TY - JOUR
T1 - Fast and catalyst-free hetero-diels-alder chemistry for on demand cyclable bonding/debonding materials
AU - Oehlenschlaeger, Kim K.
AU - Guimard, Nathalie K.
AU - Brandt, Josef
AU - Mueller, Jan O.
AU - Lin, Ching Yeh
AU - Hilf, Stefan
AU - Lederer, Albena
AU - Coote, Michelle L.
AU - Schmidt, Friedrich G.
AU - Barner-Kowollik, Christopher
PY - 2013/8/21
Y1 - 2013/8/21
N2 - A new dithioester possessing a cyano Z-group (cyano-dithioester (CDTE)) has been synthesized via a 2-step, one-pot reaction. The cyano-substituted dithioester has been found to undergo fast reversible hetero-Diels-Alder (HDA) reactions at ambient temperature, without the need for a catalyst, as demonstrated by ESI-MS and UV-Vis experiments. To apply the bonding/debonding on demand system to materials science, a cyano-dithioester di-linker was synthesized and employed as a di-functional dienophile in a HDA-based polymerization reaction with a bis-cyclopentadiene polymer. The reversible bonding of the polymer systems were demonstrated by on-line UV-Vis spectroscopy, on-line NMR spectroscopy, and on-line high temperature DLS, as well as via GPC in situ trapping experiments and high-level ab initio molecular orbital calculations.
AB - A new dithioester possessing a cyano Z-group (cyano-dithioester (CDTE)) has been synthesized via a 2-step, one-pot reaction. The cyano-substituted dithioester has been found to undergo fast reversible hetero-Diels-Alder (HDA) reactions at ambient temperature, without the need for a catalyst, as demonstrated by ESI-MS and UV-Vis experiments. To apply the bonding/debonding on demand system to materials science, a cyano-dithioester di-linker was synthesized and employed as a di-functional dienophile in a HDA-based polymerization reaction with a bis-cyclopentadiene polymer. The reversible bonding of the polymer systems were demonstrated by on-line UV-Vis spectroscopy, on-line NMR spectroscopy, and on-line high temperature DLS, as well as via GPC in situ trapping experiments and high-level ab initio molecular orbital calculations.
UR - http://www.scopus.com/inward/record.url?scp=84880419050&partnerID=8YFLogxK
U2 - 10.1039/c3py00476g
DO - 10.1039/c3py00476g
M3 - Article
SN - 1759-9954
VL - 4
SP - 4348
EP - 4355
JO - Polymer Chemistry
JF - Polymer Chemistry
IS - 16
ER -