The Polymerization of 1,1-Dichloro-2-vinylcyclopropane

Takahashi, Taro; Yamashita, Iwao; Miyakawa, Takaharu

doi:10.1246/bcsj.37.131

Cited by 30 publications

(2 citation statements)

References 6 publications

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“…1,1-Dichloro-2-vinylcyclopropane and 1,1-dibromo-2-vinylcyclopropane were the first disubstituted VCPs the polymerization behavior of which was investigated 71,79,80) . While a polymerization with cationic initiators failed, the polymerization of 1,1-dichloro-2-vinylcyclopropane with DBPO (5.0 wt.-%) resulted in a white polymer (M -n = 7 000) with a yield of 36% after 40 h at 80 8 C. Thereby, a rate increase of the radical polymerization of 1,1-dichloro-2-vinylcyclopropane in the presence of AIBN at 80 8 C with increased pressure was observed 81) .…”

Section: A 11-dihalo-2-vinylcyclopropanesmentioning

confidence: 99%

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: A 11-dihalo-2-vinylcyclopropanesmentioning

confidence: 99%

Synthesis and polymerization of vinylcyclopropanes

Moszner

Zeuner

Völkel

et al. 1999

Macromol. Chem. Phys.

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“…Generally, in addition polymerization, cyclic monomers show a smaller degree of shrinkage than vinyl monomers, but there are few monomers that afford a high molecular weight polymer by radical initiation through ring opening. Vinylcyclopropane 1 is one candidate because it can afford relatively high molecular weight polymers through radical ring-opening polymerization (Scheme ). − However, most show volume shrinkage upon polymerization. Recently, we have found that 1,1-bis(phenoxycarbonyl)-2-vinylcyclopropane ( 2 ) is a peerless high-volume-expanding monomer .…”

Section: Introductionmentioning

confidence: 99%

Free Radical Ring-Opening Polymerization of 1,1-Bis[(1-adamantyloxy)carbonyl]-2-vinylcyclopropane

1996

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A new monomer 1,1-bis[(1-adamantyloxy)carbonyl]-2-vinylcyclopropane (3) was readily synthesized and polymerized by radical initiators. Monomer 3 afforded a 1,5-addition polymer selectively and in good conversion, even at high temperatures or low monomer concentrations. Poly(3) is soluble in common organic solvents, but insoluble in ether and methanol. Poly(3) (M n = 51 000 estimated by GPC based on polystyrene standard) exhibited a grass transition at 34 °C and 10% weight loss at 377 °C under nitrogen. Monomer 3 showed a positive volume change (+4.5 ± 1.1%) upon polymerization. This phenomenon can be rationalized by several reasons, such as the depression of recyclization during propagation by bulky ester groups, conversion of the crystalline monomer to the amorphous polymer, and the fact that 3 contains a pair of large spreadable ester groups that may increase the free volume of the polymer matrix. The kinetics of the homopolymerization of 3 with AIBN was investigated in benzene. The rate of polymerization (R p) can be expressed by R p = k[AIBN]0.52[3]1.2, and the overall activation energy E a has been calculated to be 20.8 kcal/mol.

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