Solution properties of flexible chain

Table 8). This permits the interpretation of experimental data by using the electro-optical properties of flexible-chain polymers in terms of a worm-like chain model However, EB in solutions of polyelectrolytes is of a complex nature. The high value of the observed effect is caused by the polarization of the ionic atmosphere surrounding the ionized macromolecule rather than by the dipolar and dielectric structure of the polymer chain. This polarization induced by the electric field depends on the ionic state of the solution and the ionogenic properties of the polymer chain whereas its dependence on the chain structure and conformation is slight. Hence, the information on the optical, dipolar and conformational properties of macromoiecules obtained by using EB data in solutions of flexible-chain polyelectrolytes is usually only qualitative. Studies of the kinetics of the Kerr effect in polyelectrolytes (arried out by pulsed technique) are more useful since in these... 

An extensive investigation of the dilute solution properties of several acrylate copolymers has been reported (80). The behavior is typical of flexible-backbone vinyl polymers. The length of the acrylate ester side chain has Httle effect on properties. 

Two approaches to the attainment of the oriented states of polymer solutions and melts can be distinguished. The first one consists in the orientational crystallization of flexible-chain polymers based on the fixation by subsequent crystallization of the chains obtained as a result of melt extension. This procedure ensures the formation of a highly oriented supramolecular structure in the crystallized material. The second approach is based on the use of solutions of rigid-chain polymers in which the transition to the liquid crystalline state occurs, due to a high anisometry of the macromolecules. This state is characterized by high one-dimensional chain orientation and, as a result, by the anisotropy of the main physical properties of the material. Only slight extensions are required to obtain highly oriented films and fibers from such solutions. 

Usually, crystallization of flexible-chain polymers from undeformed solutions and melts involves chain folding. Spherulite structures without a preferred orientation are generally formed. The structure of the sample as a whole is isotropic it is a system with a large number of folded-chain crystals distributed in an amorphous matrix and connected by a small number of tie chains (and an even smaller number of strained chains called loaded chains). In this case, the mechanical properties of polymer materials are determined by the small number of these ties and, hence, the tensile strength and elastic moduli of these polymers are not high. 

Robinson, G., Ross-Murphy, S. B., and Morris, E. R. (1982). Viscosity-molecular weight relationships, intrinsic chain flexibility, and dynamic solution properties of guar galactomannan. Carbohydr. Res. 107 17-32. 

Cyclolinear structure of synthesized POCS-4, POCS-5 and POCS-6 polymers was proved by hydro-dynamic study of properties of their solutions [56], The expected results of these investigations should indicate the predominant influence of the equilibrium flexibility of macromolecules and other specific properties of polymeric chains in block on occurrence of the thermotropic mesophase in cyclolinear organosiloxanes. 

Several papers compare the properties of sulfobetaine (meth)acrylic polymers. NMR spectra and solution properties of 23a and 23b [59,60] are correlated with data from the corresponding polycarbobetaines [26]. The photophysical and solution properties of pyrene-labeled 23c were studied in terms of fluorescence emission. Addition of surfactants induces the formation of mixed micelles in aqueous solution [61]. Excluded volume effects of the unlabeled polymer were measured by light scattering [62], its adsorption on silica was studied by adsorbance measurement and ellipsometry [62,63], and the electrostimulated shift of the precipitation temperature was followed at various electric held intensities [64]. Polysulfobetaines may accelerate interionic reactions, e.g., oxidation of ferrocyanide by persulfate [65]. The thermal and dielectric properties of polysulfobetaines 23d were investigated. The flexible lateral chain of the polymers decreased Tg, for which a linear relationship with the number of C atoms was shown [66,67]. 

Flow birefringence is a widely used method for the investigation of optical, conformational and hydrodynamic properties of molecules of flexible-chain polymers in solution. The experimental and eoretical material avaEable is very comprehensive and has been considered in many reviews providing the basis for the... 

The situation is more favourable for the study of EB in solutions of flexible-chain polyelectrolytes for which the value of K may be higher by several orders of msg-nitude than for molecules bearing no charge This seems plausible since the uncoiling of a flexible-chain polyion by electrostatic repulsion of ionc enic groups increases the persistent length of the chain and the optical and hydrodynamic properties of the molecule approach those of a rigid-chain polymer ... 

Solution characterization of poly(phosphazenes) is an important area of concern. Some of these studies were mentioned above in conjunction with the polymer synthesis. Electrooptical properties (Kerr effect) of PTFE have been examined. The Kerr constant was significantly higher than those of flexible chain polymers which was suggested to result... 

Comparison of the values of C for the polymers with a flexible C-C or Si-O-Si backbone (as occurs in siloxane polymers) of about 6-10 with the value for the rigid-rod polymer of 125 demonstrates the fundamental difference in the solution properties of the latter polymer which has a highly extended conformation characteristic of liquid-crystal polymers. Equation (1.5) also shows that for a real chain the value of Rq would be expected to increase as the half power of the number of repeat units, i.e. the degree of polymerization, DP. ... 

This book is dedicated to the study of the static properties of flexible polymers in solution its aim is to present the vast progress made by both theory and experiment over the last fifteen years. It might be asked why this question has aroused such lively interest and why great effort has been expended in this domain. What has progressively appeared is that long polymer chains, despite the variety in their chemical composition and physical properties, behave in a universal manner when in solution. Recognition of this fact is on a par with the formulation of the critical-system concept of which the polymer in solution is a very good example. 

Reprinted from Viscosity - Molecular Weight Relationships, Intrinsic Chain Flexibility, and Dynamic Solution Properties of Guar Galactoman-nan , Copyright, 1982, with permission from Elsevier)... 

The simplicity of (2.25) is to be contrasted with the complexity of the exact P(R n) for realistic models of flexible chains for all R (and for small n). When dealing with the complicated problems of nonideal polymer solutions, etc., it is therefore customary to replace the real polymer chain by the so-called Kuhn effective random flight chain. An effective chain is one with N (in general different from n) links of size A5 such that N lS.s = L and (R ) is as given by (2.29). This substitution of a real chain by its equivalent chain is often a necessity so that we may separate errors in principle from errors arising from a poor mathematical approximation to the exact P(R n) when dealing with problems which are not exactly soluble. This equivalent chain therefore provides us with reasonable approximations to the properties of real polymer chains, provided the physical properties of interest do not depend heavily upon those chain configurations with i > L or upon chain properties over small distances for which the real chain is stiff. 

Abe et ah have studied the conformational characteristics of a series of poly[oxy(-l-alkylethylenes)]. In the first paper a comparison of the statistical weights of various conformations in poly(propylene oxide), deduced from the solution properties of isotactic and atactic chains, were compared with conformational weights derived from a potential-energy surface, and an anomeric effect identified with a discrepancy between the two. Flexible side-chains influence the main chain in a manner which is expressible in the statistical weight matrices. The dimensions of these chains are strongly influenced by their tacticity. Polymer chains containing both sulphur and oxygen heteroatoms have received the attention of... 

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