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  • Articles  (5,934)
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  • 1995  (5,934)
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  • Articles  (5,934)
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  • 2010-2014
  • 1995-1999  (5,934)
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  • 1
    ISSN: 1573-0417
    Keywords: diatoms ; temperature ; climatic change ; paleoclimate proxies ; canonical correspondence analysis ; weighted-averaging ; Yukon ; Northwest Territories
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract We identified, enumerated, and interpreted the diatom assemblages preserved in the surface sediments of 59 lakes located between Whitehorse in the Yukon and Tuktoyaktuk in the Northwest Territories (Canada). The lakes are distributed along a latitudinal gradient that includes several ecoclimatic zones. It also spans large gradients in limnological variables. Thus, the study lakes are ideal for environmental calibration of modern diatom assemblages. Canonical correspondence analysis, with forward selection and Monte Carlo permutation tests, showed that maximum lake depth and summer surface-water temperature were the two environmental variables that accounted for most of the variance in the diatom data. The concentrations of sodium and calcium were also important explanatory variables. Using weighted-averaging regression and calibration techniques, we developed a predictive statistical model to infer lake surface-water temperature, and we evaluated the feasibility of using diatoms as paleoclimate proxies. This model may be used to derive paleotemperature inferences from fossil diatom assemblages at appropriate sites in the western Canadian Arctic.
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  • 2
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    Springer
    Cellular and molecular life sciences 51 (1995), S. 260-266 
    ISSN: 1420-9071
    Keywords: Salmon ; satellite cells ; cell culture ; temperature
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Temperature is known to affect fish growth, and in Atlantic salmon there is an influence on muscle cellularity. Primary muscle cell culture makes it possible to investigate direct effects of temperature on myogenic cells. Salmon myosatellite cells were cultured for the first time in this study. The cells were cultured at either 5°C or 11°C. Increased temperature led to an increase in differentiation rate and especially hypertrophic growth (Q10=4.0). No nuclear proliferation was evident in the satellite cell population isolated at either temperature. This may be due to the presence of different subpopulations of myogenic cells at different developmental ages or the presence of indirect factors in vivo.
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  • 3
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    Springer
    Astrophysics and space science 224 (1995), S. 81-84 
    ISSN: 1572-946X
    Keywords: Chemistry ; Depletions ; Shocks ; IRAS 05338-0624 ; NGC 1333 IRAS 4
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NGC 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.
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  • 4
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    Springer
    Astrophysics and space science 233 (1995), S. 125-137 
    ISSN: 1572-946X
    Keywords: Interstellar Medium ; Dark Clouds ; Chemistry ; Bistability ; C-shock Waves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Shock waves perturb the chemical state of the interstellar gas. We consider the effects of C-shocks on the composition of molecular clouds, for a range of values of the pre-shock gas density and magnetic induction. The time required to re-establish equilibrium in the post-shock gas depends on the initial conditions and can become very large. The significance of the two known chemical phases of dark clouds and of bistability is considered in this context.
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  • 5
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    Astrophysics and space science 233 (1995), S. 161-164 
    ISSN: 1572-946X
    Keywords: Stars ; Chemistry ; Diffusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We have assessed the role of diffusion in determining chemical abundances in molecular interface regions. Chemical models have been developed which include the appropriate diffusion terms and that are appropriate to a narrow diffusion region (∼0.01pc) that may exist at the interface between a dark core and a hot, shocked T-Tauri wind. We have assumed pressure balance throughout and have calculated the chemical abundances as functions of time and position through the interface. The results show that significant enhancements of detectable molecules/transitions are expected (e.g. CO J=6→5, OH and CH). Using a realistic value of the diffusion coefficient a diffusive region of dimension 0.01pc may be established within about 104 years. In general it seems likely that diffusion processes are highly significant on these and smaller lengthscales.
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  • 6
    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: Der Einfluß von 3-Phenylenbismaleimid auf die Werkstoffeigenschaften von CaCO3 gefüllten Polypropylen-Verbundstoffen wurde untersucht. Die Verarbeitungstemperatur spielte eine entscheidende Rolle bei der Herstellung der Verbundwerkstoffe. Bei Verarbeitungstemperaturen oberhalb der Bismaleimid-Zersetzungstemperatur zeigte die Bismaleimid-Verbindung einen positiven Effekt. Die chemische Zusammensetzung der modifizierten Verbunde wurde mit den mechanischen Eigenschaften korreliert. Basierend auf ESCA-Analysen werden Wechselwirkungen zwischen dem Polymeren und CaCO, diskutiert.
