Polyisoprene networks

The study of acid-base interaction is an important branch of interfacial science. These interactions are widely exploited in several practical applications such as adhesion and adsorption processes. Most of the current studies in this area are based on calorimetric studies or wetting measurements or peel test measurements. While these studies have been instrumental in the understanding of these interfacial interactions, to a certain extent the interpretation of the results of these studies has been largely empirical. The recent advances in the theory and experiments of contact mechanics could be potentially employed to better understand and measure the molecular level acid-base interactions. One of the following two experimental procedures could be utilized (1) Polymers with different levels of acidic and basic chemical constitution can be coated on to elastomeric caps, as described in Section 4.2.1, and the adhesion between these layers can be measured using the JKR technique and Eqs. 11 or 30 as appropriate. For example, poly(p-amino styrene) and poly(p-hydroxy carbonyl styrene) can be coated on to PDMS-ox, and be used as acidic and basic surfaces, respectively, to study the acid-base interactions. (2) Another approach is to graft acidic or basic macromers onto a weakly crosslinked polyisoprene or polybutadiene elastomeric networks, and use these elastomeric networks in the JKR studies as described in Section 4.2.1. 

Thermodynamic Analysis. As reported previously, the storage modulus G of PDMS networks with tetrafunctional crosslinks is independent of frequency between 10 3 and 1 Hz (21). This behaviour which is entirely different from that of vulcanized natural rubber or synthetic polyisoprene networks, was attributed to the lack of entanglements, both trapped and untrapped, in these PDMS networks. Figure 4 shows that G of a network with comb-like crosslinks is also frequency independent within an error of 0.5%. For comparison, two curves for PDMS having tetrafunctional crosslinks are also shown. The flat curves imply that slower relaxations are highly unlikely. Hence a thermodynamic analysis of the G data below 1 Hz can be made as they equal equilibrium moduli. 

A pseudo solid-like behavior of the T2 relaxation is also observed in i) high Mn fractionated linear polydimethylsiloxanes (PDMS), ii) crosslinked PDMS networks, with a single FID and the line shape follows the Weibull function (p = 1.5)88> and iii) in uncrosslinked c/.s-polyisoprenes with Mn > 30000, when the presence of entanglements produces a transient network structure. Irradiation crosslinking of polyisoprenes having smaller Mn leads to a similar effect91 . The non-Lorentzian free-induction decay can be a consequence of a) anisotropic molecular motion or b) residual dipolar interactions in the viscoelastic state. 

QuasicrystaUine phases form at compositions close to the related crystalline phases. When solidified, the resultant strucmre has icosahedra threaded by a network of wedge disclinations, having resisted reconstruction into crystalline units with three-dimensional translational periodicity. The most well-known examples of quasicrystals are inorganic phases from the ternary intermetallic systems Al-Li-Cu, Al-Pd-Mn, Zn-Mg-Ln, Al-Ni-Co, Al-Cu-Co, and Al-Mn-Pd. In 2007, certain blends of polyisoprene, polystyrene, and poly(2-vinylpyridine) were found to form star-shaped copolymers that assemble into the first known organic quasicrystals (Hayashida et al., 2007). 

On the other hand, if the cross-link density is low (the length of the chains between cross-links is large) and the mobility of the chains is high, the cross-linked material is called an elastomer. An example of a typical elastomer is cw-l,4-polyisoprene (natural rubber), which, by means of a cross-linking reaction with sulfur (vulcanization), gives rise to a network structure (see Fig. 1.4). 

Finite chain extensibility is the major reason for strain hardening at high elongations (Fig. 7.8). Another source of hardening in some networks is stress-induced crystallization. For example, vulcanized natural rubber (cw-polyisoprene) does not crystallize in the unstretched state at room temperature, but crystallizes rapidly when stretched by a factor of 3 or more. The extent of crystallization increases as the network is stretched more. The amorphous state is fully recovered when the stress is removed. Since the crystals invariably have larger modulus than the surrounding... 

Morton, M. Fetters, L.J. Inomata, J. Rubio, D.C. Young, R.N. Synthesis and properties of uniform polyisoprene networks. I. Synthesis and characterization of a,co-dihydroxy polyisoprene. Rubber Chem. Technol. 1976, 49, 303. 

Mishra, V. Murphy, C.J. Sperling, L.H. Interpenetrating polymer networks based on thermoplastic polyurethanes (TPUs) and cis-1,4 polyisoprene. J. Appl. Polym. Sci. 1994, 53, 1425-1434. 

Moore, C.G. Trego, B.R. Structural characterization of vulcanizates. Part IV. Use of triphenylpho-sphine and sodium di-n-butyl phosphite to determine the structures of sulfur linkages in natural rubber, cis-l,4-polyisoprene, and ethylene-propylene rubber vulcanizate networks. J. Appl. Polym. Sci. 1964, 8, 1957. 

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