Poly polyacid reactions

The polyelectrolyte cements are modern materials that have adhesive properties and are formed by the cement-forming reaction between a poly(alkenoic acid), typically poly(acrylic acid), PAA, in concentrated aqueous solution, and a cation-releasing base. The base may be a metal oxide, in particular zinc oxide, a silicate mineral or an aluminosilicate glass. The presence of a polyacid in these cements gives them the valuable property of adhesion. The structures of some poly(alkenoic acid)s are shown in Figure 5.1. 

Spontaneous polymerization of 4-vinyl pyridine in the presence of polyacids was one of the earliest cases of template polymerization studied. Vinyl pyridine polymerizes without an additional initiator in the presence of both low molecular weight acids and polyacids such as poly(acrylic acid), poly(methacrylic acid), polyCvinyl phosphonic acid), or poly(styrene sulfonic acid). The polyacids, in comparison with low molecular weight acids, support much higher initial rates of polymerization and lead to different kinetic equations. The authors suggested that the reaction was initiated by zwitterions. The chain reaction mechanism includes anion addition to activated double bonds of quaternary salt molecules of 4-vinylpyridine, then propagation in the activated center, and termination of the growing center by protonization. The proposed structure of the product, obtained in the case of poly(acrylic acid), used as a template is ... 

The ratio m/n depends on the reaction conditions. One cannot exclude the possibility of branched structure. As a consequence of such mechanism of the reaction in the presence of polyacids used as templates, two types of units can be expected in the product. For instance, if poly(acrylic acid) is used as a template, the structure is ... 

Application of classical type of kinetic equations to the template polymerization was demonstrated by Kabanov at al It was shown that 4-vinylpyridine, in the presence of poly(methacrylic acid), poly(acrylic acid), poly(l-glutamic acid), and polyphosphate, polymerizes according to the classical equation and the order of reaction with respect to the monomer is 2 as demonstrated in the Figure 8.1. In log-log coordinates, for the all sets of polymerizations, experimental points fit straight lines. In the same paper dependence of the initial rate on the molar ratio of acid to monomer was examined. This relationship is shown on the Figure 8.2. The rate of polymerization in the presence of the poly(acrylic acid) is much higher than that for the low molecular analogue (acetic acid). The polymerization rate riches its maximum for the molar ratio [acid]/[monomer] 2. The authors found kinetic equation for template polymerization of 4-vinylpyridine in the presence of different polyacids in the form ... 

Zinc polycarboxylate, the first polyelectrolyte dental material, was developed and used as early as 1968 [124]. These materials are formed by the reaction of a zinc oxide powder with an aqueous solution of poly(acrylic acid). The zinc ions cross-link the polyacid chains and form a cement. A few years after the development of zinc polycarboxylate cements, Wilson and Kent introduced the first glass-ionomer cement (GIC) [125]. Glass-ionomer cements are formed... 

The reaction between poly-4-vinylpyridine and PAA in water-ethanol (1 1 by volume) solutions has been investigated by calorimetry,2). This reaction proceeds without the release of H+ or OH- ions. As the heat of dissociation of the polyacid and the heat of formation of ionic bonds between macromolecular components are near zero, the protonation heats of PVPy at different pH both in the presence or absence of PAA have been measured. It has been found that in neutral solutions the heats of polyvinylpyridine protonation in the presence of PAA considerably exceeds the corresponding values in the absence of PAA, i.e. a considerable portion of pyridine rings is protonated in the polyelectrolyte complexes (Fig. 12). This may be caused only by the cooperative trasfer of the proton from the PAA carboxy group to the pyridine ring. Similar reactions cannot occur between low molecular model substances and neither when only one component is a polymer. 

Electrically neutral substituents in macromolecular chains exhibit no peculiarities with respect to low-molecular-weight compounds in terms of constitution, nomenclature, or, in general, modes of reaction. Polymers with substituents having ionizable bonds are called polyelectrolytes. Polyelectrolytes can dissociate to form a polyion and an oppositely charged gegenion. They can be polyacids, such as poly(acrylic acid)... 

Poly(acrylic acid) and poly(methacrylic acid) undergo reactions characteristic of carboxylic acids. Neutralization of aqueous solutions of the polyacids by bases such as sodium hydroxide is of interest since it causes viscosity changes which demonstrate the presence of two different molecular conformations. Ordinarily, aqueous solutions of the polyacids have low viscosities since the polymer is tightly coiled, being only slightly ionized. As sodium hydroxide is added more and more carboxy groups become ionized mutual repulsion of... 

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