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  • Polymer and Materials Science  (62)
  • Physics  (14)
  • 1970-1974  (62)
  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Im Temperaturbereich von 60 bis 100°C wird die radikalische Polymerisation von Styrol, Methylmethacrylat und Acrylnitril von α.α′-Dicyanodibenzylen ausgelöst, die in α-und α′-Stellung mit Ester-, Nitril-, Amid- oder Phenylgruppen disubstituiert sind. Bei 100 bis 110°C ist auch das α.α.α′.α′-Tetracarboxymethyldibenzyl aktiv. Vinylacetat und Vinylchlorid werden durch diese Initiatoren kaum polymerisiert.Fur die Polymerisation des Styrols wurden die Bruttogeschwindigkeitskonstanten Kp, für viele Dibenzyle und fur Peroxide vergleichbarer Aktivitat dilatornetrisch bestirnrnt. Norrnalerweise sind die Zeit-Urnsatz-Kurven rnit den Dibenzylen und den Peroxiden vergleichbar; das Tetracyanodibenzyl allerdings bewirkt nur eine unvollstandige Polymerisation.Der große Einfiuß von Substituenten in α-Stellung oder in den Phenylringen der Dibenzyle auf die Polymerisation des Styrols wird diskutiert. Dabei ist auch die Stereochernie wichtig. Die meso-Form des Dinitrildiesters ergibt eine 2.5- bis 3.5 ma1 schnellere Polyrnerisation als das dl-Isornere.Die Dissoziationsgeschwindigkeitskonstanten kd der Initiatoren wurden NMR-spektroskopisch aus der Linienbreite bestirnmt. Die Dinitrildiester sind gute Initiatoren, wahrend die α.α′-Dicyanodibenzyle rnit weiteren Nitril- oder Phenylgruppen in α- und α′-Stellung wenig geeignet sind. SchlieBlich wurde die 1.2-Addition einiger der Dibenzyle an Styrol im Ternperaturbereich von 120 bis 150°C rnit der Methode der chernisch induzierten KernPolarisation (CIDNP) untersucht.
    Notes: The radical polymerization of styrene, methyl methacrylate and acrylonitrile is initiated by α.α′-dicyanodibenzyls α.α′-disubstituted with ester, nitrile, amide or phenyl groups in the temperature range 60 to 100°C and by α.α.α′.α′-tetracarboxymethyldibenzyl at 100 to 110°C. Vinylacetate and vinylchloride show a low reactivity.The overall polymerization rate constants Kp have been determined dilatometrically for styrene initiated by a large number of dibenzyls and comparable peroxides. The styrene polymerization curves are generally comparable with those of peroxides. A notable exception is tetracyanodibenzyl.The strong influence of α- and ring-substituents in the dibenzyls on the styrene polymerization rate is discussed. The stereochemistry is also important : the meso α.α′-dicyanodibenzyls α.α′-disubstituted with ester groups give a 2.5 to 3.5 fold faster polymerization than their dl isomers.The initiator efficiency is related to the kd values, determined from NMR line width measurements. The α.α′- dicyanodibenzyls α.α′-disubstituted with ester groups are good initiators, while those with phenyl groups and nitrile groups are inefficient.Relevant to initiation and termination, the 1.2-addition of some of the dimers to styrene at 120 to 150°C has been studied with chemically induced dynamic nuclear polarization (CIDNP).
