Preparation of Polymethylacrylic Acid Standard Samples for GPC Applications via a Precipitation Fractionation-Separated Step Hydrolysis Method

<div><p>A series of polymethylacrylic acid (PMAA) standard samples were prepared from fractionated PMMA samples followed by a two-step hydrolysis. The six PMMA standard samples with narrow molecular weight distributions were produced by free radical polymerization and fractionated with toluene-petroleum ether. Their average molecular weights ranged from 3.1 × 10<sup>3</sup> to 4.3 × 10<sup>4</sup>, dispersion coefficients were less than 1.5, and their gel permeation chromatography (GPC) peak shapes were symmetrical. The PMMA standard samples were dissolved in dioxane, and then hydrolyzed in a saturated NaOH-methanol solution for 24 h, the methanol then evaporated, and after that the PMMA samples were hydrolyzed in a 2 mol ·L <sup>−1</sup> NaOH aqueous solution for 24 h. The <sup>1</sup>H-NMR results showed that the two-step hydrolysis degree was higher than 98.70%. The PMAA standard samples were obtained after acidifying the hydrolysates, namely polymethacrylic acid sodium salt, and their molecular weights were constant during the separation process. The acid–base titration results showed the purities of the PMAA samples were greater than 98.6%, and their molecular weight distributions were symmetrical and narrow. The molecular weights of the PMAA were determined by the stoichiometric relationship of the hydrolysis reaction. Compared with viscosimetry, the results of both methods were basically the same, and their errors were less than 10%.</p></div>