Synthesis, Characterization and Thermal Properties of Poly(ethylene oxide), PEO, Polymacromonomers via Anionic and Ring Opening Metathesis Polymerization

George V Theodosopoulos; Christos Zisis; Georgios Charalambidis; Vasilis Nikolaou; Athanassios G Coutsolelos; Marinos Pitsikalis

doi:10.3390/polym9040145

Synthesis, Characterization and Thermal Properties of Poly(ethylene oxide), PEO, Polymacromonomers via Anionic and Ring Opening Metathesis Polymerization

Polymers (Basel). 2017 Apr 21;9(4):145. doi: 10.3390/polym9040145.

Authors

George V Theodosopoulos¹, Christos Zisis², Georgios Charalambidis³, Vasilis Nikolaou⁴, Athanassios G Coutsolelos⁵, Marinos Pitsikalis⁶

Affiliations

¹ Laboratory of Industrial Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece. scimaster1821@gmail.com.
² Laboratory of Industrial Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece. chriszisis1994@gmail.com.
³ Laboratory of Bioinorganic Chemistry, Department of Chemistry, University of Crete, Voutes Campus, 71003 Heraklion, Greece. gxaral@chemistry.uoc.gr.
⁴ Laboratory of Bioinorganic Chemistry, Department of Chemistry, University of Crete, Voutes Campus, 71003 Heraklion, Greece. nikolaouvasilis13@hotmail.com.
⁵ Laboratory of Bioinorganic Chemistry, Department of Chemistry, University of Crete, Voutes Campus, 71003 Heraklion, Greece. acoutsol@uoc.gr.
⁶ Laboratory of Industrial Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece. pitsikalis@chem.uoa.gr.

Abstract

Branched polymers are a valuable class of polymeric materials. In the present study, anionic polymerization techniques were employed for the synthesis of low molecular weight poly(ethylene oxide) (PEO) macromonomers bearing norbornenyl end groups. The macromonomers were characterized by SEC, MALDI-TOF and NMR spectroscopy. Subsequent ring opening metathesis polymerization (ROMP) of the macromonomers using ruthenium catalysts (Grubbs catalysts of the 1st, 2nd and 3rd generations) afforded the corresponding polymacromonomers. The effects of the macromonomer molecular weight, the type of the catalyst, the nature of the solvent, the monomer concentration and the polymerization temperature on the molecular characteristics of the branched polymers were examined in detail. The crystallization behavior of the macromonomers and the corresponding polymacromonomers were studied by Differential Scanning Calorimetry (DSC). The thermal stability and the kinetics of the thermal decomposition of the samples were also studied by Thermogravimetric Analysis (TGA). The activation energies of the thermal decomposition were analyzed using the Ozawa⁻Flynn⁻Wall and Kissinger methodologies.

Keywords: Grubbs catalyst; anionic polymerization; macromonomers; norbornene; poly(ethylene oxide); polymacromonomers; ring opening metathesis polymerization (ROMP).

Grants and funding

377252/European Union (European Social Fund-ESF) and Greek national funds through the Operational Program "Education and Lifelong Learning" of the National Strategic Reference Framework (NSRF)-Research Funding Program: THALES.