Polymerization of vinyl ethers by grignard compounds

Kray, R. J.

doi:10.1002/pol.1960.1204414323

Cited by 16 publications

(1 citation statement)

References 2 publications

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“…Grignard compounds (tert-BuMgBr) are similar effective catalysts [81]. Oxygen has been found to be a necessary cocatalyst for Grignard com pounds [82].…”

Section: Coordination-catalyzed Polymerizationmentioning

confidence: 99%

Poly(vinyl ethers)

Sandler

Karo²

1994

Polymer Syntheses

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“…Grignard compounds (tert-BuMgBr) are similar effective catalysts [81]. Oxygen has been found to be a necessary cocatalyst for Grignard com pounds [82].…”

Section: Coordination-catalyzed Polymerizationmentioning

confidence: 99%

Poly(vinyl ethers)

Sandler

Karo²

1994

Polymer Syntheses

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Polymerization of vinyl ether with magnesium compounds. II. Catalytic reactivity of magnesium compounds other than halides

Iwasaki

Fukutani

Tsuchida

et al. 1963

J. Polym. Sci. A Gen. Pap.

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SynopsisMagnesium compounds, especially Grignard reagents were studied aa catalysts in the polymerization of vinyl ethers. The Grignard reagent and diethyl magnesium possessed no activity for polymerization of vinyl ether. However, if the Grignard reagent is combined with some sort of third substances, it shows good activity. For these substances, oxygen, aldehydes, some metal oxides, and halogenated hydrocarbons seemed to be effective. The molecular weight of the polyvinyl ether obtained from this combined catalyst system is markedly higher than those of polymers obtained with the Friedel-Crafts type of cat,alyst, but the polymer of vinyl ether obtained from this mixed catalyst possesses little crystalline structure. The possible mechanism of the polymerization with this mixed catalyst is thought to be a cationic initiation type, because the true active species are regarded to be intermediate compounds which are analogous to magnesium halides or alkoxymagnesium halides. In this connection, alkoxymagnesium halides and magnesium oxide were examined. They had a good activity for polymerization but did not yield a high polymer.2 RMgX + Rzmg + MgX2

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Stereoregular polymerization of vinyl alkyl ethers with metal sulfate–sulfuric acid complex catalysts

Lal

McGrath

1964

J. Polym. Sci. A Gen. Pap.

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The polymerization of vinyl alkyl ethers at room temperature or above, to give crystallizable polymers is of considerable interest for both theoretical and practical considerations. The polymerization of these monomers has been studied with metal sulfate–sulfuric acid complex catalysts at 0°C. or above to give high molecular weight, isotactic polymers. Ferric hydrosulfate hydrate and aluminum hexahydrosulfate heptahydrate (AHS) were used as catalysts. The nature of the solvent employed during polymerization with these heterogeneous catalysts was found to be quite important from the point of view of polymerization rate and stereoregularity of the polymer. A vinyl ether having a linear alkyl group polymerizes considerably faster than a monomer having a branched alkyl group. The apparent first‐order rate constant values for the AHS‐catalyzed polymerization of vinyl alkyl ethers having n‐alkyl groups indicate the following sequence: ethyl > n‐butyl > n‐hexyl = n‐octyl. In the temperature range of 30–58°C. the overall activation energy for the polymerization of vinyl n‐butyl ether in heptane with AHS catalyst was found to be 9.7 kcal./mole. Vinyl n‐butyl ether was copolymerized with β‐vinyloxyethyl methacrylate (M2) using AHS catalyst. The average values of r1 = 0.82 and r2 = 0.004 were obtained.

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Polymerization of vinyl ethers by grignard compounds

Cited by 16 publications

References 2 publications

Poly(vinyl ethers)

Poly(vinyl ethers)

Polymerization of vinyl ether with magnesium compounds. II. Catalytic reactivity of magnesium compounds other than halides

Stereoregular polymerization of vinyl alkyl ethers with metal sulfate–sulfuric acid complex catalysts

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