Polyisoprene crosslinking

Table II. Swelling of Cl—Butyl and Polyisoprene Crosslinked Systems in Neopentane at —10°C...

Natural rubber, cis-1,4-polyisoprene, cross-linked with sulfur. This reaction was discovered by Goodyear in 1839, making it both historically and commercially the most important process of this type. This reaction in particular and crosslinking in general are also called vulcanization. 

Fig. 16. Schematic of the JKR test specimen used by Brown et al. The crosslinked polyisoprene (PI) lens is first loaded in contact with the substrate with a load P to join the interface. The load is then removed and radius of the contact zone decreases with time. The contact radius a t) is measured using an optical microscope. Reproduced from ref. [45].

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. 

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

Polyisoprene can be UV or e-beam cured [43,44]. The 3,4 units are particularly prone to crosslinking at low dose [45]. SIS and SBS are also crosslinkable, even conventional linear materials with low vinyl content however, small amounts of liquid trithiol or triacrylate compounds speed cure dramatically [44]. Like UV, e-beam cure is strongly affected by tackifier choice. Hydrogenated, non-aromatic resins provide much less interference with cure [36,37]. 

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. 

Randomly - Crosslinked PB and PI. Polybutadiene (Diene 35 NFA, Firestone Tire and Rubber Co.) and cis-polyisoprene (Natsyn 2200, Goodyear Tire and Rubber Co.) were crosslinked with dicumyl-peroxide, as for PDMS. Mc values were also calculated by means of equation 2. They are given for PI in Table I and are listed for PB in reference 2. 

Note 2 A classic example of vulcanization is the crosslinking of c/s-polyisoprene through sulfide bridges in the thermal treatment of natural rubber with sulfur or a sulfur-containing compound. 

The general correlations of structure and properties of homopolymers are summarized in Table 2.13. Some experiments which demonstrate the influence of the molecular weight or the structure on selected properties of polymers are described in Examples 3-6 (degree of polymerization of polystyrene and solution viscosity), 3-15, 3-21, 3-31 (stereoregularity of polyisoprene resp. polystyrene), 4-7 and 5-11 (influence of crosslinking) or Sects. 4.1.1 and 4.1.2 (stiffness of the main chain of aliphatic and aromatic polyesters and polyamides). 

Suppression of the Thermo-Oxidative Crosslinking of Polyisoprene by Addition of an Antioxidant... 

Because of the content of double bonds and a tertiary C-atom, polyisoprene undergoes numerous chemical transformations by the action of oxygen, light, or heat, like chain scission and crosslinking.The addition of suitable stabilizers can suppress these reactions even over a period of years. In the case of the thermo-oxidative crosslinking of polyisoprene this effect can be shown with the following experiment. 

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