The aza-Michael reaction as an alternative strategy to generate advanced silicon-based (macro)molecules and materials. (September 2017)

• Record Type: Journal Article
• Authors: Genest, Aymeric; Portinha, Daniel; Fleury, Etienne; Ganachaud, François
• Is Part Of: Progress in polymer science. Volume 72(2017)
• Page Start: 61
• Page End: 110
• Publication Date: 2017-09
• Subjects: 1°amine primary amine -- 2°amine secondary amine -- 3°amine tertiary amine -- Ac acetyl group -- Alk alkyl group -- APTMS aminopropyltrimethoxysilane -- BF base formulation -- cP centipoise -- DABCO® 1, 4-diazobicyclo [2.2.2] octane -- DBU 1, 8-diazabicyclo[5.4.0]undec-7-ene -- DMA dimethylacetamide -- DMF dimethylformamide -- DMPS dodecamethylpentasiloxane -- DP degree of polymerization -- DSC differential scanning calorimetry -- E Young's modulus -- EB electron beam -- ESO epoxidized soybean oil -- EWG electron-withdrawing group -- FTIR Fourier transform infrared spectroscopy -- GC gas chromatography -- GC–MS gas chromatography coupled with mass spectrometry -- HFIP hexafluoropropan-2-ol -- HY compound having hydrogen-bond accepting and donating abilities (amines alcohols) -- IPA isopropanol -- IR infrared -- JIS Japanese industrial standard -- k rate constant -- K equilibrium constant -- M concentration units (mol L−1) -- MEK methyletherketone -- MPa megapascal -- Mw molecular weight -- NMR nuclear magnetic resonance -- Pa Pascal -- PAMAM polyamidoamine -- PDMS polydimethylsiloxane -- PDO 1, 2-propanediol -- PEG poly(ethyleneglycol) -- PET polyethylene terephthalate -- POSS polyoctahedral silsesquioxanes -- PR Piers-Rubinsztajn -- PUR polyurethane -- PVP polyvinylpyrrolidone -- r molar ratio -- REACh Registration Evaluation Authorization and restriction of Chemicals -- RIM reaction injection molding -- RT room temperature -- RTV room-temperature vulcanization -- SEC size-exclusion chromatography -- SM surface modifier -- TFE 2, 2, 2-trifluoroethanol -- THF tetrahydrofuran -- TMPTA trimethylolpropane-triacrylate -- UV ultraviolet -- v kinetic rate -- VS versus -- WCA water contact angle -- wt weight; PDMS -- Functionalization -- Networks -- Elastomers -- Alkoxysilanes; Polymers -- Periodicals; Polymerization -- Periodicals; Polymers -- Industrial applications -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; 547.7
• DOI: 10.1016/j.progpolymsci.2017.02.002
• Languages: English
• ISSNs: 0079-6700

Abstract

Abstract: Aza-Michael reaction is a simple and accessible addition reaction performed at moderate temperature, possibly without a catalyst and without releasing by-products. Its versatility allows designing specific structures thanks to the availability of a multitude of Michael acceptors and Michael donors. The reaction rate of the aza-Michael reaction can be improved by adding different co-reactants (polar protic solvents, catalysts) and/or adjusting the external energy sources (e.g. moderate to high temperatures or high pressures). Here, we show that this addition reaction is efficient for modifying or curing silicon-containing molecules, oligomers and polymers. The pros and cons of applying the aza-Michael reaction to silicon-containing molecules (including alkoxysilanes and PDMS) are highlighted. A large variety of intermediates such as coupling agents, reactive diluents, and sol-gel precursors prepared by the aza-Michael reaction are presented. Finally, applications of these, including products ranging from functional silicone intermediates to soft (unfilled) elastomers, are reported.