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 10 (1972), S. 851-854 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 345-352 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bifunctional arylcyanoacetic esters were oxidatively coupled to high molecular weight, colorless, amorphous polymers, soluble in common organic solvents. Brittle films were obtained by casting or compression molding. Thermal stability of the polymers is poor due to the weak C—C bond formed by oxidative coupling. Radical dissociation-recombination of this bond (evidenced by ESR) results in meso-dl equilibration, lowering the Tg of the polymers.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 2509-2523 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of poly(γ-p-nitrobenzyl-L-glutamates), PNBG, has been synthesized by the polymerization of N-carboxyanhydride (NCA) derivatives of γ-p-nitrobenzyl-L-glutamate, NBG, using triethylamine as an initiator. We studied the influence of (a) the solvents dioxane, nitrobenzene, dimethylformamide (DMF), and DMF-1,2-dichloroethane mixture and (b) the anhydride-initiator ratio (A/I) for the polymerization in nitrobenzene (A/I varying from 50 to 750) on the properties of the polymers obtained. In order to improve its synthesis, NBG, was prepared by three different methods. Ten samples of PNBG, ranging in Mw from 10,000 to 50,000, were examined viscometrically in DMF and dichloroacetic acid (DCA) and by ultracentrifugation in DMF. The data for [η] and So (limiting sedimentation coefficient) as functions of Mw for PNBG in DMF were utilized, applying theories of Kuhn and Kuhn,13 Schachman,14 and Perrin, 15 for the estimation of the length per monomeric residue h. Viscosity data gave a h value of about 2.3 Å, Whereas sedimentation yielded 1.5 Å. Treating viscosity and sedimentation data for poly(γ-benzyl-L-glutamate), PBLG, in the same way leads to somewhat higher hvalues (2.4 Å and 1.7 Å, respectively).Although a nitroaromatic effect was shown to be absent for PNBG in DMF, it can be concluded that in this medium PNBG has a somewhat more compact structure than PBLG.
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Darstellung von Poly(γ-p-biphenylmethyl-L-Glutamat), PBPLG, (Poly{L-imino-1-[2-(4-biphenylmethoxycarbonyl)äthyl]-2-oxoäthylen}), (1d) wird beschrieben. Das Viskositätsverhalten dieses Polymers in Mischungen aus Benzol und Dichloressigsäure (c=0,2.10 - 3 - 1,4.10 - 3g/cm3) bei 25°CC wird untersucht. Die Ergebnisse werden verglichen mit Messungen unter den gleichen Bedingungen an Poly(γ-benzyl-L-Glutamat),PBLG, (Poly[ L-imino-l-(2-benzyloxycarbonylathyl)-2-oxoathylen]), (lc). In beiden Fallenfindet ein zweistufiger Ubergang von einer starren, von Wasserstoffbrucken stabilisiertenHelix in ein statistisches, solvatisiertes Knduel statt : PBPLG (erste Stufe CrSSX,, zweite Stufe 55-100%, Dichloressigsaure und PBLG (erste Stufe 0-70%, zweite Stufe 70-100%,Dichloressigsaure)).Die Einfiihrung eines p-Phenylsubstituenten in PBLG fuhrt deshalb in Mischungen aus Benzol- und Dichloressigsaure zu einer weniger stabilisierten Helix.Die Stabilitat und das Viskositatsverhalten von PBLG in Mischungen aus Benzol und Dichloressigsaure (c=0,2.10-3 -14.10-3g/cm3) sind denjenigen von PBLG in Mi-schungen aus m-Kresol und Dichloressigslure ( c = 1,0.10-3-4,0. 10-3g/cm3) ähnlich.
    Notes: The synthesis of poly(γ-p-biphenylmethyl-L-glutamate), PBPLG, (poly{L-imino-1-[2-(4-biphenylylmethoxycarbonyl)ethyl]-2-oxoethylene}), (1d) is described. The viscosity behavior of this polymer in benzene/dichloroacetic acid mixtures (c=0,2.10 - 3 - 1,4.10 - 3 g/cm3) at 25°CC is investigated. The results are compared with measurements on poly(γ-benzyl-L-glutamate), PBLG, (poly[L-imino-1-(2-benzyloxycarbonylethyl)-2-oxoethylene]), (1c) under the same conditions. A transition from a rigid hydrogen bonded helix to a random solvated coil occurs in two stages for both: PBPLG (first stage 0 - 55%, second stage 55 - 100% dichloroacetic acid) and PBLG (first stage 0 - 70%, second stage 70 - 100% dichloroacetic acid).Therefore, the introduction of a p-phenyl substituent in PBLG leads to a less stable helix in benzene/dichloroacetic acid mixtures.The stability and viscosity behavior of PBLG in benzene/dichloroacetic acid mixtures (c=0,2.10 - 3 - 1,4.10 - 3g/cm3) is quite similar to the behavior of PBLG in m-cresol/dichloroacetic acid mixtures (c=1,0.10 - 3 - 4,0.10 - 3 g/cm3).
