Polymer, Vol.36, No.6, 1209-1216, 1995
Influence of the Functionality of the Quaternizing Agent and the Polymer Molecular-Weight on the Viscoelastic Behavior of Alpha,Omega-(Dimethylamino)Polyisoprenes
Quaternization of the end-groups of alpha,omega-(dimethylamino)polyisoprenes with monofunctional, difunctional and trifunctional halides (iodides and bromides) has been undertaken on polymers of different molecular weights ((M) over bar(n) = 6000 and 38 000 g mol(-1)). The thermal stability of the ammonium end-groups is somewhat better when iodide counteranions are present. Quaternization increases the T-g of the material. This effect is more pronounced for low molecular weight chains, especially when a short alkyl group quaternizing agent is used. However, the size of the alkyl or aryl radical has a minor effect on polymer T-g when difunctional quaternizing agents are used. Nevertheless, the modulus of the rubber-like plateau of materials with difunctional agents is higher than with monofunctional quaternizing agents, owing to coupling reactions between the chain-ends. Rheological measurements indicate that the quaternized low molecular weight polyisoprenes exhibit an Arrhenius-type temperature dependence characterized by activation energies which vary between 121 and 146 kJ mol(-1) and suggest that the relaxations attributed to dipole-dipole interactions dominate over long chain entanglements.