    Notes: The effect of 3-phenylene bismaleimide on the mechanical performance of an inorganic filler-based polypropylene composite was studied. The selection of processing temperature played a significant role in the preparation of such composites. A positive effect of the bismaleimide compound was obtained for a processing temperature above the decomposition temperature of bismaleimide. The chemical composition of the modified composite was correlated to its mechanical strength by experimentation involving a rotatable design. An interaction between polymer and CaCO3 has been proposed based on ESCA analysis.
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  • 7
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 33-48 
    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: Chemische und mechanische Eigenschaften von Zwischenprodukten der PE-Schrumpfschlauch-Produktion wurden bei unterschiedlichen Compound-Zusammensetzungen (PE, ein aromatisches Amin oder Phenolderivat als Antioxidans und in einigen Fällen ein Flammschutzmittel und/oder eine Elastomerkomponente) untersucht.Während der Herstellung, besonders während der durch Elektronenstrahlung initiierten Vernetzung, nimmt die thermooxidative Stabilität des Materials gegenüber der des compoundierten Granulats ab. Das aromatische Amin scheint bei gleicher Zusammensetzung das wirksamere und strahlungsbeständigere Antioxidans im Vergleich zum Phenolderivat zu sein. Die Oxidationsstabilität der hergestellten Schrumpfschläuche wird nicht von der Qualität des eingesetzten PE-Ausgangsgranulats beeinflußt.Durch die Alterung des Materials ändern sich die mechanischen Eigenschaften geringfügig. Die Elastomerzugabe bewirkt keine Änderung von Zugfestigkeit und Reißdehnung. Die Stabilität des Endprodukts ist bei weitem ausreichend, um den Spannungen, die beim Schrumpfen während des Gebrauchs auftreten, standzuhalten. Die gute Zugfestigkeit des Materials wird durch die Alterung ebenfalls nicht beeinträchtigt.Bei der Extrusion des Granulats tritt keine nennenswerte Änderung des Molekulargewichts bzw. der Molekulargewichtsverteilung auf. Durch die Bestrahlung wird das Material vernetzt und zu mehr als 50% unlöslich, und seine thermooxidativen Eigenschaften ändern sich deutlich gegenüber dem ursprünglichen PE und dem daraus compoundierten Material.
    Notes: Some chemical and mechanical properties of intermediate products obtained in the production of PE heat-shrinkable tubes were studied at different compositions of the material containing PE, antioxidant (aromatic amime or phenol) and, in some cases, flame retardant and/or an elastomer.In the course of the production phase, the thermooxidative stability decreases compared to that of compounded granulate. The greatest decrease is caused by irradiation. The aromatic amine seems to be a more effective antioxidant at similar compositions than the phenol derivative, and it shows a better resistance against irradiation. The oxidative stability of the finished shrinkable tubes is not affected by the quality of commercial granulate (initial polyethylene).Mechanical properties change slightly upon ageing, and the introduction of the elastomer did not alter the tensile strength and elongation at break. The remaining stability of the end product was still high enough to bear the stress of shrinking in use, and the good tensile strength of the material did not decrease upon thermal ageing either.In the extrusion of the granulated compound no significant change in the distribution and average molecular weight took place. Irradiation produced more than 50% insoluble fraction and the thermooxidative properties of the crosslinked sample changed significantly compared to the original PE and to the compound prepared from it.
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  • 8
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    Angewandte Makromolekulare Chemie 224 (1995), S. 89-96 
    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: In the present work oxygen index (OI) measurements and thermogravimetric analysis (TG) for a series of polyurethanes based on diols and isocyanate were conducted. It was found that a correlation exists between some of the thermal degradation parameters obtained from TG and OI-values. Analysis of experimental results confirms that the amount of mass loss at 250°C is directly proportional to the OI-value. It was also found that the logarithmic temperatures of maximal decomposition rates are directly proportional to the OI-values.
    Notes: In der vorliegenden Arbeit wurden für eine Serie von Polyurethanen auf der Basis von Diol und Isocyanat der Sauerstoffindex (SI) gemessen und die thermische Zersetzung mittels thermogravimetrischer Analyse (TG) untersucht. Dabei wurde ein Zusammenhang zwischen einigen Parametern der thermischen Zersetzung und den SI-Werten gefunden. Die Auswertung der experimentellen Ergebnisse zeigte, daß die Höhe des Massenverlustes bei 250°C und die SI-Werte direkt proportional zueinander sind. Derselbe Zusammenhang besteht auch zwischen dem Logarithmus der Temperatur bei der maximalen Zersetzungsgeschwindigkeit und den SI-Werten.
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  • 9
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    Angewandte Makromolekulare Chemie 224 (1995), S. 109-114 
    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: Poly(acrylsäre-co-acrylamid) wurde mit Zinkoxid und Kryolith (Na3AlF6) in unterschiedlichen Verhältnissen gemischt und bei Raumtemperatur zu Zahnzementen ausgehärtet. IPDT, Temperaturen bei maximaler Abbaugeschwindigkeit, Aktivierungsenergien und Frequenzfaktoren des thermischen Abbaus der Proben wurden aus thermogravimetrischen Messungen ermittelt. Die Probe mit 20 Gew.-% Kryolith in der Füllstoffmischung ist thermisch sehr stabil.
