Polyisoprene sulfur vulcanisation

The chemical microstructures of cis-polyisoprene (HR) vulcanised with sulfur and N-t-butyl-2-benzothiazole sulfenamide (TBBS) accelerator were studied as a function of extent of cure and accelerator to sulfur ratio in the formulations by solid-state 13C NMR spectroscopy at 75.5 MHz [29]. Conventional (TBBS/Sulfur=0.75/2.38), semi-efficient (SEV=1.50/1.50) and efficient (EV=3.00/1.08) vulcanisation formulations were prepared, which were cured to different cure states according to the magnitude of increase in rheometer torque. The order and types of the sulfurisation products formed are constant in all the formulation systems with different accelerator to sulfur ratios. However, the amount of sulfurisation has been found to vary directly with the concentration of elemental sulfur. 

The chains must be crosslinked to form a network (cf. Fig 7.16). In most elastomers containing double bonds, covalent bonds are introduced between chains. This can be done either with sulfur or polysulfide bonds (the well known sulfur vulcanisation of natural rubber is an example), or else by direct reactions between double bonds, initiated via decomposition of a peroxide additive into radicals. Double bonds already exist in the chemical structure of polyisoprene, polybutadiene and its copolymers. When this is not the case, as for silicones, ethylene-propylene copolymers and polyisobutylene, units are introduced by copolymerisation which have the property of conserving a double bond after incorporation into the chain. These double bonds can then be used for crosslinking. This is how Butyl rubber is made from polyisobutylene, by adding 2% isoprene. Butyl is a rubber with the remarkable property of being impermeable to air. It is used to line the interior of tyres with no inner tube. 

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