Novel dialkyl vinyl ether phosphonate monomers: Their synthesis and alternated radical copolymerizations with electron‐accepting monomers

Abstract

Three new vinyl ether monomers containing phosphonate moieties were synthesized from transetherification reaction. We showed that the yield was dependent on the spacer length between the vinyl oxy group and the phosphonate moieties: when the spacer is a single methylene side reaction may occur, leading to the formation of acetal compounds. Free-radical copolymerizations of phosphonate-containing vinyl ether monomers with maleic anhydride were carried out, leading to alternated copolymers of rather low molecular weights (from 1000 to 7000 g/mol). Both gel permeation chromatography and 31 P NMR analyses enhanced possible intramolecular transfer reactions occurring from the phosphonate moieties. Kinetic investigation showed that the electron-withdrawing character of the phosphonate moieties tends to decrease the rate of copolymerization. Nevertheless, almost complete monomers conversion was reached after 30 min of reaction with dimethyl vinyloxyethylphosphonate (VEC 2 PMe). Then, radical copolymerization of VEC 2 PMe with a series of electron-accepting monomers, that is, dibutyl maleate, dibutylitaconate, itaconic anhydride, butyl maleimide, and methyl maleimide, led to a series of alternated copolymers. From kinetic investigation, we showed that the higher the electron-accepting effect, the faster the vinyl ether consumption and the higher the molecular weights.

Synthesis and characterization of novel functional vinyl ethers that bear various groups

“…In 2013, our group published the transetherification between EVE and various alcohols leading to the corresponding original VEs in 40-84% yield in a single step synthesis [18,[28][29][30][31][32][33]. A series of VEs monomers that bear diverse functional groups, such as halogenomethyl, amino, carbonate, oligo(ethylene oxide) side-groups, and oligo(fluoroether) chains, was prepared and characterized by NMR spectroscopy.…”

Radical copolymerization ofN-phenylmaleimide and diene monomers in competition with diels-alder reaction

“…Alternating radical copolymerization has many advantages for polymer synthesis, such as the production of a high‐molecular‐weight copolymer in a high yield, well‐defined alternating sequence structures independent of the comonomer ratio in the feed, and the use of various monomers . N‐Substituted maleimides (RMI) as the electron‐accepting monomers readily provide alternating copolymers with excellent thermal, optical, and mechanical properties during radical copolymerization with electron‐donating monomers, such as styrene, vinyl ethers, and isobutene . In contrast to the facile copolymerization of the RMIs with olefins, they react with 1,3‐diene compounds, such as butadiene, cyclopentadiene, and furan to predominantly yield Diels–Alder adducts rather than alternating copolymers .…”

Synthesis of dialkyl 2-(Methacryloyloxyethyl) phosphonates, their characterization and polymerization

“…This can be attributed to the ability of phosphorus to exist in variable oxidation states [10]. Phosphorus based polymers has found wide applications as dispersants [16], anticorrosion agents [16,17], lubricants [18], proton conducting fuel cell membranes for alternate energy production, adhesion promoters for paints and lacquers [15][16][17][18][19], as ion exchange resins [17,18,20], chelating agents for heavy metal salts [20], oxygen plasma resistance, poly mer supported catalysis, radiation resistance, selective metal binders [15] and in biomedical field as dental adhesives, as regenerative medicine, in tissue engi neering, as carriers for bioactive molecules, in devel oping biomimetic compounds, in drug delivery system etc. [16,18].…”