    Notes: Dental cement compositions made by mixing poly(acrylic acid-co-acrylamide) and mixtures of zinc oxide and cryolite (Na3AIF6) in various proportions of 10-50 wt.-% (w/w) were cured at room temperature. From thermogravimetric analyses of the samples, the integral procedural decomposition temperatures (IPDT), maximum decomposition temperatures, activation energies and frequency factors were evaluated. The cured cement sample containing 20 wt.-% cryolite in the filler mixture is thermally very stable.
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  • 10
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    Angewandte Makromolekulare Chemie 224 (1995), S. 133-144 
    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: Die wasserlöslichen aromatischen Diazonium-Doppelsalze p-Diazodiphenylaminchlorid/Zinkchlorid (DZS-1) und p-Diazoanisolchlorid/Zinkchlorid (DZS-2) wurden auf ihre Verwendbarkeit als photobleichbare Farbstoffe in der Kontrastverstärkungslithographie untersucht. Nach Untersuchung der Bleicheigenschaften der hergestellten Salze wurde DZS-1 in wäßrigen Lösungen mit Poly(vinylalkohol) als Kontrastverstärkungssystem eingesetzt. Die thermische Stabilität, der Resistkontrast, die Bestrahlungsparameter und andere Bleicheigenschaften wurden untersucht. Im Vergleich zu einem handelsüblichen i-Linien-Photoresist beträgt das Kontrastverhältnis der DZS-1/PVA CEL-Schicht 1,67.
    Notes: Water soluble aromatic diazonium double salts, p-diazodiphenylamine chloride zinc chloride (DZS-1) and p-diazoanisol chloride zinc chloride (DZS-2), have been evaluated as photobleachable dyes for contrast enhancement lithography. After testing the bleaching characteristics, aqueous solutions of DZS-1 and poly(vinyl alcohol) were used as a contrast enhancement material. Thermal stability, resist contrast, exposure parameters and other bleaching characteristics of the photobleachable membranes were investigated. A. commercial i-line photoresist was used to evaluate the contrast ratio of the DZS-1/PVA CEL layer. The contrast ratio obtained in this investigation is 1.67.
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  • 11
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    Angewandte Makromolekulare Chemie 224 (1995), S. 167-178 
    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: Methylen-4,4′-diphenyldiisocyanat und zwei unterschiedliche Bisoxazoline wurden für Kopplungsreaktionen in mit Carboxygruppen terminierten flüssigkristallinen Poly(ethylenterephthalat-co-oxybenzoat)en eingesetzt. Um definierte Bedingungen zu gewährleisten, erfolgte die Synthese von Copolyestern mit unterschiedlichen Carboxygruppenkonzentrationen. Die Bestimmung des Carboxygruppengehalts wird beschrieben.Es erfolgt ein Vergleich des Kopplungsverhaltens beider Arten von Kettenverlängerern. Es konnte nachgewiesen werde, daß die Bisoxazoline bedeutend schneller reagieren als das Diisocyanat. Durch einen geringen Überschuß and Bisoxazolin in der Reaktionsmischung konnte einer thermischen Schädigung vorgebeugt werden. Abhängig von der Menge an zugegebenem Koppler wurden bei den modifizierten Copolyestern Oxazolinendgruppen beobachtet. Außerdem werden mögliche Vernetzungsreaktionen und die thermische Stabilität diskutiert.
    Notes: Methylene-4,4′-diphenyldiisocyanate and two different bisoxazolines were used for coupling reactions in carboxy-terminated liquid crystalline poly(ethylene terephthalate-co-oxybenzoate). In order to guarantee defined conditions, copolyesters with different carboxylic group concentrations were synthesized. The determination of the carboxylic group content is described.The coupling behaviour of both types of chain extenders has been compared. It was evidenced that the bisoxazolines reacted significantly faster than the diisocyanate. A slight excess of bisoxazoline in the reaction mixture prevented thermomechanical degradation. Depending on the amount of coupling agent added, an oxazoline termination of the copolyester was observed. Additionally, probable crosslinking reactions and the thermal stability have been discussed.
