Glass transition temperature solutions

In addition to thermodynamic appUcations, 62 values have also been related to the glass transition temperature of a polymer, and the difference 62-61 to the viscosity of polymer solutions. The best values of 6 have been analyzed into group contributions, the sum of which can be used to estimate 62 for polymers which have not been characterized experimentally. 

Solution Polymers. Acryflc solution polymers are usually characterized by their composition, solids content, viscosity, molecular weight, glass-transition temperature, and solvent. The compositions of acryflc polymers are most readily determined by physicochemical methods such as spectroscopy, pyrolytic gas—liquid chromatography, and refractive index measurements (97,158). The solids content of acryflc polymers is determined by dilution followed by solvent evaporation to constant weight. Viscosities are most conveniently determined with a Brookfield viscometer, molecular weight by intrinsic viscosity (158), and glass-transition temperature by calorimetry. 

The Arrhenius equation holds for many solutions and for polymer melts well above their glass-transition temperatures. For polymers closer to their T and for concentrated polymer and oligomer solutions, the WiUiams-Landel-Ferry (WLF) equation (24) works better (25,26). With a proper choice of reference temperature T, the ratio of the viscosity to the viscosity at the reference temperature can be expressed as a single universal equation (eq. 8) ... 

Glass-Transition Temperature. The T of PVP is sensitive to residual moisture (75) and unreacted monomer. It is even sensitive to how the polymer was prepared, suggesting that MWD, branching, and cross-linking may play a part (76). Polymers presumably with the same molecular weight prepared by bulk polymerization exhibit lower T s compared to samples prepared by aqueous solution polymerization, lending credence to an example, in this case, of branching caused by chain-transfer to monomer. 

The glass-transition temperature in amorphous polymers is also sensitive to copolymerization. Generally, T of a random copolymer falls between the glass-transition temperatures of the respective homopolymers. For example, T for solution-polymerized polybutadiene is —that for solution-polymerized polystyrene is -HlOO°C. A commercial solution random copolymer of butadiene and styrene (Firestone s Stereon) shows an intermediate T of —(48). The glass-transition temperature of the random copolymer can sometimes be related simply as follows ... 

SBR is produced by addition copolymerization of styrene and butadiene monomers in either emulsion or solution process. The styrene/butadiene ratio controls the glass transition temperature (To) of the copolymer and thus its stiffness. T ... 

SBR latices are high-solids dispersions of rubber particles in water, the viscosity and rheology of which are, in general, independent of the polymer properties, unlike solutions. They offer a wide range of molecular weight and glass transition temperature. Three classes of SBR latices are available in the market. 

The presence of ether linkages in the polymer molecule imparts chain flexibility, lowers glass transition temperature, and enhances solubility while maintaining the desired high temperature characteristics [192]. Recently, polyether imines were prepared by the reaction of different diamines with 4,4 -[l,4-phenylene bis(oxy)] bisbenzaldehyde [184]. The polymers synthesized by the solution method were yellow to white in color and had inherent viscosities up to 0.59 dl/g in concentrated H2SO4. Some of these polyimines can be considered as... 

Polymeric binder can be added to the network either as an aqueous latex dispersion or as a solution that should be dried prior to lamination in this process. In either case, the polymer should form a film and join adjacent fibers together and thus improve the stress transfer characteristics of the fibrous network. Provided that the proper film forming conditions are available, the property profile of the bonded network is determined to a significant degree by the properties of the polymeric binder at the temperature of use [20,22]. For example, if a softer type of product is desired, a binder with a relatively low glass transition temperature Tg) is often chosen. 

Park et al. [20] reported on the synthesis of poly-(chloroprene-co-isobutyl methacrylate) and its compati-bilizing effect in immiscible polychloroprene-poly(iso-butyl methacrylate) blends. A copolymer of chloroprene rubber (CR) and isobutyl methacrylate (iBMA) poly[CP-Co-(BMA)] and a graft copolymer of iBMA and poly-chloroprene [poly(CR-g-iBMA)] were prepared for comparison. Blends of CR and PiBMA are prepared by the solution casting technique using THF as the solvent. The morphology and glass-transition temperature behavior indicated that the blend is an immiscible one. It was found that both the copolymers can improve the miscibility, but the efficiency is higher in poly(CR-Co-iBMA) than in poly(CR-g-iBMA),... 

Alloys can be classified as either homogeneous or heterogeneous. The former can be depicted as a solution with a single phase or single glass-transition temperature (7 ). A heterogeneous alloy has both continuous... 

Orientation, wet stretching For plastics whose glass transition temperature (Tg) is above their decomposition temperature, orientation can be accomplished by swelling them temporarily with plasticizing liquids to lower their Tg of the total mass, particularly in solution processing. As an example, cellulose viscous films can be drawn during coagulation. Final removal of the solvent makes the orientation permanent. 

The glass transition temperature Tgc of the composite corresponds to the intersection of the first and the last part of the curve, or it is the solution of the Equation Alcl = A1o3, from which, after some algebra, one obtains ... 

Liquid crystalline solutions as such have not yet found any commercial uses, but highly orientated liquid crystal polymer films are used to store information. The liquid crystal melt is held between two conductive glass plates and the side chains are oriented by an electric field to produce a transparent film. The electric field is turned off and the information inscribed on to the film using a laser. The laser has the effect of heating selected areas of the film above the nematic-isotropic transition temperature. These areas thus become isotropic and scatter light when the film is viewed. Such images remain stable below the glass transition temperature of the polymer. 

Reactive compatibilization can also be accomplished by co-vulcanization at the interface of the component particles resulting in obliteration of phase boundary. For example, when cA-polybutadiene is blended with SBR (23.5% styrene), the two glass transition temperatures merge into one after vulcanization. Co-vulcanization may take place in two steps, namely generation of a block or graft copolymer during vulcanization at the phase interface and compatibilization of the components by thickening of the interface. However, this can only happen if the temperature of co-vulcanization is above the order-disorder transition and is between the upper and lower critical solution temperature (LCST) of the blend [20]. 

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