M. Buback, H. Latz
Cloud Point Pressure Curves of Ethene-Poly(Ethene-co-(Meth)Acrylic Acid) Mixtures
Macromol. Chem. Phys. 204, 638-645 (2003)


Ethene-methacrylic acid (MAA) and ethene-acrylic acid (AA) copolymers of narrow polydispersity and high chemical homogeneity have been synthesized at acid unit copolymer contents up to 9 mol-% within a continuously operated stirred tank reactor at overall monomer conversions of about 2%. Cloud-point pressures (CPPs) of mixtures of 3 wt.-% copolymer in ethene (E) have been measured in an optical high-pressure cell at pressures and temperatures up to 3 000 bar and 260 °C, respectively. The CPP weakly increases with acid copolymer content up to about 3.5 mol-%. Toward higher acid contents, the CPP is strongly enhanced, in particular at the lower edge of the experimental temperature range at around 200 °C. This increase in CPP is more pronounced for the AA than for the MAA systems. The data suggest that hydrogen-bonding interactions are operative in the pressurized E/poly(E-co-(M)AA) mixtures at temperatures of 260 °C and perhaps even above. E-AA and E-MAA copolymers with acid contents of about 5.6 mol-% have also been completely methyl-esterified to yield the associated methyl esters. The CPPs of the resulting E-methyl acrylate and E-methyl methacrylate copolymers in mixtures with E are significantly below the CPPs of the corresponding E/poly(E-co-(M)AA) systems.