Poly(ethyl acrylate) in dilute solution

Poly(ethyl acrylate) (PEA), solution polymerized in methyl ethyl ketone by free radical initiation, was fractionated and the fractions were characterized by light scattering, viscometry and osmometry. Fractions obtained were in the molecular weight range of 0·3 × 10⁶ to 1·6 × 10⁶ with a polydispersity of 1.40. The following Mark-Houwink relations were established:

$\text{η]}{}^{\mathrm{<mtext>35°</mtext><mtext>C</mtext>}}{}_{\mathrm{<mtext>acetone</mtext>}}\text{=4·15×10}{}^{\mathrm{?2}}\text{M}{}^{\mathrm{0?61}}{}_{\mathrm{W}}$

$\text{η]}{}^{\mathrm{<mtext>35°</mtext><mtext>C</mtext>}}{}_{\mathrm{<mtext>MEK</mtext>}}\text{=2·03×10}{}^{\mathrm{?2}}\text{M}{}^{\mathrm{0?66}}{}_{\mathrm{W}}$

$\text{η]}{}^{\mathrm{<mtext>39.5°</mtext><mtext>C</mtext>}}{}_{\mathrm{<mtext>n-propanal</mtext>}}\text{=7·89×10}{}^{\mathrm{?2}}\text{M}{}^{\mathrm{0?50}}{}_{\mathrm{W}}$

It was found that n-propanol at 39.5°C was a theta solvent for poly(ethyl acrylate) and that acetone was a poor solvent compared to methyl ethyl ketone. A relation between the molecular dimension and the molecular weight was established. It was observed that the chain dimensions of poly(ethyl acrylate) and poly(butyl acrylate) were considerably larger than poly(ethyl methacrylate) and poly(butyl methacrylate) respectively. The validity of various extrapolation procedures that have been proposed for calculating the unperturbed dimensions have been examined. The steric factor for PEA was 2·16 compared to 2·10 for poly(ethyl methacrylate). Root mean square end-to-end distances were calculated from the Debye-Bueche and Kirkwood-Riseman methods and compared with the experimental values.