Michael addition reaction kinetics of acetoacetates and acrylates for the formation of polymeric networks

Sharlene R. Williams, Kevin M. Miller, Timothy Edward Long

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

2-Ethylhexyl acrylate and ethyl acetoacetate were reacted in a Carbon - Michael addition reaction as a model for subsequent studies of polymer networks. A statistical design of reactions was conducted in the presence of an in-situ ATR FTIR spectrometer to determine the effect of solvent, base, base concentration, and reactant stoichiometry on the observed rate constant. In particular, a central composite statistical design of experiments analysis was performed for model reactions that were catalyzed using either l,8-diazbicyclo[5.4.0]undec-7-ene (DBU) or K 2CO 3 at various concentrations. Poly(propylene glycol) bisacetoacetate (PPG BisAcAc) and poly(propylene glycol) diacrylate (PPGDA) networks were then prepared in the absence of solvent at 23°C based on optimized conditions in the presence of DBU and K 2CO 3. In a similar fashion to model studies, in-situ FTIR spectroscopy was utilized, and observed rate constants were determined. The influence of PPG BisAcAc molecular weight on dynamic mechanical properties was determined and gel fraction analysis was conducted. It appears that the selection of base significantly altered the rate of the reaction, but had an insignificant effect on mechanical properties.

Original languageEnglish
Pages (from-to)165-194
Number of pages30
JournalProgress in Reaction Kinetics and Mechanism
Volume32
Issue number4
DOIs
Publication statusPublished - 2007 Dec 6
Externally publishedYes

Fingerprint

Acetoacetates
Acrylates
Propylene Glycol
Addition reactions
acrylates
Glycols
Reaction kinetics
Propylene
reaction kinetics
propylene
glycols
Rate constants
Mechanical properties
mechanical properties
Stoichiometry
Design of experiments
Spectrometers
experiment design
Polymers
Carbon

Keywords

  • Base effects
  • Design of experiments
  • In-situ FTIR
  • Michael addition
  • Solvent effects

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Catalysis

Cite this

Michael addition reaction kinetics of acetoacetates and acrylates for the formation of polymeric networks. / Williams, Sharlene R.; Miller, Kevin M.; Long, Timothy Edward.

In: Progress in Reaction Kinetics and Mechanism, Vol. 32, No. 4, 06.12.2007, p. 165-194.

Research output: Contribution to journalArticle

Williams, Sharlene R. ; Miller, Kevin M. ; Long, Timothy Edward. / Michael addition reaction kinetics of acetoacetates and acrylates for the formation of polymeric networks. In: Progress in Reaction Kinetics and Mechanism. 2007 ; Vol. 32, No. 4. pp. 165-194.
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