Upper and lower critical solution temperatures in polybutadiene-alkane systems : Effect of the surface-to-volume ratio of the polymer

Cloud point curves (CPC) have been measured for 1–4 cis polybutadiene (M_r = 40,000–830,000) in n-hexane, 2-methyl-hexane, 2,2,3 trimethylbutane and 2,2,4 trimethylpentane. These four systems show upper and lower critical solubility temperatures which approach one another as the molecular weight increases. An hourglass-shaped CPC is found for two systems. The CPC are found to be much more dependent on polymer concentration than is usual. Calculated (Prigogine, Patterson, Flory theories) and experimental critical temperatures, critical volumes and shapes of the CPC are in much better agreement for these systems than for other systems involving polystyrene, polyisobutylene or polybutene-1. Analysis of these results with those for other systems in the literature indicates the importance of the surface-to-volume ratio s of the polymers. A small value of s = s₂/s₁ (0·5–0·8) for thick polymer chains improves the calculated value of the critical temperature while s = 1 is quite good for thin polymer chains such as polybutadiene and polyethylene.