Bulk and solution copolymerization of methyl methacrylate and vinyl acetate

Abstract

A series of batch, bulk and solution (in toluene) copolymerizations of methyl methacrylate and vinyl acetate was performed under various reaction conditions to high monomer conversions. In addition, low conversion bulk experiments were performed to estimate monomer reactivity ratios using the error in variables model method, based on terminal model (Mayo-Lewis) kinetics. A combination of the low and high conversion data with data from a previous study yielded reactivity ratio (r) estimates of 27.465 and 0.0102 for r MMA and r VAc , respectively, using the integrated copolymer composition (Meyer-Lowry) equation. In the high conversion experiments the effects of various factors on the reaction rate, cumulative copolymer composition, number-and weight-average molecular weights, and molecular weight distribution were studied. The factors included the monomer feed composition, initiator concentration, temperature, solvent concentration, and the addition of n-dodecyl mercaptan chain transfer agent. These factors were examined in light of the wide difference in the monomer reactivity ratios.

A QM Approach to the Calculation of Reactivity Ratios in Free‐Radical Copolymerization

“…In this work, the aim was to combine a computational analysis with a PLP/SEC experimental study to overcome the difficulties in the experimental investigation on VAc. In fact, unlike the ST/ x MA systems, it is difficult to study the reactivity of vinyl esters (in particular, the VAc/MMA copolymer)87, 92, 93, even with the PLP/SEC technique, because of their disparate relative reactivities 89–91. As a result, the monomer reactivity ratios ( r 1 and r 2 ) and the radical reactivity ratios ( s 1 and s 2 ) were determined at 40 °C with the 6–311+G(d,p) basis set.…”

Free‐radical terpolymerization of n‐butyl acrylate/butyl methacrylate/d‐limonene

“…25 Therein, the copolymer reactivity ratios of the acrylic comonomers were high (>5), whereas the corresponding reactivity ratios of the vinyl acetate was well below 0.1 in both cases. 28,29 In our case, the polymerization was dominated by BA and BMA, and the polymer composition exhibited very little drift initially. As the polymerization proceeded, more significant changes in composition were only observed when BA and BMA were nearly depleted.…”

“…The behavior of this terpolymer system was remarkably similar in this respect to that of BA/methyl methacrylate/vinyl acetate . Therein, the copolymer reactivity ratios of the acrylic comonomers were high (>5), whereas the corresponding reactivity ratios of the vinyl acetate was well below 0.1 in both cases . In our case, the polymerization was dominated by BA and BMA, and the polymer composition exhibited very little drift initially.…”

Copolymers of acrylic acid with 2‐acryloyloxyethyl 2,4‐dichlorophenoxyacetate: Synthesis and herbicide release

“…The situation developed when the monomer reactivity ratios differ greatly from one another has been extensively described for different systems such as copolymerization of vinyl acetate28–33 and vinylpyrrolidone34–44 with meth(acrylic) monomers.…”