Modeling the free radical polymerization of acrylates

Hakan Günaydin, Seyhan Salman, Nurcan Şenyurt Tüzün, Duygu Avci, Viktorya Aviyente*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)

Abstract

Acrylates have gained importance because of their ease of conversion to high-molecular-weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well-known monomer for free radical polymerization, but its α-methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl α-hydroxymethylacrylate (MHMA), methyl α- methoxymethylacrylate (MC1MA), methyl α-acetoxymethylacrylate (MAcMA) show even better conversions to high-molecular-weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl α-hydroxymethylacrylate (EHMA) and t-butyl in t-butyl α-hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6-31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC1MA, MAcMA, EHMA, TBHMA, MC1AN (α-methoxymethyl acrylonitrile), and MC1AA (α-methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes.

Original languageEnglish
Pages (from-to)176-189
Number of pages14
JournalInternational Journal of Quantum Chemistry
Volume103
Issue number2
DOIs
Publication statusPublished - 20 May 2005
Externally publishedYes

Keywords

  • Chain transfer
  • DFT
  • Free radical polymerization
  • Functionalized acrylates
  • Rate of propagation

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