(Co)Polymerization of vinyl levulinate by cobalt-mediated radical polymerization and functionalization by ketoxime click chemistry

Abstract

International audienceVinyl levulinate is synthesized from levulinic acid by palladium-catalyzed vinyl exchange and is characterized by NMR and ESI-HRMS techniques. Homopolymerization of vinyl levulinate and random copolymerization with vinyl acetate by cobalt-mediated radical polymerization affords well-defined ketone functionalized poly(vinyl ester)s. The impact of temperature, solvent and theoretical degree of polymerization on monomer conversion and control of the polymerization is studied by H-1 NMR and size exclusion chromatography techniques. The ketoxime conjugation of O-benzylhydroxylamine with the pendant ketone functionality of poly(vinyl levulinate-co-vinyl acetate) is demonstrated

Poly(1,2,3-triazolium)s: a new class of functional polymer electrolytes

“…72 1,2,3-Triazolefunctionalized vinyl ester monomer 33 was thus synthesized by CuAAC between 4-azidovaleric acid and 1-pentyne 27 followed by palladium-catalyzed vinyl exchange between the resulting 1,2,3-triazole-functionalized carboxylic acid and vinyl acetate. 73 This versatile yet efficient method for the synthesis of vinyl esters is of primary importance since it is able to significantly broaden the structural and functional variety of poly(vinyl ester)s. 74 Indeed, due to earlier synthetic limitations of the monomers, the structural variety of poly(vinyl ester)s has been significantly less explored than other classes of industrially relevant polymer materials. CMRP, an effective method for the CRP of non-conjugated vinyl monomers such as vinyl esters, 75 was successfully applied to the polymerization of 33 using an alkyl-cobalt(III) oligomer (R-Co(acac) 2 ) as both the initiator and the controlling agent of the polymerization process.…”

Postpolymerization modification of reactive polymers derived from vinylcyclopropane. III. Polymer sequential functionalization using a combination of amines with alkoxyamines, hydrazides, isocyanates, or acyl halides

“…However, no universal synthetic procedure for this modification can be given and, the conversion and the reaction time depend on the polymer structure. Usually, aldehydes react very fast with hydrazides or alkoxyamines and conversions of almost 100% are common, while the reaction of ketones depends on their position on the polymer backbone . In our case, it is therefore likely to assume that the presence of the amide moiety on the same carbon next to the ketone group can affect the conversion.…”

“…Modification of ketone or aldehyde containing polymers with hydrazides and alkoxyamines (hydroxylamines) has been sufficiently described in the literature . This reaction was mostly used for bioconjugation.…”

Cobalt(iii) acetylacetonate initiated RAFT polymerization of acrylonitrile and its application in removal of methyl orange after electrospinning

“…Recently, as one typical chelate ber of the podand type, polyacrylonitrile (PAN)-based nanobers (PAN-nFs) have emerged as a superior polymer for introducing amino groups. 24 Among RDRP systems, transition metal salts, especially cobalt compounds, [25][26][27][28][29] have played "living"/controlled roles in the polymerization of reactive vinyl monomers. 15,16 Generally, nFs can be easily produced by the electrospinning technique since electrical forces were rst applied to polymeric laments by A. Formhals.…”