Copolymerisation of Unsaturated Organophosphorus Monomers

Shulyndin, S.V.; Levin, Yu. A.; Ivanov, B. E.

doi:10.1070/rc1981v050n09abeh002691

Cited by 17 publications

(7 citation statements)

References 3 publications

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“… The formation of low molecular mass PDAVPs via radical polymerization has also been observed in other studies . An approach to overcome these limitations has not been achieved yet despite numerous attempts by researchers over the past decades. ,− Copolymers of DEVP and styrene, methyl methacrylate, butadiene, acrylonitrile, and other monomers are readily obtained by free radical polymerization. ,− However, conversions and phosphonate contents were found to be low and the influence of the phosphonate groups on the material properties was comparatively weak. Recently, the free radical copolymerization of DEVP and 2-chloroethyl methacrylate (CEMA) for the formation of spherical nanoparticles in water has been reported .…”

Section: Radical and Anionic Polymerization Of Vinylphosphonatesmentioning

confidence: 88%

Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers

Soller

Salzinger²,

Rieger

2015

Chem. Rev.

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This review focuses on introducing and explaining the rare earth metal-mediated group transfer polymerization (REM-GTP) of polar monomers and is composed of three main sections: poly(vinylphosphonate)s, surface-initiated group transfer polymerization (SI-GTP), and extension to N-coordinating Michael-type monomers (2-vinylpridine (2VP), 2-isopropenyl-2-oxazoline (IPOx)). The poly(vinylphosphonate)s section is divided into two parts: radical, anionic, and silyl ketene acetal group transfer polymerization (SKA-GTP) of vinylphosphonates in comparison to REM-GTP, and properties of poly(vinylphosphonate)s. The mechanism of vinylphosphonate REM-GTP is discussed in detail for initiation and propagation including activation enthalpies ΔH(‡) and entropies ΔS(‡) according to the Eyring equation. SI-GTP is presented as a method for surface functionalization, and recent trends for 2VP and IPOx polymerization are summarized. This review will serve as a good resource or guideline for researchers who are currently working in the field of rare earth metal mediated polymerization catalysis as well as for those who are interested in beginning to employ rare earth metal complexes for the synthesis of new materials from polar monomers.

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Section: Radical and Anionic Polymerization Of Vinylphosphonatesmentioning

confidence: 88%

Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers

Soller

Salzinger²,

Rieger

2015

Chem. Rev.

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“…Nevertheless, these authors mentioned that this reaction was predominant mainly with isopropyl as alkyl group (Scheme , reaction 1), thus leading to a tertiary radical that promotes fast initiation. Shulyndin et al40 proposed another mechanism also based on radical transfer reaction (Scheme , reaction 2). They claimed that intracyclization occurred between the growing radical and the phosphonate moieties, leading to the generation of an alkyl radical species and of the creation of five‐member cycle.…”

Section: Resultsmentioning

confidence: 99%

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

Iftene

David

Boutevin

et al. 2012

J. Polym. Sci. A Polym. Chem.

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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.

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“…DISP (1.0 mL, 5 × 10 -3 mol) and initiator (AIBN (0.5 mg, 3.0 × 10 -3 mmol) (0.5 g/L) or CVA (0.9 mg, 3 × 10 -3 mmol) (0.85 g/L)) were put in a Schlenk flask, which was evacuated and backfilled with nitrogen prior to the polymerization. The reaction mixture was heated to 60 °C for 12.5 h. The conversion was 35% as determined by 1 H NMR by comparing the intensities of the signal of the methine (OCH) protons of oligo-(DISP) with that of the double bonds left in the reaction medium in the 1 H NMR spectrum after polymerization.…”

Section: Methodsmentioning

confidence: 99%

“…Copolymers of vinyl phosphonates find use in the electrical, transportation, and construction industries due to their flame-retardant properties; however, relatively few investigations into the homopolymerization of vinyl phosphonates have been reported. The few reports found in the literature have investigated the free radical polymerization of diethyl vinyl phosphonate (DEVP), diisopropyl vinyl phosphonate (DISP), and dimethyl vinyl phosphonate (DMVP). , Kosolapoff et al indicated the reluctance of DEVP to polymerize, and Pike et al.…”

Section: Introductionmentioning

confidence: 99%

Characterization of Oligo(vinyl phosphonate)s by High-Resolution Electrospray Ionization Mass Spectrometry: Implications for the Mechanism of Polymerization

et al. 2008

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Dimethyl vinyl phosphonate, diethyl vinyl phosphonate, and diisopropyl vinyl phosphonate were polymerized at 60 °C via free radical polymerization to give oligomers. High-resolution electrospray ionizationmass spectrometry was used to analyze the resulting oligo(vinyl phosphonate)s in order to elucidate their polymerization mechanism. The resulting mass spectra showed no evidence of polymer chains capped with initiator derived fragments as end groups. Instead, the mass spectra indicated that transfer reactions generate activated monomer species (i.e., a monomeric radical), which then act as initiators in the polymerizations. Additionally, these studies indicate that termination takes place by chain transfer to monomer.

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Copolymerisation of Unsaturated Organophosphorus Monomers

Cited by 17 publications

References 3 publications

Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers

Rare Earth Metal-Mediated Precision Polymerization of Vinylphosphonates and Conjugated Nitrogen-Containing Vinyl Monomers

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

Characterization of Oligo(vinyl phosphonate)s by High-Resolution Electrospray Ionization Mass Spectrometry: Implications for the Mechanism of Polymerization

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