Functional monomers and polymers, 157. Inclusion polymerization of 1,3‐butadiene derivatives with bulky substituents in deoxycholic acid and apocholic acid canals

Miyata, Mikiji; Tsuzuki, Toshitaka; Takemoto, Kiichi

doi:10.1002/marc.1987.030081005

Cited by 5 publications

(2 citation statements)

References 9 publications

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“…For example, formation of polymers with highly 1,4- trans tactic structures by inclusion polymerizations of 1,3-butadiene and methyl-substituted butadiene derivatives using anti-trans–anti-trans–anti-trans- perhydrotriphenylene as a host at 25–30 °C under γ-ray irradiation corresponds to an ideal topochemical polymerization. On the other hand, inclusion polymerizations of diene monomers such as 1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene using naturally occurring deoxycholic acid , correspond to contraction polymerizations, while inclusion polymerizations of diene monomers using naturally occurring apocholic acid do to expansion ones.…”

Section: Resultsmentioning

confidence: 99%

Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes

et al. 2016

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7,7,8,-p-quinodimethanes with bulky aryloxy groups such as benzyloxy (1a), pentafluorobenzyloxy (1b), and both benzyloxy and pentafluorobenzyloxy (1c) were synthesized. We investigated effects of these bulky groups on thermal solid-state polymerization reactivities on the basis of crystal structures of 1a−1c. Thermal polymerizations gave 1,6-trans-type stereoregular polymers in quantitative yields in 1 day at 110°C for 1a, 1 day at 150°C for 1b, and 6 days at 110°C for 1c. Their initial crystal shapes were retained in appearance during polymerization to yield solid bundle assemblies of their polymeric chains. X-ray single-crystal structure analysis indicates that their crystals adopt molecular arrangements suitable for one-dimensional polymerization with the 1,6-trans-type addition along one crystallographic axis. Such arrangements led to expansion polymerization of 1b and contraction one of 1c. The resulting stereoregular polymers form less ordered bundle assemblies than those prepared by the conventional topochemical polymerization. In this manner, the bulky aryloxy groups enabled us to observe a close relation between the molecular assembly modes and the polymerization behaviors, providing the first example for proving diversity of thermal solid-state polymerizations.

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Section: Resultsmentioning

confidence: 99%

Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes

et al. 2016

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“…7 The results are summarized in Table I. The methanol-insoluble polymers were separated by filtration after the extraction of host molecules with boiling methanol.…”

Section: Resultsmentioning

confidence: 99%

Functional Monomers and Polymers CLXVII. Asymmetric Inclusion Polymerization of 1-Alkyl-1,3-butadienes in Deoxycholic Acid and Apocholic Acid Canals by Long-Lived Propagating Radicals

Miyata

Tsuzuki

Takemoto

et al. 1988

Polym J

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Asymmetric inclusion polymerization is an excellent way for obtaining highly stereoregular and optically active polymers by "through space" asymmetric induction. 1 However, applicable monomers are so far limited to only methyl-substituted 1,3-butadienes (BO), such as 1,3-pentadiene, 2 2-methyl-1,3-pentadiene, 3 2,4-hexadiene, 4 and 1,3-cyclodienes. 5 In spite of impressive progress in asymmetric synthesis over the past decade, 6 there seem to be only a few studies on asymmetric polymerization of BO derivatives except for the inclusion method.thermally stable propagating radicals in the canals. This finding enabled us to challenge the inclusion polymerization of many diene monomers not applicable so far.In a series of extensive studies on inclusion polymerization using deoxycholic acid (OCA, I) and apocholic acid (ACA, II) as the host molecules, we showed that even butadiene monomers with bulky and/or polar substituent groups can be polymerized in the canals of the hosts. 7 • 8 The reason for the success lies in the possible prolonged postpolymerization due to We report here the first example of asymmetric inclusion polymerization of five prochiral monomers, that is, propyl, isopropyl, butyl, in OCA and ACA canals by long-lived propagating radicals. ESR observation of the propagating radicals is also described.

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Polymerization in Clathrates

Silvestro

Sozzani

1989

Comprehensive Polymer Science and Supplements

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Functional monomers and polymers, 157. Inclusion polymerization of 1,3‐butadiene derivatives with bulky substituents in deoxycholic acid and apocholic acid canals

Cited by 5 publications

References 9 publications

Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes

Formation of Bundle Assemblies of Stereoregular Polymers in Thermal Solid-State Polymerization of 7,7,8,8-Tetrakis(aryloxycarbonyl)-p-quinodimethanes

Functional Monomers and Polymers CLXVII. Asymmetric Inclusion Polymerization of 1-Alkyl-1,3-butadienes in Deoxycholic Acid and Apocholic Acid Canals by Long-Lived Propagating Radicals

Polymerization in Clathrates

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