Electron density distribution in unsaturated ethers and esters, and their reactivity in cationic polymerization

Éizner, Yu.Ye.; Skorokhodov, S. S.; Zubova, T. P.

doi:10.1016/0014-3057(71)90052-8

Cited by 11 publications

(1 citation statement)

References 7 publications

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“…This is in agreement with calculated electron density distributions, from which it was also concluded that vinyl carbonates should be active in cationic polymerization if one could suppress the addition of the initiator or the active end of the growing polymer chain to the carbonyl group. 50 Schaefgen failed to polymerize 3 by an anionic mechanism with lithium aluminium hydride in decalin although these conditions gave the best yield of poly(tert-butyl acrylate). 28,29 This can be easily explained by the electron withdrawing behavior of the acrylate group that stabilizes the propagating anion that is not present in vinyl carbonates.…”

Section: Ionic Polymerizationmentioning

confidence: 99%

Vinyl carbonates, vinyl carbamates, and related monomers: synthesis, polymerization, and application

Husár

Liska

2012

Chem. Soc. Rev.

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Although acrylates and methacrylates are the state-of-the-art monomers for protective and decorative coatings, skin and inhalation irritancy and potential cytotoxicity of monomers present serious health hazards. Monomers like vinyl carbonates or vinyl carbamates can overcome these problems with their generally lower cytotoxicity and yet similar photoreactivity to (meth)acrylates. The reviewed classes of monomers have not attracted industry's attention until now due to expensive synthetic methods though recently developed affordable routes offer prospect for their increasing use (88 references).

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Section: Ionic Polymerizationmentioning

confidence: 99%

Vinyl carbonates, vinyl carbamates, and related monomers: synthesis, polymerization, and application

Husár

Liska

2012

Chem. Soc. Rev.

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Cationic polymerization of vinyl ethers as synthetic path to diphylic polymers and potential complexants

Skorokhodov

1986

Makromolekulare Chemie. Macromolecular Symposia

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The polymers of universal solubility like dimethyl ether of ethylene glycol and dioxane are synthesised by cationic polymerization of cis‐1,2‐dimethoxyethylene and p‐dioxene. Some specific features of polymerization, going on long‐lived active centers, are observed. In the case of polymerization of cis‐1,2‐dimethoxyethylene, conducted under usual conditions, the possibility of obtaining polymers with molecular weights as high as 106 and M̄w/M̄N<1.5 is shown. Improved procedures of cyclopolymerization of divinyl ethers of mono‐, di‐, and triethylene glycols are described. Some solution properties of polymers obtained, including conformational transitions and metal ion complexing, are discussed.

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Effect of pressure on free‐radical copolymerization kinetics. I. A concept of additivity of partial molar volumes of activation

Meer

German

Heikens

1977

J. Polym. Sci. Polym. Chem. Ed.

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SynopsisA short review of the effect of pressure on copolymerization kinetics shows the necessity of simple models for a better understanding of activation volumes. Therefore, a simple concept, possibly generally valid for free-radical polymerization, is proposed, based on the assumption that molar volumes of activation can be expressed as an addition of a characteristic radical and a monomer contribution, regardless of the combination involved. The scheme may facilitate the visualization of the transition state and contribute to the understanding of reaction mechanisms of radical polymerizations. Ethylene-vinyl acetate copolymerization at 62OC with tert -butyl alcohol as solvent agrees with the proposed scheme, appearing from the pressure independence of the product of reactivity ratios at the different levels (35,600, and 1200 kg/cm2). Implicitly it can be shown that an ethylene monomer contributes about 2 cm3/mole more to the activation volumes of the propagation reactions than does the vinyl acetate monomer, whereas for the radicals the difference of the respective contributions to the activation volumes is opposite in sign.

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Electron density distribution in unsaturated ethers and esters, and their reactivity in cationic polymerization

Cited by 11 publications

References 7 publications

Vinyl carbonates, vinyl carbamates, and related monomers: synthesis, polymerization, and application

Vinyl carbonates, vinyl carbamates, and related monomers: synthesis, polymerization, and application

Cationic polymerization of vinyl ethers as synthetic path to diphylic polymers and potential complexants

Effect of pressure on free‐radical copolymerization kinetics. I. A concept of additivity of partial molar volumes of activation

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