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  • 12
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    Angewandte Makromolekulare Chemie 224 (1995), S. 201-201 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 13
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    Angewandte Makromolekulare Chemie 225 (1995), S. 11-20 
    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: Der Einfluß von 3-Phenylenbismaleimid auf die Werkstoffeigenschaften von mit Talkum und Zeolith gefüllten Polypropylen-Verbundstoffen wurde untersucht. Durch geeignete Planung des Aufbaus kann die Produkteigenschaft optimiert werden. Die Kapazität zur Füllstoffaufnahme schwankt bei Polypropylen je nach Art des Füllstoffs. Ein hochbelastbarer Verbundstoff kann aus einem geeignet modifizierten, mit Zeolith gefüllten Polypropylen hergestellt werden, auch wenn der Füllstoff in der Verbundmatrix dominiert. Als Ursache dieser Verstärkung wird eine verbesserte Wechselwirkung zwischen dem Polymeren und dem Füllstoff angenommen.
    Notes: The effect of 3-phenylene bismaleimide as a modifier for talc and zeolite-filled polypropylene composites has been studied. The usefulness of the experimental design to assure best product properties has also been illustrated. Polypropylene shows a variable degree of filling capacity depending on the type of filler. A high-strength composite can be prepared with suitably modified zeolite-filled polypropylene even if filler is the dominant phase in the composite matrix. An improved interfacial interaction between polypropylene and filler is proposed to be the reason for this improvement of strength.
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  • 14
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    Angewandte Makromolekulare Chemie 225 (1995), S. 51-61 
    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: Die katalytische Oligomerisation von 1-Decen wurde mit Komplexverbindungen mehrerer Übergangsmetalle (Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V)) und Alkyl-aluminiumhalogeniden als Cokatalysatoren durchgeführt. Mit einem Chrom(III)-Et3Al2Cl3-Katalysatorsystem konnten Dimere (C20), Trimere (C30) und Tetramere (C40) von 1-Decen erhalten werden. Die kinematischen Viskositäten und Fließpunkte der hydrierten Oligomere wurden bestimmt und mit den Werten handelsüblicher Proben verglichen. Ein Mechanismus für die Oligomerisation von 1-Decen mit diesem Katalysatorsystem wird vorgeschlagen.
    Notes: The catalytic oligomerization of 1-decene has been carried out employing several transition metal complexes of Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V) in combination with alkyl aluminum halides as cocatalysts. The chromium(III)-Et3Al2Cl3 system exhibits good oligomerizing activity yielding dimers (C20), trimers (C30) and tetramers (C40) of 1-decene. The kinematic viscosities and pour points of hydrogenated oligomers have been determined and compared with those of commercial samples. The probable mechanism of oligomerization of 1-decene on this catalyst is described.
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  • 15
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    Angewandte Makromolekulare Chemie 225 (1995), S. 99-107 
    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: Single-component formulations of epoxy resins with reactive accelerators must be storable. The preparation of several blocked accelerators is described. The basicity of tertiary amines, which correlates with accelerating effects, as well as acidity and structure of polyphenols and modified novolacs influences the extend of blocking. The curing process was investigated by measurements of gel time and viscosity.
    Notes: Einkomponentige Epoxidharzsysteme mit effizienten Reaktionsbeschleunigern müssen lagerstabil sein. Daher wurden Versuche unternommen, Beschleuniger auf Basis von tertiären Aminen mit modifizierten Phenolnovolaken zu blockieren. Das Ausmaß der Blockierung ist sowohl von der Basizität der Amine, die mit der beschleunigenden Wirkung korreliert, als auch von der Acidität und dem strukturellen Aufbau der modifizierten Phenole abhängig. Die Bewertung der Härtungseigenschaften erfolgte über Gelzeitbestimmungen und Viskositätsmessungen.
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  • 16
    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: Die Bruchzähigkeit von Phenolphthalein-Poly(etherketon) bei 190°C wurde mit zwei verschiedenen Methoden bestimmt, der konventionellen Rißwachstumsmethode und der „stress whitening zone“-Methode. Die gute Übereinstimmung der Ergebnisse zeigt, daß letztere Methode zur Bestimmung der Rißinitiierung einiger Polymerer herangezogen werden kann, für die das „blunting line concept“ nicht geeeignet ist.
    Notes: Fracture toughness values of phenolphthalein poly(ether ketone) (PEK-C) at 190°C were determined by two different methods, i.e. the conventional crack growth method and the crack stress whitening zone method, which show consistent results. This indicates that the crack stress whitening zone method can be used to determine the crack initiation of some polymers for which the blunting line concept is unsuitable.
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  • 17
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    Angewandte Makromolekulare Chemie 226 (1995), S. 13-22 
    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: Stabilitätskonstanten und zugehörige thermodynamische Parameter (ΔH°, ΔS°) eines intermakromolekularen Komplexes aus Poly(acrylsäure-co-acrylamid), Poly(methacrylsäure-co-acrylamide) und Poly(N-vinylpyrrolidon) wurden mit bekannten Methoden bei verschiedenen Temperaturen bestimmt. Dabei wurde eine stufenweise Auflösung des Komplexes in Abhängigkeit von der Temperatur beobachtet, die mit den Stabilitätskonstanten und den thermodynamischen Parametern korreliert wurde.
