Polymerization of cyclic monomers, 4. Synthesis and radical polymerization of bi‐ and trifunctional 2‐vinylcyclopropanes

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.

Section: Polymerization Of Cross-linking and Oligomeric Vinylcycloprocontrasting

confidence: 52%

Section: Polymerization Of Cross-linking and Oligomeric Vinylcyclopromentioning

confidence: 98%

Synthesis and polymerization of vinylcyclopropanes

Moszner

Zeuner

et al. 1999

Macromol. Chem. Phys.

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“…Ethyl a-hydroxymethylacrylate was prepared according to the literature 9) . 1-Methoxycarbonyl-2-vinylcyclopropane-1-carboxylic acid was synthesised as previously described 8) . 4-Dimethylaminopyridine (DMAP) and 1,3-dicyclohexylcarbodiimide (DCC) were used without further purification.…”

Section: Experimental Partmentioning

confidence: 99%

“…The radical bulk polymerisation is carried out in sealed glass tubes as previously described 8) . C: 100 MHz) using tetramethylsilane (TMS) as the standard and CDCl 3 or dimethyl sulfoxide-d 6 as the solvent.…”

Section: Polymerisationmentioning

confidence: 99%

“…Examples of hybrid vinylcyclopropanes are few and concern, for example, 1-vinyl-6-methylene-4,8-dioxaspiro [2.5]octane or 1-vinyl-5,7-dimethyl-6-methylene-4,8-dioxaspiro-[2.5]octane, both of which undergo a ring-opening polymerisation in the presence of radical initiators 5) . Previously, we reported the synthesis and polymerisation of symmetric and asymmetric 1,1-bissubstituted 2-vinylcyclopropane derivatives 6,7) , and of crosslinking 2-vinylcyclopropanes 1,8) . This short paper briefly describes the synthesis and radical polymerisation of hybrid vinylcyclopropanes 1a-c:…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Polymerisation of cyclic monomers, 8. Synthesis and radical polymerisation of hybrid 2-vinylcyclopropanes

Moszner¹,

Macromol. Rapid Commun.

Fischer

et al. 1999

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SUMMARY: Hybrid 2-vinylcyclopropanes were synthesised by the esterification of 1-methoxycarbonyl-2-vinylcyclopropane-1-carboxylic acid with hydroxy group containing (meth)acrylates in the presence of 1,3-dicyclohexylcarbodiimide (DCC). The structure of the new hybrid monomers was confirmed by elemental analysis, IR, 1 H NMR and 13 C NMR spectroscopy. The radical polymerisation of the hybrid monomers in bulk with 2,29-azoisobutyronitrile (AIBN) results in transparent cross-linked polymers, whereas solution polymerisation partially results in soluble polymers with pendant 2-vinylcyclopropyl groups.

Polymerization of cyclic monomers. VII. Synthesis and radical polymerization of 1,3-bis[(1-alkoxycarbonyl-2-vinylcyclopropane-1-yl)carboxy]benzenes

Moszner

Zeuner

et al. 1999

J. Appl. Polym. Sci.

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1,3-Bis[(1-alkoxycarbonyl-2-vinylcyclopropane-1-yl)carboxy]benzenes 1 [RO: CH 3 O (a), C 2 H 5 O (b)] were synthesized by the esterification of the corresponding 1-alkoxycarbonyl-2-vinylcyclopropane-1-carboxylic acids with resorcinol. The structure of the new vinylcyclopropanes was confirmed by elemental analysis and infrared (IR), 1 H nuclear magnetic resonance ( 1 H-NMR), and 13 C nuclear magnetic resonance ( 13 C-NMR) spectroscopy. The radical polymerization of difunctional 2-vinyl-cyclopropanes in bulk with 2,2Ј-azoisobutyronitrile (AIBN) results in hard, transparent, crosslinked polymers. During the bulk polymerization of the crystalline bis[(1-methoxycarbonyl-2-vinylcyclopropane-1-yl)carboxy]benzene 1a, an expansion in volume of about 1% took place. The radical solution polymerization of 1a resulted in a soluble polymer with pendant 2-vinylcyclopropane groups.