Solvent effect on the free‐radical copolymerization of 2‐hydroxyethyl methacrylate with t‐butyl acrylate

Abstract

The free‐radical copolymerization of 2‐hydroxyethyl methacrylate with t‐butyl acrylate was carried out at 50 °C in bulk and in 3 mol · L−1 1,4‐dioxane and N,N′‐dimethylformamide solutions. Differences between the apparent reactivity ratios determined in this work indicated a noticeable solvent effect. This is explained with a qualitative bootstrap effect. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2043–2048, 2001

Monomer reactivity ratios and glass‐transition temperatures of copolymers based on dimethyl amino ethyl methacrylate and two structural hydroxy‐functional acrylate isomers

“…For a comparative view to be obtained of the propagation rate coefficients of HEMA and EHMA, it has been thought that the k p value of EHMA in bulk might be at least as high as those found in toluene and benzene, two nonpolar solvents, which are not expected to undergo any specific interaction with the monomer 27, 28. From HEMA and EHMA activation and pre‐exponential factor parameters, it can be inferred that the propagation rate coefficient for EHMA is approximately twice that for HEMA 11, 12.…”

On the origin and consequences of high DMAEMA reactivity ratio in ATRP copolymerization with MMA: An experimental and theoretical study#

“…These are expected to make less negative the DH o associated to the ligation decreasing more the reactant enthalpy and Gibbs' energy, which ought to reduce the equilibrium constant and hence the concentration of the complex. Exploiting experimental results on the copolymerization of MMA and DMAEMA via ATRP in toluene, in this work we have provided evidences that unexpectedly marked reactivity effects can be induced even in absence of strong intermolecular forces such as hydrogen bonds [61][62][63] and between copolymerization methods that are usually considered to provide similar results. Such conclusion emerges by comparing the mentioned results with both literature and ATRP data (the latter, again, by ourselves) obtained in different reaction environments (bulk, DMF, chloroform, acetonitrile, and dioxane).…”

Diphenylselenonium 2,3,4,5‐tetraphenylcyclopentadienylide‐initiated polymerization of styrene and acrylonitrile: Synthesis, characterization, reactivity ratios, and thermal properties

“…may be varied with in wide limits. The utility of the copolymerization is exemplified on the one hand by the fundamental investigations of structure-property relations [4][5][6][7][8][9] and on the other hand by the wide range of commercial applications. 10,11 The kinetics and elucidation of copolymer structure are the major concerns for the prediction of copolymer properties and the correlation between structure and properties.…”