    Notes: Stability constant and related thermodynamic parameters (ΔH° and ΔS°) of a multicomponent intermacromolecular complex consisting of poly(acrylic acid-coacrylamide), poly(methacrylic acid-co-acrylamide) and poly(N-vinylpyrrolidone) have been determined using known methods. A distinct stepwise disintegration of the complex at different temperatures has been observed, and this could be correlated with the stability constant and thermodynamic parameters calculated at various temperatures.
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  • 18
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    Angewandte Makromolekulare Chemie 226 (1995), S. 53-57 
    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: Der Einfluß von Ultraschall auf die Polymerisation und Depolymerisation von Ethylmethacrylat und der Mechanismus des Kettenabbruchs wurden untersucht. Der Polymerisationsumsatz war unabhängig von den verwendeten Ultraschallbedingungen (800 W, 35 kHz). Depolymerisationsversuche mit Ultraschall bei 20°C zeigten, daß Kettenabbruch im wesentlichen durch Disproportionierung stattfindet; dabei werden Molekulargewichte nicht unter ca. 500000 erreicht.
    Notes: The effect of ultrasound in ethyl methacrylate polymerization and depolymerization and the chain termination mechanism for ethyl methacrylate have been studied. Polymerization conversion at 60°C did not depend on energy (80 W) and frequency (35 kHz) of ultrasound applied. In ultrasound depolymerization studies at 20°C the governing termination mechanism was found to be disproportionation and the lower limiting molecular weight was Mn = 500 000.
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  • 19
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    Angewandte Makromolekulare Chemie 226 (1995), S. 71-87 
    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: The copolymerization of acrylonitrile with maleic anhydride was investigated to synthesize acylic reactive polymers for manufacture of membranes that serve as support for covalent enzyme immobilization. The free-radical copolymer synthesis was carried out in solution (N,N-dimethylformamide (DMF), dimethylacetamide (DMAC), γ-butyrolactone, ethylene carbonate), by precipitation polymerization (dioxane) as well as bulk polymerization. The polymers were characterized using IR spectroscopy, elementary analysis, NMR spectroscopy, gel permeation chromatography, viscosity measurements, osmometry and potentiometry.The kinetic parameters were followed by dilatometric measurements up to high conversions. The anhydride content in the monomer mixtures showed a significant influence on the rate of polymerization and the molecular weight. With raised concentration of anhydride the polymerization rate and molecular weights decreased. Film forming polymers (M̄η 〉 30 000 g/mol) can be obtained by all copolymerization procedures with exception of solution polymerization in DMF and DMAC, respectively. The content of maleic anhydride in the membrane polymers did not exceed 5 mol-%, even though the maleic anhydride content in the monomer mixtures was raised up to the equimolar mixture. Nevertheless, such low maleic anhydride content of prepared membranes is enough for successful enzyme immobilization with amyloglucosidase (copolymer was prepared in γ-butyrolactone, M̄η = 49 000 g/mol, cPMSA = 0,3 mol-%).
    Notes: Die Copolymerisation des Acrylnitrils mit Maleinsäureanhydrid (MSA) wurde mit dem Ziel untersucht, acylfunktionalisierte Reaktivpolymere mit Filmbildungseigenschaften herzustellen, um diese in der Anwendung als Membran für kovalente Enzymfixierungen zu nutzen. Die radikalinitiierte Synthese der Copolymeren wurde in Lösung (Dimethylformamid (DMF), Dimethylacetamid (DMAC), γ-Butyrolacton, Ethylencarbonat), durch Fällungscopolymerisation (Dioxan) sowie in Substanz durchgeführt.Die Polymercharakterisierung erfolgte durch IR-Spektroskopie, Elementaranalyse, Kernresonanzspektroskopie, Gelpermeationschromatographie, Viskosimetrie, Osmometrie und Potentiometrie.Die Kinetik wurde durch dilatometrische Untersuchungen bis zu hohen Umsätzen verfolgt. Danach weist der Anhydridgehalt im Monomergemisch einen signifikanten Einfluß auf die Bruttopolymerisationsgeschwindigkeit und die Molmasse der Polymeren auf. Mit steigendem Anhydridanteil wird die Bruttopolymerisationsgeschwindigkeit herabgesetzt und eine Verringerung der Molmasse herbeigeführt. Die Copolymerisation von Acrylnitril und Maleinsäureanhydrid führt mit Ausnahme der Lösungspolymerisation in DMF bzw. DMAC zu Polymeren mit Molmassen oberhalb 30 000 g/mol, was ihre Anwendung als Membran ermöglicht. Die Einbaurate an Maleinsäureanhydrid in den Membranpolymeren ist bis einschließlich einer äquimolaren Zusammensetzung des Monomergemischs nicht größer als 5 mol-%. Derartig niedrige MSA-Reaktivgruppenanteile erweisen sich jedoch als ausreichend, um an einer aus einem Lösungspolymerisat (γ-Butyrolacton, M̄η = 49 000 g/mol, cPMSA = 0,3 mol-%) formierten Membran eine Enzymimmobilisierung mit Amyloglucosidase nachzuweisen.
