Equilibrium distribution between segments

Analysis of the poly(methyl methacrylate) sequences obtained by anionic polymerization was undertaken at the tetrad level in terms of two different schemes (10) one, a second-order Markov distribution (with four independent conditional probabilities, Pmmr Pmrr, Pmr Prrr) (44), the other, a two-state mechanism proposed by Coleman and Fox (122). In this latter scheme one supposes that the chain end may exist in two (or more) different states, depending on the different solvation of the ion pair, each state exerting a specific stereochemical control. A dynamic equilibrium exists between the different states so that the growing chain shows the effects of one or the other mechanism in successive segments. The deviation of the experimental data from the distribution calculated using either model is, however, very small, below experimental error, and, therefore, it is not possible to make a choice between the two models on the basis of statistical criteria only. 

Other lattice polymer efforts have been based on the self-consistent fleld theory of Scheutjens and Fleer (150,151). This approach differs from previously posed statistical theories for chain molecules in that the partition function is expressed in terms of the distribution of chain conformations rather than the distribution of segment densities. The equilibrium distribution of chain (ie model protein) conformations is thus calculable. Quantities predicted using this approach include the force between parallel plates coated with protein (152,153), the adsorption isotherm (154,155), and the segmental density distribution (154-157). 

Alexander s treatment, the grafted brush is assumed to have a uniform segment density (step function distribution), and each chain to consist of connected semidilute blobs. The osmotic repulsion between blobs tends to stretch the chains, while the elastic free energy of the chains has the opposite effect. For a single brush, the minimization of the overall free energy with respect to the brush thickness yields the equilibrium brush thickness L0, given by... 

For densely cross-linked networks, values of equilibrium modulus higher than 10 Pa are obtained. In this case the molecular weight between cross-linking points may become so low that Gaussian distributions of the segments between cross-links can no longer be assumed. The fact, however, that the modulus is approximately proportional to absolute temperature... 

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