Network-forming polymers

As discussed in the previous section, this book focusses on reactive polymer systems, from network-forming polymers to reactively modified polymer systems. Network polymers may be defined as polymer systems that contain chemical or physical networks between the constituent molecules of the system. Within the term reactively modified polymers we include polymer systems that have been modified by grafting, chemical reaction or high-energy radiation. Typically network or reactively modified polymers are manufactured by various... 

Thermosets are network-forming polymers. Unlike thermoplastic polymers, whose processing requires only physical changes such as melting, thermosets are distinguished by the bulk chemical reactions that are involved in their use. 

Scott, J.E., Cummings, C., Brass, A., Chen, Y. (1991) Secondary and tertiary structures of hyaluronan in aqueous solution, investigated by rotary shadowing-electron microscopy and computer simulation. Hyaluronan is a very efficient network-forming polymer. Biochemical Journal, 274, 699-705. 

We briefly summarize a lattice theory of network-forming polymer solutions [5, 6]. Let (/>(j I) be the volume fraction of the clusters of type (j I). The free energy change on passing from the standard reference states (polymers and solvent molecules being separated in hypothetical crystalline states) to the final solution, at equilibrium with respect to cluster formation, is given by the expression... 

Coagents ate often used with peroxides to increase the state of cure. Some coagents, such as polybutadiene or multifimctional methacrylates, are used at high levels to form polymer grafts or interpenetrating networks. Other coagents such as triaHyl cyanurate, triaHyl trimelHtate, and y /i -phenjiene bismaleimide are used at low levels to reduce the tendency of the polymer to degrade by chain scission. 

Peroxides or other additives, eg, chlorinated paraffin, may also cause the thermoplastic resin to cross-link with the siloxanols. In this case, a tme interpenetrating polymer network forms, in which both phases are cross-linked. 

Gels are viscoelastic bodies that have intercoimected pores of submicrometric dimensions. A gel typically consists of at least two phases, a soHd network that entraps a Hquid phase. The term gel embraces numerous combinations of substances, which can be classified into the following categories (2) (/) weU-ordered lamellar stmctures (2) covalent polymeric networks that are completely disordered (2) polymer networks formed through physical aggregation that are predominantly disordered and (4) particular disordered stmctures. 

A polymer is a large molecule built up by the repetition of small, simple chemical units. In some cases the repetition is linear while in other cases the chains are branched or interconnected to form three-dimensional networks. The polymer can be formed not only through linear addition, but also through condensation of similar units as well. 

Crosslinked polymers have two or more polymer chains linked together at one or more points other than their ends. The network formed improves the mechanical and physical properties of the polymer. 

The second step is the condensation reaction between the methylolphe-nols with the elimination of water and the formation of the polymer. Crosslinking occurs hy a reaction between the methylol groups and results in the formation of ether bridges. It occurs also by the reaction of the methylol groups and the aromatic ring, which forms methylene bridges. The formed polymer is a three-dimensional network thermoset ... 

Rubber-modified amorphous polymers The brittleness of amorphous polymers has been a hindrance in their commercial development. Fortunately, for reasons still not fully understood, the addition of rubbery polymers as dispersed droplets, or sometimes in a network form, into the glassy polymer can often lead to substantial increases in impact strength, albeit usually at... 

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. 

Similarly, a composite of hydroxyapatite and a network formed via cross-linking of chitosan and gelatin with glutaraldehyde was developed by Yin et al. [ 169]. A porous material, with similar organic-inorganic constituents to that of natural bone, was made by the sol-gel method. The presence of hydroxyapatite did not retard the formation of the chitosan-gelatin network. On the other hand, the polymer matrix had hardly any influence on the high crystallinity of hydroxyapatite. 

IPNs are found in many applications though this is not always recognised. For example conventional crosslinked polyester resins, where the polyester is unsaturated and crosslinks are formed by copolymerisation with styrene, is a material which falls within the definition of an interpenetrating polymer network. Experimental polymers for use as surface coatings have also been prepared from IPNs, such as epoxy-urethane-acrylic networks, and have been found to have promising properties. 

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. 

Not until the 1940 s did suitable methods, both experimental and theoretical, become available for reducing the constitution of polymers, including the nonlinear, network-forming types, to tractable quantitative terms. Since such means are a prerequisite to the quantitative treatment of polymer properties in relation to constitution, advances in this direction necessarily were delayed. 

If chain transfer of the radical center to a previously formed polymer molecule is followed ultimately by termination through coupling with another similarly transferred center, the net result of these two processes is the combination of a pair of previously independent polymer molecules. T. G. Fox (private communication of results as yet unpublished) has suggested this mechanism as one which may give rise to network structures in the polymerization of monovinyl compounds. His preliminary analysis of kinetic data indicates that proliferous polymerization of methyl acrylate may be triggered by networks thus generated. 

According to Ref. [12], template for synthesis of nanomaterials is defined as a central structure within which a network forms in such a way that removal of this template creates a filled cavity with morphological or stereochemical features related to those of the template. The template synthesis was applied for preparation of various nanostructures inside different three-dimensional nanoporous structures. Chemically, these materials are presented by polymers, metals, oxides, carbides and other substances. Synthetic methods include electrochemical deposition, electroless deposition, chemical polymerization, sol-gel deposition and chemical vapor deposition. These works were reviewed in Refs. [12,20]. An essential feature of this... 

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... 

Multimolecular helical inclusion networks formed by rigid alicyciic diols, urea, deoxycholic acid, and tri-o-thymotide are described and contrasted, followed by discussion of DNA intercalates, amylose compounds, and other inclusion systems formed by helical polymers. 

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. 

Thermoset polymers (sometimes called network polymers) can be formed from either monomers or low MW macromers that have a functionality of three or more (only one of the reagents requires this), or a pre-formed polymer by extensive crosslinking (also called curing or vulcanisation this latter term is only applied when sulfur is the vulcanising or crosslinking agent.) The crosslinks involve the formation of chemical bonds — covalent (e.g., carbon-carbon bonds) or ionic bonds. 

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