Rearrangements of the propagating chain end in the cationic polymerization of vinylcyclopropane and related compounds

Ketley, A. D.; Berlin, Alvin J.; Fisher, L. P.

doi:10.1002/pol.1967.150050121

Cited by 22 publications

(10 citation statements)

References 14 publications

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“…In the cationic polymerization of VCP in the presence of AlBr 3 at -78 8 C, the number of double bonds per repeating unit was 0.10 72) , showing that the rearrangement of cation (I) to (II) might be slower than the addition of cation (I) on the VCP.…”

Section: Polymerization Of Vinylcyclopropane and Monosubstituted Derimentioning

confidence: 96%

“…If the a -hydrogen of the vinyl group was substituted by the small methyl group (isopropenylcyclopropane), a polymer with predominately 1,2-structural units was formed 69) . If the substituent was a bulky 2,4-dimethylphenyl group 72) , the formed polymer contained no cyclopropyl groups but 1,5-structural and also cyclobutyl units. Moreover, in case of the more bulky 4-isopropylphenyl substituent, the exclusive formation of a cyclobutyl groups containing polymer was found 72) and, thereby, the rearrangement of cation (I) to the nonclassical, resonance stabilized bicyclobutonium ion (III) was postulated (Scheme 11).…”

Section: Polymerization Of Vinylcyclopropane and Monosubstituted Derimentioning

confidence: 99%

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Synthesis and polymerization of vinylcyclopropanes

Moszner

Zeuner

Völkel

et al. 1999

Macromol. Chem. Phys.

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SUMMARY: Vinylcyclopropanes are important synthetic intermediates in organic chemistry and are mostly synthesized by the simultaneous introduction of the cyclopropane and the vinyl unit, e. g., by the reaction of trans-1,4-dihalobutenes with b -dicarbonyl compounds or the addition of carbenes to dienes. The polymerization of vinylcyclopropane itself results in vinyl polymers with predominantly 1,2-structural units. The radical polymerization of substituted vinylcyclopropanes results in polymers with mainly 1,5-ring-opened units, whereby radical stabilizing substituents or electron-withdrawing groups increase the radical polymerizability and the ring-opening ability. The vinylcyclopropanes undergo a radical copolymerization with other vinyl monomers, such as methacrylates, and, in comparison to the polymerization of these linear vinyl monomers, the vinylcyclopropanes show a significantly lower volume shrinkage during ring-opening polymerization. Hybrid vinylcyclopropanes are polymerized step-by-step under formation of reactive polymers or polymer networks. Multifunctional cross-linking vinylcyclopropanes can be used as new low-shrinking matrix monomers for photopolymerizable materials. In addition, the sol-gel process of trialkoxysilyl-functionalized vinylcyclopropanes affords low shrinking organic-inorganic nanocomposites.

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Section: Polymerization Of Vinylcyclopropane and Monosubstituted Derimentioning

confidence: 96%

Section: Polymerization Of Vinylcyclopropane and Monosubstituted Derimentioning

confidence: 99%

Synthesis and polymerization of vinylcyclopropanes

Moszner

Zeuner

Völkel

et al. 1999

Macromol. Chem. Phys.

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“…Molecular weights were determined between 1 100 and 7 100 g Á mol À1 . Cationic polymerization of such monomers using AlBr 3 was investigated by Fischer et al [11] They obtained polymers with 1,2-, 1,5-and cyclobutane structures. Depending on the substituents of the vinyl double bond the part of 1,5-structures reaches up to 60%.…”

Section: Introductionmentioning

confidence: 99%

Photoinitiated Cationic Polymerization of Substituted Vinylcyclopropanes

Al-Doaiss

Günther

Klemm

et al. 2005

Macro Chemistry & Physics

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Summary: The photoinitiated cationic polymerization of 1‐cyclopropyl‐l‐phenyl‐ethylene, 1‐cyclopropyl‐l‐(p‐methoxyphenyl)ethylene and 1‐cyclopropyl‐l‐(p‐fluorophenyl)ethylene at ambient temperatures in bulk and in solution was investigated using (η5‐2,4‐cyclopentadiene‐l‐yl)[l,2,3,4,5,6‐η] (l‐(methylethyl) benzene)iron(I) hexafluorophosphate (Irgacure 261, I‐1) and ditolyliodonium hexafluorophosphate (I‐2). In contrast to our results in the polymerization of 2‐cyclopropyl‐4‐methylene‐l,3‐dioxolanes, partial ring‐opening of the cyclopropane ring could be detected. A volume shrinkage of about 11% was found.

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“…[6,7] These electrophiles underwent rapid addition to cyclopropane or alkylsubstituted cyclopropane derivatives. [8] In the polymer of vinylcyclopropane a major portion of the cyclopropyl groups remain intact. reported about rearrangements of the propagating chain end in the cationic polymerization of vinylcyclopropane and related compounds.…”

Section: Introductionmentioning

confidence: 99%