Elastomers networking

Bmin P, Veensda GJ, Nijenhuis AJ, and Pennings AJ. Design and synthesis of biodegradable poly(ester-urethane) elastomer networks composed of non toxic building blocks. Makromol Chem Rapid Common, 1988, 9, 589. 

Case,L.C., Wargin,R.V. Elastomer behavior. IV. The loop structure of elastomer networks. Makromol. Chem. 77,172-184 (1964). 

The stress-optical coefficient, Ka, of an elastomer network is a constant, independent of extension ratio and crosslink density. It is directly proportional to the difference between the longitudinal and transverse polarizabilities of the statistical chain segment (fei — 2) ... 

A powerful technique for the study of orientation and dynamics in viscoelastic media is line shape analysis in deuteron NMR spectroscopy [1]. For example, the average orientation of chain segments in elastomer networks upon macroscopic strain can be determined by this technique [22-31]. For a non-deformed rubber, a single resonance line in the deuterium NMR spectrum is observed [26] while the spectrum splits into a well-defined doublet structure under uniaxial deformation. It was shown that the usual network constraint on the end-to-end vector determines the deuterium line shape under deformation, while the interchain (excluded volume) interactions lead to splitting [26-31]. Deuterium NMR is thus able to monitor the average segmental orientation due to the crosslinks and mean field separately [31]. 

Although the major interest in experimental and theoretical studies of network formation has been devoted to elastomer networks, the epoxy resins keep apparently first place among typical thermosets. Almost exclusively, the statistical theory based on the tree-like model has been used. The problem of curing was first attacked by Japanese authors (Yamabe and Fukui, Kakurai and Noguchi, Tanaka and Kakiuchi) who used the combinatorial approach of Flory and Stockmayer. Their work has been reviewed in Chapter IV of May s and Tanaka s monograph Their experimental studies included molecular weights and gel points. However, their conclusions were somewhat invalidated by the fact that the assumed reaction schemes were too simplified or even incorrect. It is to be stressed, however, that Yamabe and Fukui were the first who took into account the initiated mechanism of polymerization of epoxy groups (polyetherification). They used, however, the statistical treatment which is incorrect as was shown in Section 3.3. 

Epoxy networks may be expected to differ from typical elastomer networks as a consequence of their much higher crosslink density. However, the same microstructural features which influence the properties of elastomers also exist in epoxy networks. These include the number average molecular weight and distribution of network chains, the extent of chain branching, the concentration of trapped entanglements, and the soluble fraction (i.e., molecular species not attached to the network). These parameters are typically difficult to isolate and control in epoxy systems. Recently, however, the development of accurate network formation theories, and the use of unique systems, have resulted in the synthesis of epoxies with specifically controlled microstructures Structure-property studies on these materials are just starting to provide meaningful quantitative information, and some of these will be discussed in this chapter. 

A large number of macroscopic properties of elastomer networks are closely related to the density of network junctions and the extent of their fluctuations. Qualitatively, any increase of network density causes an increase in stress, whereas fluctuations of network junctions leads to a decreasing stress. It is generally believed that a formation of additional network junctions resulting fi-om the presence of filler particles in the elastomer matrix is one of the reasons for the improvement of mechanical properties of filled elastomers. However, the application of macroscopic techniques does not provide reliable results for the network structure in filled elastomers. Furthermore, a lack of information exists on the dynamic behavior of adsorption junctions. The present study fills the gap of knowledge in this area. 

IPN s and related materials) in fact) have a long history. For example) IPN s were first synthesized to produce smooth sheets of bulk polymerized homopolymers (11), IPN s were next used as solution polymerized ion exchange resins. (12) 13) Further development of IPN s included the syntheses oT interpenetrating elastomer networks (lEN s) and simultaneous interpenetrating networks (SIN s) (14). lEN s consist of a mixture of different emulsion polymerized elastomers which are both crosslinked after coagulation. SIN s are formed by the simultaneous polymerization of mixed monomers by two noninterfering reactions (3 ) 16). 

Static H Multiple Quantum (MQ) NMR spectroscopy, on the other hand, has shown the ability to more reliably quantitatively characterize elastomer network structure and heterogeneities (14-19). H MQ NMR methods allow for the measurement of absolute residual dipolar couplings (cooperative dynamics without interference from magnetic susceptibility and field gradients which complicate relaxation measurements (13, 14, 20,21). It has previously been shown that the residual dipolar couplings are directly related to the dynamic order parameter, Sb, and the crosslink density (1/N)(P) ... 

This section seeks to make a quantitative evaluation of the relation between the elastic force and elongation. The calculation requires determining the total entropy of the elastomer network as a function of strain. The procedure is divided into two stages first, the calculation of the entropy of a single chain, and second, the change in entropy of a network as a function of strain. 

When elastomer networks are formed, the segments of chains that are close to each other in space may be crosslinked, independently of their locations along the chain. Therefore, the network has a totally random structure in which the number of cross-linking points and their locations... 

Another way to deform an elastomer network is to put it in contact with a solvent. In this case molecules of solvent are absorbed in the network, giving rise to a phenomenon known as swelling. Swelling of a network by the... 

The reinforcement of rubber by the presence of active fillers is a complex phenomenon that depends on the characteristics of the elastomer network and the properties of the fillers. The influential properties are the particle size, the morphology of particle aggregates, and the surface properties. The role of the geometrical characteristics of the tiller is well understood, whereas the significance of the surface properties is more difficult to analyze. This situation stems essentially from the lack of adequate methods to analyze the surface of such small particles and from the fact that fillers differ from each other and need to be considered individually. 

A simple model of an elastomer network is depicted in Fig. 7.1.8. The segmental motion of inter-cross-link chains is fast but anisotropic at temperatures of 100-150 K above the glass transition temperature The end-to-end vector R of such a chain reorients on a much slower timescale because it appears fixed between seemingly static cross-link points. As a result of the fast but anisotropic motion, the dipolar interaction between spins along the cross-link chains is not averaged to zero, and a residual dipolar coupling remains [Cohl, Gotl, Litl]. 

Figure 1.14. A schematic diagram of a crosshnked elastomer network and the changes in the (circled) section of the network when it is deformed in the direction shown by the arrows and then...

An important methodology established early on is an equilibrium volume swelling approach and application of the Flory-Rehner equation [134, 135]. While this is satisfactory for simple one component elastomer networks it is not particularly convenient experimentally and is of dubious value for multi-component elastomers. 

The total change in free energy of the elastomer network due to the deformation is simply the difference between equations (6-36) and (6-38) ... 

The parameter rl r, sometimes referred to as the front factor, can be regarded as the average deviation of the network chains from the dimensions they would assume if they were isolated and free from all constraints. For an ideal elastomer network, the front factor is unity. 

In contrast to earlier polymer-supported complex catalysts in which complexes were immobilized through electrostatic interaction, covalent bonds, or coordinative bonds, in this case the complex is captured in Ihe elastomer network by occlusion in a dense polymer in Ihe absence of any supplementary chemical bonding and only as result of steric restrictions. In the hydrogenation of methyl acetoacetate by this catalyst an ee of 70% was obtained in polyethyleneglycol solution at 60 °C. Afer regeneration of the catalyst and reuse, its activity and enantioselectivity were almost unchanged. 

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