main purpose was to synthesize new monomers from glycidyl methacrylate to use in dental restorative materials. Structural characterization of the monomers was carried out through FTIR and NMR 1H, and eight composites were produced from the new monomers, by addition of silane-treated alumino silicate particles (inorganic filler) and a photocuring system (camphorquinone and ethyl 4-dimethylaminebenzoate). The composites were analyzed by environmental scanning electronic microscopy and the water sorption and solubility, compressive strength and elastic modulus were determined. A commercial composite resin [Z100 (3M)] was used to comparison effect. The new composites presented general characteristics similar to the commercial ones; however, they didn t present the properties expected. This behavior was attributed to the lower degree of monomer reaction and to the granulometry and size distribution of the mineral filler in the polymeric matrix

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams

Caracterização de poliacrilamida parcialmente hidrolisada em regime concentrado

A partially hydrolyzed polyacrylamide (HPAM) is a copolymer composed of acrylamide and sodium acrylate. Due to its wide range of applications there are different methods for its quantification and characterization in solution systems. Evaluation of C* is important to describe the transition from dilute to semi-dilute, behavior, when the solution will have its characteristic viscosity at concentrations above C*. This dissertation describes the determination of the critical concentration of overlap C* by potentiometry of partially hydrolyzed polyacrylamide - HPAM under acidic conditions. Based on the law of mass action and the proper treatment of the constant of aggregate formation, polymer molecular weight, degree of polymerization and hydrolysis were calculated. The inflection point was determined by the intersection of the resulting equation and mathematical development, statistically satisfy the experimental points relating the number of moles of monomers (n), equilibrium constant of formation of the entanglements (K*), pH, C* and acidity constant of the polymer (Ka). The viscometric parameters of C* showed a percentage difference compared to potentiometers. The results for the determination of C*, and degree of copolymerization molar mass proved to be a simple alternative for the characterization of polymers with protonated monomers and water soluble

Novos monômeros obtidos a partir do metacrilato de glicidila, bisfenol A e 4, 4 isopropilidenodicicloexanol : síntese, caracterização estrutural e propriedades de compósitos para utilização em resinas de restauração dental

Nowadays, composite resins are the direct restorative materials more important in dental clinical performance, due to their versatility and aesthetic excellence. Bis-GMA (2,2-bis[4(2-hydroxy-3-metacryloxypropoxy)phenil]propane) is the base monomer more frequently used in restorative composite resins. However, this monomer presents some disadvantages, such as high viscosity and two aromatic rings in its structure that can promote allergic reactions to the humans. In this work, the main purpose was to synthesize new monomers from glycidyl methacrylate to use in dental restorative materials. Structural characterization of the monomers was carried out through FTIR and NMR 1H, and eight composites were produced from the new monomers, by addition of silane-treated alumino silicate particles (inorganic filler) and a photocuring system (camphorquinone and ethyl 4-dimethylaminebenzoate). The composites were analyzed by environmental scanning electronic microscopy and the water sorption and solubility, compressive strength and elastic modulus were determined. A commercial composite resin [Z100 (3M)] was used to comparison effect. The new composites presented general characteristics similar to the commercial ones; however, they didn t present the properties expected. This behavior was attributed to the lower degree of monomer reaction and to the granulometry and size distribution of the mineral filler in the polymeric matrix

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products