Organophosphorus polymers. I. Peroxide‐initiated polymerization of diethyl and diisopropyl vinylphosphonate

Abstract

It was shown that diethyl vinylphosphonate and diisopropyl vinylphosphonate are polymerized by peroxide initiators to clear, light‐yellow, viscous liquid polymers of low molecular weight. It was found that the yield of the isolated polymers varied directly, while the molecular weight varied inversely, with the concentration of the initiator. Infrared spectra of the monomers used and the polymers obtained established that polymerization occurs through the vinyl group. It is postulated that the low molecular weight is due to the result of chain transfer with polymer and/or monomer through the alkoxy groups attached to the phosphorus atom.

Fireproofing of polyurethane elastomers by reactive organophosphonates

“…Moreover, the SEC chromatogram of the phosphonate diol I is very narrow, which is in agreement with the absence of allylic polymerization during the thiol–ene addition, as mentioned in the literature 15. 16, 19 Some experiments were carried out with an excess of double bonds (R = [thiol]/[allyl] = 0.5 and 0.75) in order to promote radical polymerization and to obtain an oligomer diol with a higher percentage of phosphorus.…”

“…The low reactivity of allyl and vinyl dialkyl phosphonates with regard to radical polymerization has been described by many authors 15. 16 Several papers deal with free radical thiol–ene addition processes on various phosphorus monomers bearing fluoro,17 silyl18 or hydroxyl19 groups.…”

Synthesis and cyclopolymerization of diallylammoniomethanesulfonate

“…and , respectively. The absence of any residual alkene proton or carbon signal in the spectra indicated the chain transfer process for the termination reaction involving the macroradical abstracting the labile allylic hydrogen of monomer 7 . Note that the NMR signals of PSB 16 are shifted downfield than that of APE 17 as a result of the former having the presence of electron‐withdrawing positive nitrogens (Fig.…”

Aspartic acid in a new role: Synthesis and application of a pH-responsive cyclopolymer containing residues of the amino acid

“…1 and 2, respectively. The low molecular weights of the polymers and the absence of any residual alkene in the NMR spectra of the polymers suggested the presence of the chain termination process by abstraction of an allylic proton of the monomer [31] as well as by the coupling process [32]. After hydrolysis, the OCH 3 signals in 7 completely disappear in the NMR spectra of 9.…”