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  • 20
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    Angewandte Makromolekulare Chemie 226 (1995), S. 143-160 
    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: Die Synthesen einer Aryl-alkyl-azodiisocyanat-Verbindung und einer Azoharnstoff-Modellsubstanz werden beschrieben. Aus dem Azodiisocyanat wurden durch Grenzflächen-Polyaddition neuartige Azoharnstoff-Polymer hergestellt. Die zahlenmittleren Molekulargewichte, bestimmt mit der Gelpermeationschromatographie (GPC), lagen zwischen 6000 und 9000. Die Photolyse- und Thermolysereaktionen der Modellsubstanzen und der Polymeren wurden mittels UV-Spektroskopie und Differentialkalorimetrie (DSC) verfolgt und mit den Ergebnissen von ähnlichen Azoamiden verglichen. Der photochemische Polymerabbau wurde mittels GPC untersucht.
    Notes: The synthesis of an aryl alkyl azo diisocyanate and a model azo urea is described. From the azo diisocyanate new azo polyureas were created by interfacial polyaddition. Molecular weights Mn in the range of 6000 to 9000 were determined by gel permeation chromatography (GPC). Photolysis and thermolysis of both, model compounds and polymers, were studied by UV-spectroscopy and differential scanning calorimetry (DSC), respectively, and the results were compared with those of similar azo amides. Photochemical polymer degradation was followed by GPC.
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  • 21
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    Angewandte Makromolekulare Chemie 226 (1995), S. 219-219 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 22
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    Angewandte Makromolekulare Chemie 227 (1995), S. 69-85 
    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: Thermotrop flüssigkristalline Copolyester aus Vanillinsäure (V), 4-Hydroxybenzoesäure (B) und Polyethylenterephthalat (E) wurden mittels 1H-NMR-Spektroskopie und Gelpermeationschromatographie (GPC) untersucht. Die neun möglichen Diaden konnten detektiert und zugeordnet werden. Die Abfolge der Grundeinheiten der V/B/E-Copolyester ändert sich mit zunehmendem B-Anteil von statistischer Verteilung zur Blockbildung und ist außerdem geringfügig von der Katalysatorkonzentration und der Polykondensationsdauer abhängig. Die GPC-Ergebnisse deuten darauf hin, daß die V/B/E-Copolyester engere Molekulargewichtsverteilungen aufweisen als die B/E-Copolyester. Mit von 0 bis 5 mol-% steigendem V-Anteil verengt sich die Molekulargewichtsverteilung. Die Gelpermeationschromatogramme der meisten V/B/E-Copolyester weisen im Unterschied zu den Einzelsignalen der B/E-Copolyester Dublett-Peaks auf.
    Notes: Thermotropic liquid-crystalline copolyesters made from vanillic acid (V), 4-hydroxybenzoic acid (B) and poly(ethylene terephthalate) (E) were examined by 1H-NMR and GPC investigations. Nine possible diads could be identified and assigned. The sequence distribution of V/B/E copolyesters tends to change from random to block with an increase of B content in the copolyesters. The sequence distribution also varies slightly with catalyst concentration and polycondensation time. GPC results suggest that the V/B/E copolyesters have narrower molecular weight distribution (MWD) than B/E copolyesters. The MWD of the copolyesters narrows gradually with increasing V content from zero to 5 mol-%. The GPC chromatograms of the most V/B/E copolyesters show double peaks, which is different from the single peak of the GPC chromatograms of the B/E copolyesters.
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  • 23
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    Angewandte Makromolekulare Chemie 227 (1995), S. 111-120 
    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: Die Strahlungsbeständigkeit von vorbestrahltem Polypropylen mit 2,5 Gew.-% Ethylenanteil wurde mitr einem Copolymeren aus Polypropylen und einem nukleierenden Agens im Hinblick auf die Strahlungssterilisation von medizinischen Geräten verglichen. Die Transparenz des Propylen-Ethylen-Copolymeren wurde durch die Vorbehandlung verbessert. Im Vergleich mit der ebenfalls verbesserten Transparenz des Copolymeren aus Polypropylen und dem nukleierenden Agens wurde durch die Vorbestrahlung die Strahlungsbeständigkeit während der Bestrahlung und bei der Lagerung des bestrahlten Materials verbessert. Dies wird auf die geringere Kristallinität des vorbestrahlten Polypropylens aufgrund von bei der Bestrahlung gebildeten Verzweigungen zurückgeführt.
