Α, ω-Di(vinylene carbonate) telechelic polyolefins: Synthesis by metathesis reactions and studies as potential precursors toward hydroxy-oxazolidone-based polyolefin NIPUs. (July 2019)

• Record Type: Journal Article
• Authors: Chauveau, Cyril; Fouquay, Stéphane; Michaud, Guillaume; Simon, Frédéric; Carpentier, Jean-François; Guillaume, Sophie M.
• Is Part Of: European polymer journal. Volume 116(2019)
• Page Start: 144
• Page End: 157
• Publication Date: 2019-07
• Subjects: Telechelic polyolefin -- Metathesis -- Oxazolidone -- Vinylene carbonate -- Non-isocyanate polyurethane (NIPU); Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2019.03.052
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Highlights: Synthesis of original vinylene carbonate (VC) compounds. Tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclic olefins. α, ω-Di(vinylene carbonate) telechelic polyolefins. Reactivity of 4, 5-dimethyl-1, 3-dioxol-2-one (DMDO). Poly(di(hydroxy-oxazolidone)polyolefin). Polyaddition toward non-isocyanate polyurethanes (NIPUs). Abstract: Current polyurethane (PU) industrial and academic research aims at developing non-isocyanate PUs, referred to as NIPUs. Within this context, we report herein the synthesis of original vinylene carbonate (VC) compounds, subsequently used as chain-transfer agents (CTAs) towards the preparation of α, ω-di(VC) telechelic (co)polyolefins from the tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclic olefins. Thus, (5-methyl-2-oxo-1, 3-dioxol-4-yl)methyl acrylate (VC1 ), bis((5-methyl-2-oxo-1, 3-dioxol-4-yl)methyl) fumarate (VC2 ), and bis((5-methyl-2-oxo-1, 3-dioxol-4-yl)methyl) ( E )-hex-3-enedioate (VC3 ) were synthesized from 4-(hydroxymethyl)-5-methyl-1, 3-dioxol-2-one (DMDO-OH). Among these, onlyVC3 successfully and selectively afforded well-defined α, ω-di(vinylene carbonate) telechelic polyolefins, namely di(VC3 )-PCOE and di(VC3 )-P(NB -co- CDT), from the ROMP/CM of COE, and norbonene (NB)/ trans, trans, cis -1, 5, 9-cyclododecatriene (CDT), respectively, using Grubbs' 2nd-generation ruthenium catalyst (G2 ) under mild operating conditions (CH2 Cl2, 40 °C, 3 h). Preliminary investigations on the reactivity of a model VC, namely 4, 5-dimethyl-1, 3-dioxol-2-one (DMDO), towards nucleophiles such as a primary or secondary amine, promisingly showed the formation of hydroxy-oxazolidone compounds1 and2, and oxo-urethane3 species, respectively. Yet, the ultimate reaction of di(VC3 )-PCOE with 2, 2′-(ethylenedioxy)bis(ethylamine) (EDR-148) did not give the expected poly(di(hydroxy-oxazolidone)polyolefin) polyaddition type of NIPUs; competing amidation and/or dehydration or urea formation reactions evidenced by detailed NMR, FTIR and MS analyses, were proposed to account for this inefficiency.