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 10 (1972), S. 851-854 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 8 (1970), S. 805-808 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 1893-1899 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal bulk polymerization of cholesteryl acrylate was carried out in the solid phase, the mesomorphic phase, and the liquid phase to study the effect of monomer ordering on polymerization rate and polymer properties. The rate increased with decreasing ordering (or enhanced mobility) of the monomer. Formation of inhibitive by-products during the polymerization limited conversions to 35%. The sedimentation constant S0 = 6.2 S was the same for the polymers obtained in the three phases. The weight-average molecular weight (M̄w) was 480,000 as determined by ultracentrifugation. Poly-(cholesteryl acrylate) formed in bulk is randomly coiled when dissolved in tetrahydrofuran. The thermal properties of the monomer are given.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 23 (1972), S. 1008-1012 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Kathodenschutz in Fracht/Ballast-Tanks von RohöltankernAm Boden und auf der Oberseite von Ballasttanks kann Lochfraß auftreten, wenn kein besonderer Schutz vorgesehen wird. Gewöhnlich verwendet man einen Teilanstrich (waagrechte Flächen) in Verbindung mit Kathodischem Schutz durch Opferanoden. Über zwei Jahre durchgeführte Beobachtungen an gestrichenen und ungestrichenen kathodisch geschützten Behältern zeigen, daß die Anodenleistung durchweg über 90% beträgt und in vielen Fällen 100% erreicht. Die Stromdichten sind dabei stark von dem Meßpunkt im Tank abhängig und sind  -  besonders bei angestrichenen Böden  -  am Boden höher. Aufgrund der Meßergebnisse ist es möglich, den Schutzstrombedarf für horizontale und vertikale Flächen vorauszuberechnen.
    Notes: Unless a special protection is provided pitting corrosion may occur on top and at the bottom of ballast tanks. Usually a partial coating (horizontal areas) is used in connection with cathodic protection by sacrificial anodes. More than two years' observation of coated and uncoated, cathodically protected containers has shown, that anode efficiency is generally better than 90%, and in many cases as high as 100%. The current densities measured depend from the point of measurement and are higher at the bottom, in particular when the latter is coated. On the basis of the measurement results it is possible to assess the protective current requirements for horizontal anc vertical surfaces.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 19 (1971), S. 121-134 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Verschiedene copolymere Anhydridimide wurden aus Dicarbonsäuren mit vorgebildeter Imidgruppe erhalten. Dazu wurde zunächst Trimellitsäureanhydrid mit verschiedenen aromatischen und aliphatischen Aminen zu den entsprechenden Dicarbonsäuren mit Imidgruppen umgesetzt. Dann wurden aus diesen Dicarbonsäuren durch Reaktion mit Essigsäureanhydrid die entsprechenden gemischten Anhydride hergestellt. Unter bestimmten Bedingungen wurden daraus dann unter Abspaltung von Essigsäureanhydrid polymere Anhydride gewonnen.Die Polymeren sind kristallin und zeigen hohe thermische Stabilität und gute elektrische Eigenschaften. Ihre Struktur wurde IR-spektroskopisch und durch Elementaranalyse bestimmt; Beziehungen zwischen Struktur und Eigenschaften wurden untersucht.
    Notes: Various copolyanhydride-imides have been obtained from diacids containing the preformed imide group by directly reacting of trimellitic anhydride with various aromatic and aliphatic amines. The polymerization process took place in several stages. In the first stage the diacetyl derivatives were obtained from the corresponding diacids by reactions with acetic anhydride. Under special temperature and pressure conditions, polymers were obtained from these derivatives and the chain grew by developing acetic anhydride between contiguous molecules.The polymers obtained are crystalline, have high thermal stability and good electrical properties. Their structures were determined by IR spectroscopy and elementary analysis and the relationships between their properties and the polymer structures were investigated.
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