Homopolymers, interactions

For h < 26, the situation is much more complex. One not only needs to know 4>(z) for each layer, but how 4>(z) changes as the two particles approach, i.e. 4>(z,h) this may well depend on the time-scale of the approach, i.e. the equilibrium path may not be followed. Scheutjens and Fleer (25) in an extension of their model for polymer adsorption have analysed the situation for two interacting uncharged parallel, flat plates carrying adsorbed, neutral homopolymer, interacting under equilibrium conditions. Only a semi-quantitative picture will be presented here. 

Critical micelle concentration ( >cmc is expected to decrease strongly with diminished diblock asymmetry rc as low rc values favor easier creation of highly curved micelle interfaces. Theory of micelle formation [231,260] also indicates that the overall copolymer degree of polymerization Nc, as well as the anchor -homopolymer interaction parameter %AP have to be considered to explain properly the onset of micelle segregation as observed by Shull et al. [260]. Using this theory, experimenters are able to choose systems where only individual copolymers segregate. 

This type of reaction is one in which a homopolymer interacts with a polyfunctional agent to build molecular weight by chain extension or branching. 

The Adsorption (qv) of polyelectrolytes from solution onto solid, liquid, or gas interfaces defines a vast field, one that encompasses innumerable phenomena and many technologies. To simplify, only the grossest and most common issues are introduced here (268-270). Figure 20 displays pictorially how flexible polyelectrolyte homopolymers interact with a flat, charged surface (269). The left-hand side of this cartoon indicates behavior at low Cg, a condition typically dominated... 

It distinguishes between three different interactions in the system, one for each solvent-homopolymer interaction (gxa and gxp) and a third for the comonomer a—fi interaction (g ), but neglects differences in size and shape between the various units. If allowance for such differences is made, the strictly regular treatment leads to the following expression for A, which replaces the term Eq. (15) [84] ... 

Other A- and U (or T)-containing complexes. We shall consider here ribo- and deoxyribopolymers with alternating sequences, such as poly(dA-dT), as well as homopolymer interactions, such as poly(dA) poly(dT) or poly(rA) poly(dT). This series of compounds had been designed and studied... 

LefSvre N et al. Self-assembly in thin films of mixtures of block copolymers and homopolymers interacting by hydrogen bonds. Macromolecules 2010 43(18) 7734—7743. 

Similariy, van der Waals complexes of PMMA form most easily in protic solvents such as acetone and are disrupted in carbon tetrachloride or methylene chloride. In the absence of solvent, complexes are formed when heteropolymer interaction free energies are stronger than homopolymer interaction free energy. In the later case, phase separation would occur leading to separate homopolymer domains. 

In homopolymers all tire constituents (monomers) are identical, and hence tire interactions between tire monomers and between tire monomers and tire solvent have the same functional fonn. To describe tire shapes of a homopolymer (in the limit of large molecular weight) it is sufficient to model tire chain as a sequence of connected beads. Such a model can be used to describe tire shapes tliat a chain can adopt in various solvent conditions. A measure of shape is tire dimension of tire chain as a function of the degree of polymerization, N. If N is large tlien tire precise chemical details do not affect tire way tire size scales witli N [10]. In such a description a homopolymer is characterized in tenns of a single parameter tliat essentially characterizes tire effective interaction between tire beads, which is obtained by integrating over tire solvent coordinates. 

The basic features of folding can be understood in tenns of two fundamental equilibrium temperatures that detennine tire phases of tire system [7]. At sufficiently high temperatures (JcT greater tlian all tire attractive interactions) tire shape of tire polypeptide chain can be described as a random coil and hence its behaviour is tire same as a self-avoiding walk. As tire temperature is lowered one expects a transition at7 = Tq to a compact phase. This transition is very much in tire spirit of tire collapse transition familiar in tire theory of homopolymers [10]. The number of compact... 

