Networks of polymers

We noted above that the presence of monomer with a functionality greater than 2 results in branched polymer chains. This in turn produces a three-dimensional network of polymer under certain circumstances. The solubility and mechanical behavior of such materials depend critically on whether the extent of polymerization is above or below the threshold for the formation of this network. The threshold is described as the gel point, since the reaction mixture sets up or gels at this point. We have previously introduced the term thermosetting to describe these cross-linked polymeric materials. Because their mechanical properties are largely unaffected by temperature variations-in contrast to thermoplastic materials which become more fluid on heating-step-growth polymers that exceed the gel point are widely used as engineering materials. 

These four types of forces are responsible for the adaptive behavior of smart gels. The different forces come into play when the network of polymer chains composing a gel is disturbed, (a) Charged ionic regions can attract or repel each other, (b) Nonpolar hydrophobic regions exclude water, (c) Hydrogen bonds may form from one chain to another, (d) Dipole-dipole interactions can attract or repel chains. 

Models of regular structures, such as zeolites, have been extensively considered in the catalysis literature. Recently, Garces [124] has developed a simple model where the complex pore structure is represented by a single void with a shell formed by n-connected sites forming a net. This model was found to work well for zeolites. Since polymer gels consist of networks of polymers, other approaches, discussed later, have been developed to consider the nature of the structure of the gel. 

Many fluids show a decrease in viscosity with increasing shear rate. This behavior is referred to as shear thinning, which means that the resistance of the material to flow decreases and the energy required to sustain flow at high shear rates is reduced. These materials are called pseudoplastic (Fig. 3a and b, curves B). At rest the material forms a network structure, which may be an agglomerate of many molecules attracted to each other or an entangled network of polymer chains. Under shear this structure is broken down, resulting in a shear... 

Traditionally, we create thermoset polymers during step growth polymerization by adding sufficient levels of a polyfunctional monomer to the reaction mixture so that an interconnected network can form. An example of a network formed from trifimctional monomers is shown in Fig. 2.12b). Each of the functional groups can react with compatible functional groups on monomers, dimers, trimers, oligomers, and polymers to create a three-dimensional network of polymer chains. 

When a water-soluble polymer is dissolved in water, a complex network is formed that includes the polymer backbone, free water, and water in various degrees of bonding to the polymer. Depending on the concentration of polymer, its molecular weight, and several other factors, the network of polymer and bound water can assume the volume of the solution. This, of course, leads to the high viscosity that these solutions develop. The volume occupied by the polymer and the associated water in the system are said to be the hydrodynamic volume. As this volume increases because of increases in molecular weight or in the water shell surrounding the molecule, the viscosity of the solution increases. 

Fig. 8. — Partial Model of Primary Cell-Wall in Lupin Hypocotyl, Proposed by Monro and Coworkers.49 [The half of the Figure labeled (A) represents the extensin-hemicellulose network, and the half labeled (B) represents the separate, pectic network, which is believed not to involve the wall glycoprotein (extensin). Thus, the cellulose microfibrils (M) are separately cross-linked by two networks of polymers, the first (A) being composed of the wall glycoprotein and polysaccharide (probably hemicelluloses), and the second (B) being composed of the pectic polymers. These two networks have been separated in the Figure for clarity. This model is tentative and incomplete, as the nature of the linkages between the polymers in these two networks has not yet been identified. The...

We synthesized [13] IPNs composed of polyethylene oxide) (PEO) (polymer A) and poly(N-acryloylpyrrolidine) (PAPy) (polymer B). The IPN was synthesized by simultaneous crosslinked polymerization of APy and PEO. The overall reaction scheme for IPN synthesis by radical polymerization for APy (polymer A) and addition polymerization for PEO (polymer B) is shown in Fig. 3. This pair shows simple coacervation behavior in water. The IPN is constructed from PEO and PAPy networks as shown in Fig. 4. Chemically independent networks of polymer A and polymer B are interlocked and macroscopic phase separation in water swollen states is avoided. 

When the polymer wets the solid (0 = 0), polymer films are thermodynamically stable. For 0 > 0 the films are only metastable. When a thin, metastable film is heated above the glass transition temperature, holes start to form spontaneously, usually at small defects. The holes increase in size until only a network of polymer lines is formed which eventually breaks up into individual droplets (Fig. 7.19) [150], The film stability of films with a thickness of 1-100 nm is determined by long-range surface forces, mainly van der Waals forces [151,268, 294,295],... 

VIRTUALLY CROSSLINKEO/EXTENDED NETWORK of POLYMER PRIMARY CHAINS... 

On A crosslinked polymer composed of a network of polymer 1 chains. 

Co-polymerization of pentaerythritol and two other monomers—an unsaturated acid and benzene 1,3-dicarboxylic acid—gives a network of polymer chains branching out from the quaternary carbon atom at the centre of pentaerythritol. The reaction is simply ester formation by a carbonyl substitution reaction at high temperature (> 200°C). Ester formation between acids and alcohols is an equilibrium reaction but at high temperatures water is lost as steam and the equilibrium is driven over to the right. 

It is not necessary to have quite such a highly branched cross-linking agent to make a network of polymer chains. A triply branched compound is the basis for one of the strongest polymers known— one that we take for granted every time we use the kitchen. It is made by a very simple reaction. 

Gel structures are ubiquitous in foods and responsible for many of their physical properties. The space-filling network of polymers or aggregates provides solidlike properties in the presence of an enormous amormt of water. They are a form of solid water at ambient temperature and in fact they are used to immobilize free water in dietetic products. Gels have been extensively used as model systems to study strue-ture-property relationships due to their simple biphasic nature and the faet that the kinetics of structural changes can be continuously followed by oseiUatory rheometry. 

Because the influence of drying parameters is not the same for all materials, optimal drying conditions vary depending on the final objective volatile retention, preservation of enzymatic activity and avoidance of protein denaturation, fat oxidation or crystallisation. Furthermore, some interactive influences may appear between components, an effect that is positive for protection of labile compounds by a network of polymers as polysaccharides, gums, proteins (Dumoulin and Bimbenet 1998). The phenomena may vary between centre and surface of drops, with some possible segregation by internal movement in the drop. 

Colloids have been described as classic polymer gels, and their dynamics in seawater may be understood in terms of polymer gel theory (Chin et al., 1998). Polymer gels are stable, three-dimensional networks of polymers and seawater (Figure 11). Gels assemble spontaneously from... 

Polymerisation is a process of reacting the same monomer together chemically to form a three-dimensional network of polymer chains. There are many forms of polymerisation... 

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