    Notes: The radiation stability of the pre-irradiated copolymer of polypropylene containing 2.5 wt.-% ethylene units is compared with a copolymer of polypropylene with a nucleating agent with regard to radiation sterilization of medical devices. It is found that transparency property of the propylene-ethylene copolymer is improved through pre-irradiation processes. This finding was compared with the co-polypropylene with nucleating agent which also gives a better transparency property. In comparison, it is found that pre-irradiated copolymer exhibits better radiation stability during irradiation and during storage after irradiation. The radiation stability of the pre-irradiated copolymer is due to its lower crystallinity caused by the formation of branches during the pre-irradiation process.
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  • 24
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    Angewandte Makromolekulare Chemie 227 (1995), S. 193-193 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 25
    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: Polydiaryldiazosulfide wurden durch Grenzflächenpolykondensation aus aromatischen Bisdiazoniumionen und Benzol-1,3-dithiol erhalten. Auf diese Weise wurden Molekulargewichte Mn von 3400 bis 11700 erreicht (GPC).Die neue Polymerklasse zeichnet sich durch hohe Photolabilität und relativ geringe Thermostabilität aus. Mittels UV-Spektroskopie wurde die Photolyse von Modellver-bindungen und Polymeren verfolgt, wobei in nahezu allen Fällen ein Zerfall 1. Ordnung beobachtet wurde. Der photochemische Kettenabbau konnte durch GPC-Untersuchungen verfolgt werden. Die thermische Stabilität der polymeren Diazosulfide wurde durch DSC-Messungen untersucht.
    Notes: Poly(diaryl diazosulfide)s were synthesized from aromatic bisdiazonium ions and benzene-1,3-dithiol via interfacial polycondensation. Number-average molecular weights Mn in the range of 3400 to 11700 were determined by gel permeation chromatography (GPC).The new polymer class is distinguished by high photosensitivity and low thermostability. First order kinetics during photolysis of nearly all polymers and model compounds under investigation was observed by means of UV spectroscopy. Polymer degradation upon irradiation was verified by GPC measurements. Thermal decay was followed by differential scanning calorimetry (DSC).
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  • 26
    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: Three different titration methods were proved with respect to accuracy, reproducibility and handling for the determination of maleic anhydride (MSA) content in acrylonitrile (AN) copolymers in form of poly(AN-co-MSA) and poly(AN-co-styrene-co-MSA). The comparison comprises (i) the combined method A/H characterized by the reaction of anhydride groups (AG) with aniline and titration of the formed monoacid with methanolic KOH (A) and the complete hydrolysis of AG and titration of acid groups (SG) with aqueous NaOH (H), (ii) method B based on the conversion of AG with n-butylamine (BA) and back-titration of unreacted amine with HClO4 in glacial acetic acid and (iii) method C consisting of the reaction of AG with p-chloroaniline (pCA) followed by Cl-determination after the Schöniger-decomposition. Whereas all mentioned methods are suitable for the determination of AG in the presence of initial SG, the combination of A/H additionally allows the simultaneous determination of AG and SG. In comparison with the other methods the combination of A/H is to be favoured due to the possibility to obtain additional information about SG and because of the better results in accuracy, reproducibility and handling. By means of FTIR spectroscopy the content of AG and SG was estimated qualitatively and a correlation between the spectroscopic and potentiometric data of AG was discovered.
    Notes: Zur Bestimmung des Maleinsäreanhydrid(MSA)-Gehaltes in Acrylnitril(AN)-Copolymeren des Typs Poly(AN-co-MSA) bzw. Poly(AN-co-Styrol-co-MSA) wurden drei verschiedene Titrationsmethoden hinsichtlich ihrer Richtigkeit, Reproduzierbarkeit sowie ihres Zeitaufwandes geprüft. Miteinander verglichen wurden (i) eine Methodenkombination A/H bestehend aus dem Teilschritt A, einer Umsetzung der Anhydridgruppen (AG) mit Anilin einschließlich der Titration der Monosäuregruppen mit methanolischer KOH, und dem Teilschritt H, einer vollständigen Hydrolyse der AG und Titration der Säuregruppen (SG) mit wäßriger NaOH, (ii) Methode B basierend auf der Reaktion der AG mit n-Butylamin (BA) und der Rücktitration des nicht umgesetzten Amins mit Perchlorsäure (HClO4) in Eisessig und (iii) Methode C, beruhend auf der Umsetzung der AG mit p-Chloranilin (pCA) und nachfolgender Chlorbestimmung durch Schöniger-Aufschluß. Während sich alle genannten Methoden prinzipiell für die AG-Bestimmung in Gegenwart initialer SG empfehlen, ist darüber hinaus über A/H eine simultane Bestimmung von AG und SG möglich. Wegen dieses zusätzlichen Informationsgewinns, ihrer besseren Reproduzierbarkeit, der erhöhten Richtigkeit sowie des geringeren zeitlichen und apparativen Aufwandes ist die Kombination A/H zu favorisieren. Mit Hilfe der FTIR-Spektroskopie wurde der Gehalt an AG und SG qualitativ verfolgt und eine Korrelation zwischen den Bandenintensitäten der AG und den potentiometrisch erhaltenen Werten gefunden.
