Synthesis of poly(2‐furyloxirane) with high molecular weight and improved regioregularity using macrocyclic ether as a cocatalyst to potassium tert‐butoxide

Abstract

Abstract2‐Furyloxirane (FO), a monomer usually obtained from a nonpetroleum route, was prepared from the epoxidation reaction of furfural and trimethylsulfonium chloride. About 200–300 g FO can be obtained in each preparation process. Although anionic polymerization of FO generally gives low‐ molecular‐weight polymers even after long periods of polymerization, the reaction was greatly improved when macrocyclic ether was used as a cocatalyst to potassium tert‐butoxide. When 18‐crown‐6 was used as a cocatalyst, poly(2‐furyloxirane) (PFO) with a number‐average molecular weight (Mn) of 41.5 kg/mol and a polydispersity index of 1.3 was obtained at 94% yield after polymerization at 40 °C for 72 h. The PFO obtained contained a 61.7% head‐to‐tail (H‐T) structure in the absence of the macrocyclic ether, and it reached 70.6% when cryptand[2,2,2] was used as a cocatalyst. PFO with higher regioregular structures showed improved thermal properties. For PFO with Mn of around 20.0 kg/mol, its glass transition temperature (Tg) increased from −3 to 6 °C when the H‐T content was increased from 61.7 to 70.6%. Raising the Mn of PFO also raised Tg. For PFO with 68.9% H‐T structure, its Tg could reach 7 °C when Mn was increased to 40 kg/mol. This study shows two effective ways to improve the thermal and mechanical performances of the polymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Synthesis and properties of regio-regular poly(2-furyloxirane) using tri-isobutyl aluminium as catalyst

“…[14] The 13 C-NMR spectrum of PFO catalyzed by 18-crown-6/potassium tert-butoxide was also shown Fig. 2, [16] it was similar to that of PFO catalyzed by Al(i-Bu) 3 , except for the region from 70 ppm to 75 ppm, which were assigned to head-to-head and tail-totail structures. There were no signals in Fig.…”

“…The solution or bulk polymerization of FO initiated by potassium tert-butoxide has been studied by Gandini and coworkers, PFO with M n of 2.5 kg/mol was obtained in 80% yield in 6 weeks by solution polymerization, while PFO with M n of 10.1 kg/mol was obtained in 82% yield at room temperature in 3 days by bulk polymerization [14,15]. The resulted PFO contained a 61.7% headto-tail structure(H-T) caused by both C α and C β oxirane ring opening of FO during polymerization [16]. PFO with higher regio-regular structure was obtained from a bulk polymerization catalyzed by aluminum isopropoxide at room temperature, however the polymerization proceeded too violently, and difficult to give explicit discussion [14].…”

New Kind of Polymer Materials Based on Selected Complexing Star-Shaped Polyethers

“…Complexing compounds are very popular because of the wide application range. They are used among other things: in medicine as a capture and neutralize metal ions compounds [3,4,5], as catalysts in polymerization reactions [6,7,8,9,10,11,12,13], as crown ether complex cation ionic liquids catalysts [14,15,16], as activators [17,18], as protecting groups in organic synthesis [19], as chiral gels utilized as memory-erasing recycle system or logic gates based on the stimuli-responsive gel–sol transition, as chiral selectors to separate amino acid enantiomers in capillary electrophoresis analysis of amino acid enantiomers [20,21,22,23], as effective sensors [24,25,26,27,28,29], as a component of ion-selective membrane electrode [30,31], as extractants for various elements [32,33,34,35,36], and as hydraphiles—synthetic ionophores designed to mimic some properties of protein channels that conduct cations such as sodium [37].…”