Radical ring‐opening polymerization of 10‐methylene‐9,10‐dihydroanthryl‐9‐spirocyclopropane

Cho, Iwhan; Song, Ki Yong

doi:10.1002/pola.1994.080320921

Cited by 17 publications

(23 citation statements)

References 7 publications

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“…As indicated in Table 1, 16 monomers were grouped into monomers polymerized via (1) selective ring-opening polymerization (1-7), 34 (2) both ring-opening and vinyl-type polymerizations (8)(9)(10)(11), and (3) selective vinyl-type polymerization (12)(13)(14)(15)(16). The ring-opening degrees of the polymerizations of the monomers polymerized via partial ring opening (i.e., 8-11) exceed 80%, indicating the high tendencies of their radical ring openings.…”

Section: Resultsmentioning

confidence: 99%

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Computational evaluation of radical ring‐opening polymerization

Ochiai

Endō

2007

J. Polym. Sci. A Polym. Chem.

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The tendencies of ring-opening processes in radical ring-opening polymerizations were evaluated by AM1 and PM3 semi-empirical calculations and 6-31G*-level calculations based on the density functional theory (DFT) B3LYP models. Sixteen cyclic monomers bearing vinyl or exomethylene groups were categorized into ring-opening and no-ring-opening monomers by the evaluation of the differences of the internal energies and the lengths of the cleaving bonds between the ground states of the initial radicals and the activated states in the ring-opening processes. Although the semi-empirical calculations not parameterized to radical reactions resulted in the moderate categorization of the ring-opening monomers, the DFT calculation clearly distinguished the ringopening and no-ring-opening monomers. The ring-opening tendencies were also evaluated with the changes in the internal energies throughout the ring-opening processes, but this method could not group the ring-opening and no-ring-opening monomers clearly.

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Section: Resultsmentioning

confidence: 99%

“…Relationship between Dd and DE { values in the ring-opening processes calculated by (a) AM1, (b) PM3, and (c) DFT B3LYP/6-31G*//AM1: (n) selective ring-opening monomers(1-7), (l) partial ring-opening monomers(8)(9)(10)(11), and (~) selective vinyltype polymerization monomers(12)(13)(14)(15)(16).…”

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confidence: 99%

Computational evaluation of radical ring‐opening polymerization

Ochiai

Endō

2007

J. Polym. Sci. A Polym. Chem.

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“…The cyclic monomer, MDS, was prepared by Wittig reaction of anthrone‐9‐spirophenylcyclopropane, according to a method reported previously 24, 33. The monomer was highly reactive and the neat product could not be handled at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…In our previous system,24 MDS was employed as a cyclic monomer, and the resulting polymer actually had a perfect alternating structure composed of the anthracene moiety and styrene unit, owing to the ring‐opening polymerization system. There are two possible mechanisms for the homopolymerization of MDS;24, 25, 33, 34 conventional 1,2‐vinyl addition to afford a vinyl polymer having the cyclopropane ring in the side chain, and a ring opening reaction to directly furnish the anthracene moiety in the main chain. In our system, ring‐opening of the cyclic monomer was found to proceed predominantly during radical polymerization in the presence of a suitable CTA 24, 25.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Assembled Structures, and Optoelectronic Properties of Amphiphilic Block Copolymers Containing Anthracene Units in the Main Chain

Mori

Tanaka

2011

Macro Chemistry & Physics

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Novel amphiphilic block copolymers containing the anthracene unit in the main chain are synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization of a cyclic monomer, 10‐methylene‐9,10‐dihydroanthryl‐9‐spirophenylcyclopropane (MDS). A hydrophilic macro‐chain transfer agent is prepared by RAFT polymerization of 2‐hydroxyethyl acrylate (HEA). The polymerizations of MDS using the poly(HEA) afford amphiphilic block copolymers, in which the hydrophobic poly(MDS) segment has a perfectly alternating structure composed of an anthracene unit and a styrene unit, owing to the ring‐opening polymerization system. Characteristic assembled structures and optoelectronic properties of the amphiphilic block copolymers are investigated in various selective solvents.

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“…9 10-Methylene-9,10-dihydroanthryl-9-spirocyclopropane is regarded as a vinylcyclopropane derivative; it undergoes RROP with the release of the ring strain of the cyclopropane ring and the formation of a stable aromatic ring as the driving force (Scheme 11). 10 A vinylcyclobutane also undergoes RROP to afford a polymer with double bonds in the main chain similarly to vinylcyclopropanes (Scheme 12). 11 Vinyloxirane 12 and vinylthiirane, 13 analogues of a vinylcyclopropane undergo RROP, but the polymers formed contain some indeterminable structures, probably because of some side reactions such as hydrogen radical abstraction at the allylic positions (Scheme 13).…”

Section: Methodsmentioning

confidence: 99%