Density Functional Theory Study of Free-Radical Polymerization of Acrylates and Methacrylates: Structure−Reactivity Relationship

wim — Mon, 03 Oct 2011 08:25:31 +0000

I. Değirmenci, D. Avci, V. Aviyente, K. Van Cauter, V. Van Speybroeck, G.B. Marin, M. Waroquier

Macromolecules

40 (26), 9590–9602

2007

Abstract

Radical polymerization processes occur through a complex network of many different reactions. It is well-known that the polymerization rate is directly related to the monomer structure. The experimental polymerizability behavior is expressed as kp/kt1/2, where kp is the rate coefficient of propagation and kt is the rate coefficient of termination. In this study, the reactivity of a series of acrylates and methacrylates is modeled in order to understand the effect of the pendant group size, the polarity of a pendant group, and the nature of the pendant group (linear vs cyclic) on their polymerizability. The geometries and frequencies are calculated with the B3LYP/6-31+G(d) methodology whereas the energetics and kinetics of these monomers have been studied using the two-component BMK/6-311+G(3df,2p)//B3LYP/6-31+G(d) level of theory. For rotations about forming/breaking bonds in the transition state, an uncoupled scheme for internal rotations has been applied with potentials determined at the B3LYP/6-31+G(d) level. Generally the rate constants for propagation kp mimic the qualitative polymerization trend of the monomers modeled and can be used with confidence in predicting the polymerizability behavior of acrylates. However in the case of 2-dimethylaminoethyl acrylate, chain transfer is found to play a major role in inhibiting the polymerization. On the other hand, the disproportionation reaction turns out to be too slow to be taken into consideration as a termination reaction.

DOI

http://dx.doi.org/10.1021/ma071106i

Private attachment

07 macromolecules 40(26)9590 degirmenci.pdf

Rationalization of the polymerization of acrylates

samuel — Wed, 05 Feb 2020 15:07:02 +0000

V. Aviyente, I. Değirmenci, D. Avci, V. Van Speybroeck, K. Van Cauter, M. Waroquier

ISBN/ISSN:0065-7727

Talk

Conference / event / venue

233rd National Meeting of the Cellulose-and-Renewable-Materials-Division of the American-Chemical-Society (ACS)

Chicago, IL, USA

Sunday, 25 March, 2007 to Thursday, 29 March, 2007

Center for Molecular Modeling - D. Avci

Density Functional Theory Study of Free-Radical Polymerization of Acrylates and Methacrylates: Structure−Reactivity Relationship

Abstract

DOI

Private attachment

Rationalization of the polymerization of acrylates

Conference / event / venue