Finally, we briefly mention interactions due to adsorbing polymers. Block copolymers, witli one block strongly adsorbing to tire particles, have already been mentioned above. Flere, we focus on homopolymers tliat adsorb moderately strongly to tire particles. If tliis can be done such tliat a high surface coverage is achieved, tire adsorbed polymer layer may again produce a steric stabilization between tire particles. 

PRISM (polymer reference interaction-site model) method for modeling homopolymer melts... 

Polymer alloys are physical mixtures of structurally different homopolymers or copolymers. The mixture is held together by secondary intermolecular forces such as dipole interaction, hydrogen bonding, or van der Waals forces. 

There are many examples known where a random copolymer Al, comprised of monomers 1 and 2, is miscible with a homopolymer B, comprised of monomer 3, even though neither homopolymer 1 or 2 is miscible with homopolymer 3, as illustrated by Table 2. The binary interaction model offers a relatively simple explanation for the increased likelihood of random copolymers forming miscible blends with other polymers. The overall interaction parameter for such blends can be shown (eg, by simplifying eq. 8) to have the form of equation 9 (133—134). 

Another important feature of some random copolymers is the abihty to achieve miscibility in either a homopolymer or a second random copolymer. This "copolymer effect" has been shown empirically for quite some time, eg, PVC is miscible with random copolymers of ethylene and vinyl acetate (52). Such systems are effective because repulsions between the dissimilar segments in the copolymer are enough to overcome the repulsions between these segments and those of the second component in the mixture. In other words, in the above example, the ethylene units "hate" vinyl acetate units more than either of them "hate" PVC. Thus there is a net negative interaction energy and the two materials are miscible (53). 

When viscometric measurements of ECH homopolymer fractions were obtained in benzene, the nonperturbed dimensions and the steric hindrance parameter were calculated (24). Erom experimental data collected on polymer solubiUty in 39 solvents and intrinsic viscosity measurements in 19 solvents, Hansen (30) model parameters, 5 and 5 could be deterrnined (24). The notation 5 symbolizes the dispersion forces or nonpolar interactions 5 a representation of the sum of 8 (polar interactions) and 8 (hydrogen bonding interactions). The homopolymer is soluble in solvents that have solubility parameters 6 > 7.9, 6 > 5.5, and 0.2 < <5.0 (31). SolubiUty was also determined using a method (32) in which 8 represents the solubiUty parameter... 

The solubility parameter is calculated at 20 MPa and therefore the polymer is swollen by liquids of similar cohesive forces. Since crystallisation is thermodynamically favoured even in the presence of liquids of similar solubility parameter and since there is little scope of specific interaction between polymer and liquid there are no effective solvents at room temperature for the homopolymer. 

It should also be pointed out that the Tg of the soft blocks, which consist of fairly short polymer chains, will be somewhat lower than for a corresponding homopolymer of high molecular weight, for the reasons given in Section 4.2. This effect may, however, be more than compensated by the loss of molecular freedom due to the presence of and interaction with the hard phase polymer present. 

The toughness of interfaces between immiscible amorphous polymers without any coupling agent has been the subject of a number of recent studies [15-18]. The width of a polymer/polymer interface is known to be controlled by the Flory-Huggins interaction parameter x between the two polymers. The value of x between a random copolymer and a homopolymer can be adjusted by changing the copolymer composition, so the main experimental protocol has been to measure the interface toughness between a copolymer and a homopolymer as a function of copolymer composition. In addition, the interface width has been measured by neutron reflection. Four different experimental systems have been used, all containing styrene. Schnell et al. studied PS joined to random copolymers of styrene with bromostyrene and styrene with paramethyl styrene [17,18]. Benkoski et al. joined polystyrene to a random copolymer of styrene with vinyl pyridine (PS/PS-r-PVP) [16], whilst Brown joined PMMA to a random copolymer of styrene with methacrylate (PMMA/PS-r-PMMA) [15]. The results of the latter study are shown in Fig. 9. 

In addition to the abovementioned parameters, various factors such as viscosity of the copolymer and its interaction with the homopolymers also play a major role in the compatibilization process. 

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