TY - JOUR
T1 - Heterofunctionalized Multiarm Star Polymers via Sequential Thiol-para-Fluoro and Thiol-Ene Double "click" Reactions
AU - Cakir, Nese
AU - Tunca, Umit
AU - Hizal, Gurkan
AU - Durmaz, Hakan
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/3/1
Y1 - 2016/3/1
N2 - The successful postfunctionalization of multiarm star polystyrene (PS) with pentafluorophenyl and allyl moieties at the periphery is demonstrated employing modular thiol-para-fluoro and photoinduced radical thiol-ene double "click" reactions, respectively. α-Fluoro and α-allyl functionalized PS (α-fluoro-PS and α-allyl-PS) are in situ prepared by atom transfer radical polymerization of styrene and their mixture is used as macroinitiator in a crosslinking reaction with divinyl benzene (DVB) yielding (fluoro-PS)m-polyDVB-(allyl-PS)m multiarm star polymer. It is found that the multiarm star polymer includes nearly identical number of arms possessing pentafluorophenyl and allyl moieties at the periphery. The obtained multiarm star polymer is then reacted with 1-propanethiol through thiol-para-fluoro "click" reaction to give (propyl-PS)m-polyDVB-(allyl-PS)m multiarm star polymer, which is subsequently reacted with N-acetyl-l-cysteine methyl ester via radical thiol-ene "click" reaction in order to give well-defined heterofunctionalized (propyl-PS)m-polyDVB-(cysteine-PS)m multiarm star polymer, with higher molecular weight and narrow molecular weight distribution. Multiarm star polymers are characterized by using viscotek triple detection gel permeation chromatography, 1H, and 19F NMR.
AB - The successful postfunctionalization of multiarm star polystyrene (PS) with pentafluorophenyl and allyl moieties at the periphery is demonstrated employing modular thiol-para-fluoro and photoinduced radical thiol-ene double "click" reactions, respectively. α-Fluoro and α-allyl functionalized PS (α-fluoro-PS and α-allyl-PS) are in situ prepared by atom transfer radical polymerization of styrene and their mixture is used as macroinitiator in a crosslinking reaction with divinyl benzene (DVB) yielding (fluoro-PS)m-polyDVB-(allyl-PS)m multiarm star polymer. It is found that the multiarm star polymer includes nearly identical number of arms possessing pentafluorophenyl and allyl moieties at the periphery. The obtained multiarm star polymer is then reacted with 1-propanethiol through thiol-para-fluoro "click" reaction to give (propyl-PS)m-polyDVB-(allyl-PS)m multiarm star polymer, which is subsequently reacted with N-acetyl-l-cysteine methyl ester via radical thiol-ene "click" reaction in order to give well-defined heterofunctionalized (propyl-PS)m-polyDVB-(cysteine-PS)m multiarm star polymer, with higher molecular weight and narrow molecular weight distribution. Multiarm star polymers are characterized by using viscotek triple detection gel permeation chromatography, 1H, and 19F NMR.
KW - multiarm star polymer
KW - orthogonal double "click" reactions
KW - thiol-ene "click" reaction
KW - thiol-para-fluoro substitution reaction
KW - triple detection GPC
UR - http://www.scopus.com/inward/record.url?scp=84960430432&partnerID=8YFLogxK
U2 - 10.1002/macp.201500300
DO - 10.1002/macp.201500300
M3 - Article
AN - SCOPUS:84960430432
SN - 1022-1352
VL - 217
SP - 636
EP - 645
JO - Macromolecular Chemistry and Physics
JF - Macromolecular Chemistry and Physics
IS - 5
ER -