TY - JOUR

T1 - Fast and solvent-free microwave-assisted synthesis of thermoresponsive oligo(glycidyl ether)s

AU - Stöbener, Daniel D.

AU - Donath, Dorian

AU - Weinhart, Marie

N1 - Funding Information: M.W. is grateful to financial support from the Federal Ministry of Education and Research through grant FKZ: 13N13523. The authors would thank Anke Hoppensack for proof reading this manuscript. Publisher Copyright: © 2018 Wiley Periodicals, Inc.

PY - 2018/11/1

Y1 - 2018/11/1

N2 - Low-molecular weight linear poly(glycidyl ether)s are typically synthesized via the “classical,” oxy-anionic ring-opening polymerization (ROP) of glycidyl ether monomers at elevated temperatures. To reduce reaction times, a fast process was developed to synthesize oligo(glycidyl ether)s (OGEs) in bulk at a gram-scale utilizing microwave heating. Well-defined thermoresponsive copolymers comprising glycidyl methyl ether and ethyl glycidyl ether with molecular weights of up to 3 kDa were synthesized via microwave-assisted ROP with reaction times of approximately 10 min. The fast reaction kinetics were attributed to the rapid and uniform heating and high temperatures reached during the reaction. Consequently, no significant microwave-specific acceleration of the oxy-anionic ROP was observed. The temperature-triggered phase transition of the OGEs in aqueous solution revealed cloud point temperatures that are highly dependent on the OGE molecular weight, concentration, and comonomer composition, which extends previously reported data. Furthermore, oligo(glycidyl ether) acrylates (OGEAs) with reactive, functional end groups were directly accessible via in situ quenching of the anionic, microwave-assisted ROP with acrylic acid chloride. The obtained thermoresponsive OGEA macromonomers represent a promising material for the functionalization of surfaces via radical grafting methods to obtain functional, thermoresponsive coatings with potential application in cell culture.

AB - Low-molecular weight linear poly(glycidyl ether)s are typically synthesized via the “classical,” oxy-anionic ring-opening polymerization (ROP) of glycidyl ether monomers at elevated temperatures. To reduce reaction times, a fast process was developed to synthesize oligo(glycidyl ether)s (OGEs) in bulk at a gram-scale utilizing microwave heating. Well-defined thermoresponsive copolymers comprising glycidyl methyl ether and ethyl glycidyl ether with molecular weights of up to 3 kDa were synthesized via microwave-assisted ROP with reaction times of approximately 10 min. The fast reaction kinetics were attributed to the rapid and uniform heating and high temperatures reached during the reaction. Consequently, no significant microwave-specific acceleration of the oxy-anionic ROP was observed. The temperature-triggered phase transition of the OGEs in aqueous solution revealed cloud point temperatures that are highly dependent on the OGE molecular weight, concentration, and comonomer composition, which extends previously reported data. Furthermore, oligo(glycidyl ether) acrylates (OGEAs) with reactive, functional end groups were directly accessible via in situ quenching of the anionic, microwave-assisted ROP with acrylic acid chloride. The obtained thermoresponsive OGEA macromonomers represent a promising material for the functionalization of surfaces via radical grafting methods to obtain functional, thermoresponsive coatings with potential application in cell culture.

KW - cloud point temperature

KW - lower critical solution temperature

KW - oxy-anionic ring-opening polymerization

KW - thermoresponsive macromonomer

UR - http://www.scopus.com/inward/record.url?scp=85053660632&partnerID=8YFLogxK

U2 - 10.1002/pola.29227

DO - 10.1002/pola.29227

M3 - Article

AN - SCOPUS:85053660632

VL - 56

SP - 2496

EP - 2504

JO - Journal of Polymer Science, Part A: Polymer Chemistry

JF - Journal of Polymer Science, Part A: Polymer Chemistry

SN - 0887-624X

IS - 21

ER -