Phase Behavior of Poly(ethylene-co-norbornene) in Hydrocarbon Solvents: Effect of Polymer Concentration and Solvent Structure

Phase behavior information is necessary for accomplishing homogeneous copolymerization to obtain high yield of copolymers and prevent a fouling problem. Cloud-point data to $160^{\circ}C$ and 1,450 bar are presented for five $C_6$ hydrocarbon solvents, normal hexane, 2,2-dimethyl butane, 2,3-dimethyl butane, 2-methyl pentane, and 3-methyl pentane, with poly(ethylene-co-53 mol% norbornene) ($PEN_{53}$). The pressure-concentration isotherms measured for $PEN_{53}$/n-hexane have maximums that range between 5 and 12 wt% $PEN_{53}$. The cloud-point curves for $PEN_{53}$ all have negative slopes that decrease in pressure with temperatures. The single-phase region of $PEN_{53}$ in n-hexane is larger than the regions in 2,2-dimethyl butane, 2,3-dimethyl butane, 2-methyl pentane, and 3-methyl pentane. The cloud-point curve of $PEN_{53}$ in 2,2-dimethyl butane is located at higher temperatures and pressures than the curve in 2,3-dimethyl butane due to the reduced dispersion interactions with and limited access of 2,2-dimethyl butane to the copolymer. Similar cloud-point behavior is observed for $PEN_{53}$ in 2-methyl pentane and 3-methyl pentane.