Kinetics of early stages of resorcinol-formaldehyde polymerization investigated by solution phase nuclear magnetic resonance spectroscopy

Katarzyna Z. Gaca, John A. Parkinson, Jan Sefcik

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6 Citations (Scopus)

Abstract

Resorcinol and formaldehyde reactions were quantitatively monitored by means of 1H and 13C NMR spectroscopy at room temperature (293 K) before heat treatment leading to formation of organic gels. We found that resorcinol substitution with formaldehyde starts with an initial surprisingly rapid step followed by a more gradual depletion of the reactants. Substituted species with both monomeric and dimeric hydroxymethyl groups were observed immediately after mixing of the reagents with the proportion of formaldehyde-based solution species consumed between 30 and 50%. Substituted resorcinol species can be all accounted for by solution-phase NMR at ambient conditions before they form nanoscale clusters upon heating. It can therefore be expected that the final properties of resorcinol-formaldehyde gels depend not only on the composition of reaction mixtures and duration of the high temperature treatment but also on the manner and period of reagent mixing (a hitherto overlooked synthesis step), as different amounts of alternatively substituted resorcinol can be produced before heat treatment commences.
LanguageEnglish
Pages62-73
Number of pages12
JournalPolymer
Volume110
Early online date28 Dec 2016
DOIs
Publication statusPublished - 10 Feb 2017

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Formaldehyde
Nuclear magnetic resonance spectroscopy
Polymerization
Kinetics
Gels
Heat treatment
Substitution reactions
Nuclear magnetic resonance
Heating
Temperature
resorcinol
Chemical analysis

Keywords

  • resorcinol-formaldehyde gels
  • nuclear magnetic resonance
  • reaction mechanism
  • sol-gel
  • reaction kinetics
  • hydroxymethyl resorcinol derivatives
  • nanoporous organic gels
  • sol-gel synthesis
  • polymerization

Cite this

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title = "Kinetics of early stages of resorcinol-formaldehyde polymerization investigated by solution phase nuclear magnetic resonance spectroscopy",
abstract = "Resorcinol and formaldehyde reactions were quantitatively monitored by means of 1H and 13C NMR spectroscopy at room temperature (293 K) before heat treatment leading to formation of organic gels. We found that resorcinol substitution with formaldehyde starts with an initial surprisingly rapid step followed by a more gradual depletion of the reactants. Substituted species with both monomeric and dimeric hydroxymethyl groups were observed immediately after mixing of the reagents with the proportion of formaldehyde-based solution species consumed between 30 and 50{\%}. Substituted resorcinol species can be all accounted for by solution-phase NMR at ambient conditions before they form nanoscale clusters upon heating. It can therefore be expected that the final properties of resorcinol-formaldehyde gels depend not only on the composition of reaction mixtures and duration of the high temperature treatment but also on the manner and period of reagent mixing (a hitherto overlooked synthesis step), as different amounts of alternatively substituted resorcinol can be produced before heat treatment commences.",
keywords = "resorcinol-formaldehyde gels, nuclear magnetic resonance, reaction mechanism, sol-gel, reaction kinetics, hydroxymethyl resorcinol derivatives, nanoporous organic gels, sol-gel synthesis, polymerization",
author = "Gaca, {Katarzyna Z.} and Parkinson, {John A.} and Jan Sefcik",
year = "2017",
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doi = "10.1016/j.polymer.2016.12.069",
language = "English",
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T1 - Kinetics of early stages of resorcinol-formaldehyde polymerization investigated by solution phase nuclear magnetic resonance spectroscopy

AU - Gaca, Katarzyna Z.

AU - Parkinson, John A.

AU - Sefcik, Jan

PY - 2017/2/10

Y1 - 2017/2/10

N2 - Resorcinol and formaldehyde reactions were quantitatively monitored by means of 1H and 13C NMR spectroscopy at room temperature (293 K) before heat treatment leading to formation of organic gels. We found that resorcinol substitution with formaldehyde starts with an initial surprisingly rapid step followed by a more gradual depletion of the reactants. Substituted species with both monomeric and dimeric hydroxymethyl groups were observed immediately after mixing of the reagents with the proportion of formaldehyde-based solution species consumed between 30 and 50%. Substituted resorcinol species can be all accounted for by solution-phase NMR at ambient conditions before they form nanoscale clusters upon heating. It can therefore be expected that the final properties of resorcinol-formaldehyde gels depend not only on the composition of reaction mixtures and duration of the high temperature treatment but also on the manner and period of reagent mixing (a hitherto overlooked synthesis step), as different amounts of alternatively substituted resorcinol can be produced before heat treatment commences.

AB - Resorcinol and formaldehyde reactions were quantitatively monitored by means of 1H and 13C NMR spectroscopy at room temperature (293 K) before heat treatment leading to formation of organic gels. We found that resorcinol substitution with formaldehyde starts with an initial surprisingly rapid step followed by a more gradual depletion of the reactants. Substituted species with both monomeric and dimeric hydroxymethyl groups were observed immediately after mixing of the reagents with the proportion of formaldehyde-based solution species consumed between 30 and 50%. Substituted resorcinol species can be all accounted for by solution-phase NMR at ambient conditions before they form nanoscale clusters upon heating. It can therefore be expected that the final properties of resorcinol-formaldehyde gels depend not only on the composition of reaction mixtures and duration of the high temperature treatment but also on the manner and period of reagent mixing (a hitherto overlooked synthesis step), as different amounts of alternatively substituted resorcinol can be produced before heat treatment commences.

KW - resorcinol-formaldehyde gels

KW - nuclear magnetic resonance

KW - reaction mechanism

KW - sol-gel

KW - reaction kinetics

KW - hydroxymethyl resorcinol derivatives

KW - nanoporous organic gels

KW - sol-gel synthesis

KW - polymerization

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SP - 62

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SN - 0032-3861

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