Chain cross-link

Halogenated Butyl Rubber. Halogenation at the isoprene site ia butyl mbber proceeds by a halonium ion mechanism leading to a double-bond shift and formation of an exomethylene alkyl haUde. Both chlorinated and brominated mbber show the predominate stmcture (1) (>80%), by nmr, as described eadier (33,34). Halogenation of the unsaturation has no apparent effect on the isobutylene backbone chains. Cross-linked samples do not crystallize on extension due to the chain irregularities introduced by the halogenated isoprene units. 

It is somewhat difficult conceptually to explain the recoverable high elasticity of these materials in terms of flexible polymer chains cross-linked into an open network structure as commonly envisaged for conventionally vulcanised rubbers. It is probably better to consider the deformation behaviour on a macro, rather than molecular, scale. One such model would envisage a three-dimensional mesh of polypropylene with elastomeric domains embedded within. On application of a stress both the open network of the hard phase and the elastomeric domains will be capable of deformation. On release of the stress, the cross-linked rubbery domains will try to recover their original shape and hence result in recovery from deformation of the blended object. 

FIGURE 7.25 Sephadex gels are formed from dextran chains cross-linked with 1 CH, 1 -... 

For polymerization reactors, the main concern is the characteristics of the product that relate to the mechanical properties. The distribution of molar masses in the polymer product, orientation of groups along the chain, cross-linking of the polymer chains, copolymerization with a mixture of monomers, and so on, are the main considerations. Ultimately, the main concern is the mechanical properties of the polymer product. 

The elastic contribution to Eq. (5) is a restraining force which opposes tendencies to swell. This constraint is entropic in nature the number of configurations which can accommodate a given extension are reduced as the extension is increased the minimum entropy state would be a fully extended chain, which has only a single configuration. While this picture of rubber elasticity is well established, the best model for use with swollen gels is not. Perhaps the most familiar model is still Flory s model for a network of freely jointed, random-walk chains, cross-linked in the bulk state by connecting four chains at a point [47] ... 

For the shortness let us confine to the numerical analysis of the isothermal and adiabatic deformation of natural rubber, which at comparatively low chains cross-linking can be described as a melt. 

Figure 12.12 PET chains cross-linked by the reaction with pentaerythritol...

The standard gel-forming reaction is shown in Figure 8.2. Acrylamide and the cross-linker N, A-methylenebisacrylamide (bis) are mixed in aqueous solution and then copolymerized by means of a vinyl addition reaction initiated by free radicals.1317 Gel formation occurs as acrylamide monomer polymerizes into long chains cross-linked by bis molecules. The resultant interconnected meshwork of fiberlike structures has both solid and liquid components. It can be thought of as a mass of relatively rigid fibers that create a network of open spaces (the pores) all immersed in liquid (the buffer). The liquid in a gel maintains the gel s three-dimensional shape. Without the liquid, the gel would dry to a thin film. At the same time, the gel fibers retain the liquid and prevent it from flowing away. 

Thermal stability. The presence of side chains, cross-linking, and benzene rings in the polymer s "backbone increase the melting temperatures. For example, a spectrum of polymers with increasing melting temperatures would be polyethylene, polypropylene, polystyrene, nylon, and polyimide. 

Chain Cross-Linking Photopolymerization of Tetraethyleneglycol Diacrylate... 

Fig. 14 Crystal structure of BTCA, with the three crystallographically independent molecules displayed in different colours (A, greerv, B, blue, C, red) (a) a hydrogen-bonded chain of A and C molecules viewed approximately along the c-axis, and (b) the complete crystal structure viewed along the b-axis (the AC chains run into the page, with adjacent AC chains cross-linked by hydrogen bonding to B molecules)...

Polymer networks can be formed by chemical reactions between polymer chains (cross-linking) or by using trifunctional comonomers during the polymerisation. If such a network is dissolved in a second monomer and this second monomer is again polymerized into a second network, one obtains a structure in which both polymers are intertwined. These polymer chains only have very local mobility. In cases where both polymers are partially or completely immiscible the L1/L2 phase-separation is reduced to a very small scale. The properties of such an IPN are completely different from the uncross-linked polymer blend [15]. 

Metal-Chelated Side-Chain Cross-links... 

Fig. 5. Presentation of molecular structure of a sheet composed of phosphate-cation chains cross-linked in a planar pattern. Such structures are known from calcium monohydrogen phosphate dihydrate CaHPC>4 2 H2O and from monohydrate CaHP04 H2O (after MacLennan and Beevers65) Beevers64 )...

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