Diphenylbutadiyne polymerization

Берлин, А. А.; Cherkashin, Μ. I.; Chauser, M. G.; Shifrina, R.R.

doi:10.1016/0032-3950(67)90259-6

Cited by 20 publications

(13 citation statements)

References 6 publications

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“…11 Diphenyldiacetylene has been reported to polymerize both with and without the addition of catalyst in either melt or solution. 16,17,29,30 The resulting polymer is generally of low molecular weight. Polymer fractions have been reported which are soluble in either ethanol or aromatic solvents, which is in contrast with the insolubility in common solvents usually found for solid-state polymerized diacetylenes.…”

Section: Discussionmentioning

confidence: 99%

Solid-state polymerization of diacetylenes

Baughman¹

1972

Journal of Applied Physics

179

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Differences in the solid-state reactivity of two substituted diacetylenes with identical lattice symmetry (P2/c) are described in terms of the molecular rotational and translational motion necessary for 1,4-addition polymerization. The structural relationship between monomer and polymer has been investigated in detail for the solid-state polymerization of 2,4-hexadiynediol. For the thermal, uv, or y-ray-induced polymerization of this monomer the same crystallographic relationship was found between the polymer chain direction and the monomer lattice. Mutually reacting monomer molecules are related by a unit-cell translation along the 0/ c diagonal, which is perpendicular to the unique axis of this monoclinic crystal. X-ray diffraction determination of unit-cell parameters for or-ray-irradiated samples of differing conversion have confirmed that the polymer enters the monomer lattice as a solid solution and verify the mentioned polymerization mechanism. When these irradiated samples were thermally annealed, phase separation occurred, producing discrete monomer and amorphous polymer phases. Despite the instability of the partially polymerized 2,4-hexadiynediol lattice, ir measurements reveal no free hydroxyl hydrogens either before or after phase separation. Neighboring monomer molecules are indirectly hydrogen bonded together in the c-axis direction, but no hydrogen bonding exists between mutually reacting monomer molecules in disagreement with a previously suggested model for lattice-controlled diacetylene polymerizations. During the polymerization of 2,4·hexadiynediol the center-to-center separation of mutually reacting molecules must change by -0.44 A and the conjugated molecular rods must rotate by an angle of at least 28°. This large required molecular rotation suggests that the activation energy for rotation contributes significantly to the activation energy for polymerization. The high entropy of fusion (17.0 ± 1.2 eu) measured for this compound is consistent with low solid-state rotational mobility. No solid-state phase transitions were observed calorimetrically for 2,4-hexadiynediol from -loooe to the melting point (114.5+0.3 'C). The low solid-state reactivity observed for diphenyldiacetylene is reasonable in light of the much larger translati(;n and rotation necessary for 1,4-addition polymerization, respectively, -\.14 A and 37.s°.No ethanol insoluble polymer was obtained for y-ray radiation dosages which resulted in high monomer-to-polymer conversions for 2,4-hexadiynediol. No measurable difference was observed in the melting behavior of y-ray-irradiated and nonirradiated samples of this high entropy of fusion compound (14.1±0.7 eu).

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Section: Discussionmentioning

confidence: 99%

Solid-state polymerization of diacetylenes

Baughman¹

1972

Journal of Applied Physics

179

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“…The polymers were insoluble and practically depleted of the reactive functional -Ca"CH groups. Besides this, the used methods for polymers synthesis had serious limitations for their possible industrial scale implementation [3][4][5][6][7][8][9][10][11][12][13].…”

Section: Polymers Of Phenyldiacetylenes -Functional Thermostable Addimentioning

confidence: 99%

“…Thermal block-polymerization of DPD was performed at approximate temperatures of 423-468 К. About 61 % of insoluble fraction was already formed at 468 К. Polymer macromolecules contained polyenic as well as polyacenic fragments [3,4]. Thermal polymerization of DPD in mass gave appreciable yields after dozens of hours only at temperatures above 393 К [5].…”

Section: Polymers Of Phenyldiacetylenes -Functional Thermostable Addimentioning

confidence: 99%

“…Thermal polymerization of DPD in mass gave appreciable yields after dozens of hours only at temperatures above 393 К [5]. DPD polymerization in the presence of complex initiators i-Bu 3 Al-TiCl 4 and vanadyl acetylacetonate resulted in lowconversion formation of amorphous polyenes with low molecular weight [3,6,7]. Bonds C≡C of side-chain C≡CPh substituents in poly-DPD were inactive in intermolecular reactions leading to formation of threedimensional polymeric networks.…”

Section: Polymers Of Phenyldiacetylenes -Functional Thermostable Addimentioning

confidence: 99%

“…It is known that polydiphenyldiacetylene (poly-DPD) and poly-p-diethynylbenzene (poly-DEB), similar to other phenyl-substituted polyacetylenes, are characterized by a high thermostability and thermooxidation resistance [3][4][5][6][7][8][9][10][11][12][13]. It is explained by a specific intermolecular structure of polyconjugated polymers, as well as by a high content of carbon in the polymers (up to 95.2 %) which are lacking other heteroatoms (oxygen, nitrogen, sulfur) in macromolecules.…”

Section: Introductionmentioning

confidence: 99%

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Polymers of Phenyldiacetylenes – Functional Thermostable Additions to Industrial Resins

Misin¹,

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Misin³

2010

Ch&Cht

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Organische Halbleiter, Teil I. Physikalische Grundlagen, Charakterisierung und Anwendungsmöglichkeiten

Koßmehl

Manecke

1967

Chemie Ingenieur Technik

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sich die anorganischen Halbleiter in den verschiedenen Bereichen der Elektrotechnik bereits seit Jahren einen festen Platz erworben haben, werden organische Halbleiter bisher erst sehr vereinzelt angewandt, obwohl f u r viele dieser Verbindungen aui Grund ihrer besonderen physikalischen und chemischen Eigenschaiten die unterschiedlichsten Anwendungsmoglichkeiten denkbar sind. lm Teil I dieser Arbeit sollen daher zunachst die physikalischen Grundlagen der organischen Halbleiter behandelt sowie ein Oberblick uber die MeBmethoden zu ihrer Charakterisieruq und die bisher vorgeschlagenen Anwendungen gegeben werden. -Teil 11 wird sich mil den elektrischen Eigenschaften der wichtigsten organischen halbleitenden Verbindungen beiassen, und es werden die Zusammenhange zwischen der chemischen Slruktur und der elektrischen Leitfahigkeit diskutiert.Die ersten Untersuchungen uber die elektrischen Eigenschaften organischer Verbindungen wurden zu Beginn dieses Jahrhunderts durchgefuhrt. 1906 beschrieb A. Pochettinol) die Photoleitfahigkeit des Anthracens, und 1910 konnten J.

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Diphenylbutadiyne polymerization

Cited by 20 publications

References 6 publications

Solid-state polymerization of diacetylenes

Solid-state polymerization of diacetylenes

Polymers of Phenyldiacetylenes – Functional Thermostable Additions to Industrial Resins

Organische Halbleiter, Teil I. Physikalische Grundlagen, Charakterisierung und Anwendungsmöglichkeiten

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