Isothermal cis-trans isomerization behavior of polyacetylene films

Isothermal cis-trans isomerization behavior was studied by differential scanning calorimetry for conventional Shirakawa polyacetylene (S-PA) film and highly stretchable polyacetylene (hs-x) films synthesized using catalysts aged at high temperature. The rate of isomerization is slower for S-PA than for hs-x. Kinetic results of isomerization are analyzed by a stretched exponential function with exponent n (0 < n < 1), which is different from the previously assumed single exponential function. An activation energy of 31 kcal/mol was obtained for all the samples. © 1995 John Wiley & Sons, Inc.     

Grain boundary relaxation phenomena in block and graft copolymers

Summary The grain boundary relaxation phenomena, which have been found in the mechanical relaxation of the cast films of a series ofgraft copolymers ofpoly(methyl acrylate) with styrene, are examined again, in order to understand its relaxation mechanism, by using some particular series of heterogeneous systems of two components having different interaction between the two phases and, subsequently, different grain boundary structure; i. e., two series of poly(vinyl acetate) filled with two types of carbon blacks having relatively high and low surface activities, respectively, a series ofmechanical mixtures ofpoly(vinyl acetate) with polystyrene, and a series of styrene-isoprene-styrene tri-block copolymers.The grain boundary relaxation phenomena are again detected for the series of the tri-block copolymers but definitely not for the series of the mechanical mixtures, suggesting that the grain boundary relaxation phenomena must arise not from the heterogeneous structures themselves but from characteristic arrangements of molecular chains at the boundary of the two phases. That is, there must be a considerably strong interaction between the two phases, and there exists an intermediate phase in which the polymer segments of soft component are rigidified while the other polymer segments of hard component are softened. In other words, there must be a cooperative motions of chain segments of the two components to produce a mechanical relaxation under a certain environmental condition, such as temperature and time scale of observation.

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Zusammenfassung Die Korngrenzenrelaxationsphänomene, die in der mechanischen Relaxation einer Serie von aus Graft-Copolymeren von Polymethylacrylat mit Styrol gefunden wurden, wurden erneut geprüft, um den Relaxations-mechanismus zu verstehen, unter Verwendung einer besonderen Serie von heterogenen Systemen zweier Komponenten, die verschiedene Wechselwirkungen zwischen den zwie Phasen besitzen und deshalb verschiedene Korgrenzenstrukturen. Das heißt, wir verwendeten zwei Serien von Polyvinylacetaten, gefüllt mit zwei Rußtypen von vergleichsweise hoher und niedriger Oberflächenaktivität, eine Serie von mechanischen Mischungen aus Polyvinylacetat mit Polystyrol und eine Serie von Styrol-Isopren-Dreiblockcopolymeren. Die Korngrenzenrelaxationsphänomene, wurden für die Serie der Dreiblockcopolymeren wiederum festgestellt, aber definitiv nicht für die Serie der mechanischen Mischungen. Das läßt vermuten, daß Korngrenzenrelaxation nicht von heterogenen Strukturen selbst, sondern von charakteristischen Anordnungen der molekularen Kette an der Grenze von zwei Phasen herrührt. Das heißt, es muß eine beträchtlich strenge Wechselwirkung zwischen den zwei Phasen bestehen, und es muß eine Zwischenphase existieren, in welcher die Polymersegmente der weichen Komponente versteift werden, während die anderen Polymersegmente der harten Komponente erweicht werden. Mit anderen Worten, es müssen cooperative Bewegungen von Kettensegmenten der zwei Komponenten vorhanden sein, um eine mechannische Relaxation unter gewissen Umgebungsbedingungenzuerzeugen, Umgebungsbedingungen wie Temperatur und Zeitskala der Beobachtungen.

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With 6 figures and 13 tables

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Presented at the 20th Annual Symposium on Rheology, Japan, Fukui, Oct. 18, 1972.     

Regio-controlled hydrogen-deuterium exchange of biologically important indoles under uv irradiation

Photochemical hydrogen-deuterium exchange reaction of biologically important indoles is reported. The regioselectivity of the photodeuteration was found to be controlled by the ammonium group of the side chain.     

Monooxygen transfer potential of the transannular ozonide of 9-tert-butyl-10-methylanthracene

The efficiency of oxygen transfer from the transannular ozonide 1 to several organic substrates was investigated. The efficiency was estimated to be as high as 90% in the case of Ph₃P as the substrate.     

Novel oxy-perfluoroalkylation

(Perfluoroalkyl)phenyliodonium sulfonates underwent novel oxy-perfluoroalkylation with alkenes under oxygen atmosphere in the presence of a base.     

Nonexponential proton relaxation in (NH4)2 HPO4

Nonexponential relaxation of protons in (NH₄)₂HPO₄ was found from 420 K to 110 K and was interpreted by the three-bath model below 167 K; inter-NH₄ group dipolar coupling above 167 K, and was attributed to non-equivalent NH₄ groups in a molecule.     

A structure analysis of Ag-adsorbed Si(111) surface by LEED/CMTA

The Ag induced superstructures on the Si(111) surface have been studied by low energy electron diffraction constant momentum transfer averaging (LEED/CMTA) technique. The vertical displacements of the atoms are determined from the analysis of the specularly reflected (00) beam intensities. Unexpected behavior of the Ag atoms is clarified: For the √3 × √3-Ag surface it is verified that the Ag atoms are embedded in the first double layer of Si, leading to a considerable rearrangement of the substrate. In contrast, for the 3 × 1-Ag surface, the Ag atoms are riding on the Si surface and the reconstruction of the substrate is small.