Poly molecular weight effects

Concentration and Molecular Weight Effects. The viscosity of aqueous solutions of poly(ethylene oxide) depends on the concentration of the polymer solute, the molecular weight, the solution temperature, concentration of dissolved inorganic salts, and the shear rate. Viscosity increases with concentration and this dependence becomes more pronounced with increasing molecular weight. This combined effect is shown in Figure 3, in which solution viscosity is presented as a function of concentration for various molecular weight polymers. 

Fig. 22. Molecular weight effect of synthetic polymer adsorption. Molecular weight (MW) distribution of poly(vinyl chloride) in solution and in the adsorbed layer at equilibrium. Note that the adsorbed material has a higher average MW than the bulk solution (from Ref.1001, p. 120)...

Rebar VA, Santore MM. Molecular weight effects and the sequential dynamic nature of poly(ethyleneoxide) adsorption on silica from polydisperse aqueous solution. Macromolecules 1996 29 6273—6283. 

Tsuji, H., Ikada, Y., 1996. Blends of isotactic and atactic poly(lac-tide)s 2. Molecular-weight effects of atactic component on crystallization and morphology of equimolar blends from the melt. Polymer 37, 595—602. 

Zhao, B., Haasch, R. T., Maclaren, S. (2004). Solvent-induced self-assembly of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica Substrates molecular weight effect. Journal of the American Chemical Society, 126, 6124-6134. 

Tucker PS, Barlow JW, Paul DR. Molecular-weight effects on phase-behavior of blends of poly(phenylene oxide) with styrenic triblock copolymers. Macromolecules 1988 21 2794-800. 

We shall be interested in determining the effect of electrolytes of low molecular weight on the osmotic properties of these polymer solutions. To further simplify the discussion, we shall not attempt to formulate the relationships of this section in general terms for electrolytes of different charge types-2 l, 2 2, 3 1, 3 2, and so on-but shall consider the added electrolyte to be of the 1 1 type. We also assume that these electrolytes have no effect on the state of charge of the polymer itself that is, for a polymer such as, say, poly (vinyl pyridine) in aqueous HCl or NaOH, the state of charge would depend on the pH through the water equilibrium and the reaction... 

The molecular weight of a polymer can be controlled through the use of a chain-transfer agent, as well as by initiator concentration and type, monomer concentration, and solvent type and temperature. Chlorinated aUphatic compounds and thiols are particularly effective chain-transfer agents used for regulating the molecular weight of acryUc polymers (94). Chain-transfer constants (C at 60°C) for some typical agents for poly(methyl acrylate) are as follows (87) ... 

Derivatives of hemicellulose components have properties similar to the ceUulosic equivalents but modified by the effects of thek lower molecular weight, more extensive branching, labile constituents, and more heterogeneous nature. Acetates, ethers, carboxymethylxylan (184), and xylan—poly(sodium acrylate) (185) have been prepared. 

T is the glass-transition temperature at infinite molecular weight and is the number average molecular weight. The value of k for poly(methyl methacrylate) is about 2 x 10 the value for acrylate polymers is approximately the same (9). A detailed discussion on the effect of molecular weight on the properties of a polymer may be found in Reference 17. 

Bulk Polymerization. This is the method of choice for the manufacture of poly(methyl methacrylate) sheets, rods, and tubes, and molding and extmsion compounds. In methyl methacrylate bulk polymerization, an auto acceleration is observed beginning at 20—50% conversion. At this point, there is also a corresponding increase in the molecular weight of the polymer formed. This acceleration, which continues up to high conversion, is known as the Trommsdorff effect, and is attributed to the increase in viscosity of the mixture to such an extent that the diffusion rate, and therefore the termination reaction of the growing radicals, is reduced. This reduced termination rate ultimately results in a polymerization rate that is limited only by the diffusion rate of the monomer. Detailed kinetic data on the bulk polymerization of methyl methacrylate can be found in Reference 42. 

Tempera.ture Effect. Near the boiling point of water, the solubiUty—temperature relationship undergoes an abmpt inversion. Over a narrow temperature range, solutions become cloudy and the polymer precipitates the polymer caimot dissolve in water above this precipitation temperature. In Figure 4, this limit or cloud point is shown as a function of polymer concentration for poly(ethylene oxide) of 2 x 10 molecular weight. 

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