Polymer, Vol.35, No.21, 4623-4626, 1994
Studies of Cyclic and Linear Poly(Dimethylsiloxane)S .31. Effect of Molecular Architecture Topology on Blends of Poly(Methylphenylsiloxane) and Poly(Dimethylsiloxane)
The phase behaviour of binary mixtures of cyclic poly(dimethylsiloxane) (PDMS) and linear poly(methyl-phenylsiloxane) (PMPS) was investigated using a static wide-angle light-scattering technique. Evidence for the effect of component molecular architecture/topology (cyclic or linear) on the phase separation of blends was sought through cloud point measurements and by examining the composition dependence of the resulting phase diagram. The cyclic-linear blend exhibited an upper critical solution temperature (UCST) and showed a dependence on the molecular architecture/topology in that the critical temperature T(c) for the cyclic-linear blend was lower than expected when compared with PDMS-PMPS blends in which both components had a linear polymeric structure. The interaction energy density parameter LAMBDA12 for the polymers was evaluated via the Flory-Huggins treatment for the thermodynamics of mixing of two polymers. The blending of cyclic PDMS led to a lower LAMBDA12 when compard with the corresponding linear-linear binary blend, again because of the chain architecture/topology effect. For this UCST system, it thus appears that PDMS cyclics are more soluble/compatible than their linear analogues of the same degree of polymerization. These findings are consistent with the current, but very limited, experimental data in the literature for large ring systems.
Keywords:GLASS-TRANSITION TEMPERATURES;PHASE-SEPARATION KINETICS;NEUTRON-SCATTERING;SILOXANES);POLYSILOXANES;POLY(PHENYLMETHYLSILOXANE);CHEMISTRY;TOPOLOGY;BEHAVIOR;POLYMERS