Jump to main content
Jump to site search

Issue 19, 2016
Previous Article Next Article

The role of local chemical hardness and van der Waals interactions in the anionic polymerization of alkyl cyanoacrylates

Author affiliations

Abstract

Because of their unique adhesive properties, cyanoacrylates (CA) have various applications in many technological fields. We therefore study the anionic polymerization of five types of CAs (methyl-CA, ethyl-CA, allyl-CA, 2-phenylethyl-CA and β-methoxy-CA) up to the addition of seven monomers, using density functional theory (DFT) and DFT with dispersion correction (DFT-D3). We found that the polymerization reactions are exothermic and become nearly constant after the attachment of three monomers, which means that all of these alkyl CAs undergo steady anionic polymerization until terminated by a cation. We examine the factors that can explain this energetic trend. Polymerization energies of the CAs from DFT-D3 show consistent stabilization relative to DFT, underlining the importance of intra-chain dispersion interactions. Population analysis shows that around 97% of net anionic charge is always localized between the latest added monomer's cyano and carbonyl groups, regardless of chain length, and this local chemical hardness can account for the computed energetics. The HOMO–LUMO energy gap of the CA polymers decreases as the degree of polymerization increases, with HOMO and LUMO energies becoming equal from the ninth degree of methyl-CA polymerization onwards, but this does not affect the charge distribution or consequently the polymerization reaction.

Graphical abstract: The role of local chemical hardness and van der Waals interactions in the anionic polymerization of alkyl cyanoacrylates

Back to tab navigation

Supplementary files

Publication details

The article was received on 02 Feb 2016, accepted on 23 Mar 2016 and first published on 24 Mar 2016


Article type: Paper
DOI: 10.1039/C6PY00201C
Citation: Polym. Chem., 2016,7, 3236-3243
  •   Request permissions

    The role of local chemical hardness and van der Waals interactions in the anionic polymerization of alkyl cyanoacrylates

    H. Ablat, I. Povey, R. O'Kane, S. Cahill and S. D. Elliott, Polym. Chem., 2016, 7, 3236
    DOI: 10.1039/C6PY00201C

Search articles by author

Spotlight

Advertisements