Polymer chain rotation .

In a real polymer chain, rotation around backbone bonds is likely to be hindered by a potential energy barrier of height AEr. If AEr < RT, the population of the... 

Figure 17.11 Proposed structure of active site and dormant site for styrene polymerization (a) Active site (b) dormant site by the coordination error of monomer (c) dormant site by the polymer chain rotation...

The diffusion coefficients in a number of w-alkanes have been investi-gated, which show the influence of the rotator phase assisting the motion of the polymer chains. Rotator phases have been reported in chains with as... 

Figure 3.12 The effect of shear rates on polymer chain rotation. Hydrodynamic work is converted into heat, resulting in an increased solution viscosity.

Growing polymer chain > = Rotation prevented by agostic... 

This kind of perfect flexibility means that C3 may lie anywhere on the surface of the sphere. According to the model, it is not even excluded from Cj. This model of a perfectly flexible chain is not a realistic representation of an actual polymer molecule. The latter is subject to fixed bond angles and experiences some degree of hindrance to rotation around bonds. We shall consider the effect of these constraints, as well as the effect of solvent-polymer interactions, after we explore the properties of the perfectly flexible chain. Even in this revised model, we shall not correct for the volume excluded by the polymer chain itself. 

A still more intricate pattern of potential energy may be expected if the repeat units of the polymer chain carry other substituents, such as the phenyl groups in polystyrene, but these examples establish the general method for quantitatively describing the effects of steric hindrance on rotation. 

In order for a plasticizer to enter a polymer stmcture the polymer should be highly amorphous. Crystalline nylon retains only a small quantity of plasticizer if it retains its crystallinity. Once it has penetrated the polymer the plasticizer fills free volume and provides polymer chain lubrication, increa sing rotation and movement. 

Polar substituents such as chlorine increase the interchain forces and hinder free rotation of the polymer chain. Hence polydichlorostyrenes have softening points above 100°C. One polydichlorostyrene has been marketed commercially as Styramic HT. Such polymers are essentially self-extinguishing, have heat distortion temperatures of about 120°C and a specific gravity of about 1.40. 

Even in the absence of flow, a polymer molecule in solution is in a state of continual motion set forth by the thermal energy of the system. Rotation around any single bond of the backbone in a flexible polymer chain will induce a change in conformation. For a polyethylene molecule having (n + 1) methylene groups connected by n C — C links, the total number of available conformations increases as 3°. With the number n encompassing the range of 105 and beyond, the number of accessible conformations becomes enormous and the shape of the polymers can only be usefully described statistically. 

Pulsed deuteron NMR is described, which has recently been developed to become a powerftd tool for studying molectdar order and dynamics in solid polymers. In drawn fibres the complete orientational distribution function for the polymer chains can be determined from the analysis of deuteron NMR line shapes. By analyzing the line shapes of 2H absorption spectra and spectra obtained via solid echo and spin alignment, respectively, both type and timescale of rotational motions can be determined over an extraordinary wide range of characteristic frequencies, approximately 10 MHz to 1 Hz. In addition, motional heterogeneities can be detected and the resulting distribution of correlation times can directly be determined. 

It has been shown [56] that if we measure the areas under the approach and retract curves of the force-distance plot we can get quantitative values of the resilience. Resilience is closely related to the ability of the polymer chain to rotate freely, and thus will be affected by rate and extent of deformation, as well as temperature. Different materials will respond differently to changes in these variables [46] hence, changing the conditions of testing will result in a change in absolute values of resilience and may even result in a change in ranking of the materials. Compared to more traditional methods of resilience measurement such as the rebound resiliometer or a tensUe/compression tester. 

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