Anionic flow polymerizations toward functional polyphosphoesters in microreactors: Polymerization and UV-modification. (July 2016)

• Record Type: Journal Article
• Authors: Baeten, Evelien; Vanslambrouck, Stephanie; Jérôme, Christine; Lecomte, Philippe; Junkers, Thomas
• Is Part Of: European polymer journal. Volume 80(2016:Jul.)
• Page Start: 208
• Page End: 218
• Publication Date: 2016-07
• Subjects: Microreactor -- Poly(phosphoester) -- Continuous flow -- Thiol–ene -- Postpolymerization modification -- Coupled flow reactors; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2016.02.012
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Highlights: Poly(phosphoester)s, PPEs have been successfully polymerized in microstructured flow reactors. By using flow chemistry, reaction rates are increased and side reactions reduced. Alkene-functional PPEs have been obtained that allow for UV-induced modification of the backbone, also in flow. The thermally activated polymerization could be directly coupled to the UV modification in a reactor cascade. Abstract: The polymerization of cyclic phosphates to poly(phosphoester)s, PPEs, is optimized for chip-based microreactors under continuous flow conditions. The anionic ring-opening polymerization of 2-isobutyoxy-2-oxo-1, 3, 2-dioxaphospholane (iBP) via the use of two organocatalytic systems allowed to polymerize to nearly quantitative monomer conversion within 10 or 3 min, respectively at a reaction temperature of 40 °C. Further, the optimized polymerization protocol was applied to 2-butenoxy-2-oxo-1, 3, 2-dioxaphospholane (BP) which yields a polymer that carries an alkene functionality per monomer repeating unit. This material can be postmodified in an UV-induced radical thiol–ene reaction, which was also shown to proceed with very high efficiency under UV-flow conditions. Eventually, both reactions were coupled in a two-stage reactor setup, showing that the thermally-activated polymerization can be coupled with high efficiency to the UV-activated post-polymerization modification reaction. The introduced reactor setup can in the future be used to produce and screen a broad variety of functional PPE materials with various functionalities and physical properties.