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  • 27
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    Angewandte Makromolekulare Chemie 229 (1995), S. 15-27 
    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: Die Härtung eines ungesättigten Polyesterharzes mit niedrigem Exotherm-Peak wurde mit der Standardmethodik und der Differential-Kalorimetrie (DSC) untersucht. Ein Kupfersalz und α-Methylstyrol wurden als Polymerisationsverzögerer benutzt. Der Einfluß der Verzögerer auf die Temperatur des exothermen Peaks, die Gelzeit, die Härtungsenthalpie und die Polymerisationskinetik wurden untersucht.
    Notes: The curing behavior of an unsaturated polyester resin with low exotherm peak was studied by a standard procedure and by differential scanning calorimetry (DSC). A copper salt and α-methylstyrene were used as the polymerization retarders. The influence of the retarders on the exotherm peak temperature, gelation time, exothermic heat and the polymerization kinetics was investigated.
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  • 28
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    Angewandte Makromolekulare Chemie 229 (1995), S. 93-112 
    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: Propen und 1-Octen wurden mit dem syndiospezifischen Metallocen-Katalysator Me2C(Cp)(Flu)ZrCl2/MAO copolymerisiert. Es wurde ein hoher, statistischer Octeneinbau beobachtet. Niedrige Octenkonzentrationen beeinflußten die Aktivität des Katalysators nur wenig; Molekulargewicht, Kristallinität, E-Modul und Glastemperatur wurden dagegen mit ansteigendem Octengehalt erniedrigt. Blends aus ataktischem Oligopropen und syndiotaktischem Polypropen bzw. Poly(propen-co-octen) wurden aus einer Toluol-Lösung hergestellt. Diese Lösungsblends wurden mit einem Reaktorblend verglichen, der mit einem Hybrid-Katalysator bestehend aus einer Mischung von syndiospezifischem Me2C(Cp)(Flu)ZrCl2/MAO und unspezifischem Cp2ZrCl2/MAO hergestellt wurde. Das ataktische Oligopropen wirkte als Weichmacher, der E-Modul und Glastemperatur der Blends erniedrigte.
    Notes: Propene and 1-octene were copolymerized with the syndiospecific homogeneous metallocene catalyst Me2C(Cp)(Flu)ZrCl2/MAO. Large amounts of octene were incorporated randomly. While catalyst activity was not affected markedly by low octene content, molecular weight, crystallinity, Young's modulus, and glass transition temperature were reduced with increasing octene content. Blends of atactic oligopropene with syndiotactic polypropene and poly(propene-co-octene) were prepared from toluene solution and compared with a reactor blend prepared with a hybrid catalyst containing a mixture of syndiospecific Me2C(Cp)(Flu)ZrCl2/MAO and non-specific Cp2ZrCl2/MAO. Atactic oligopropene acted as plasticizer reducing Young's modulus and glass transition temperature of the blends.
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  • 29
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    Angewandte Makromolekulare Chemie 229 (1995), S. 175-184 
    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: Die innere Oberfläche und das Hohlraumsystem von verschiedenartigen Celluloseregeneratfasern werden mit Röntgenkleinwinkelstreuung untersucht. Dabei wird gefunden, daß alle Fasern ein Hohlraumsystem von 0,01 bis 0,1% (Volumenanteil 10-4-10-3) aufweisen. Es zeigt sich jedoch, daß die Größe des Hohlraumsystems für die mechanischen Eigenschaften wenig Bedeutung hat. Es ist vielmehr die Gestalt der Hohlräume und ihre Orientierung, die hier wesentlich sind. Es wird gefunden, daß langgestreckte Hohlräume, vermutlich orientiert, für gute mechanische Eigenschaften verantwortlich sind. Damit können auch verbesserte textile Eigenschaften von Lyocellfasern des NMMO-Typs erklärt werden.
    Notes: Both the inner surface and the void system of different cellulose regenerate fibers are investigated with X-ray small angle scattering. Thereby it turns out that all fibers have a void system of 0.01 to 0.1% (volume fraction 10-4-10-3). However, the amount of the void system has little influence on the mechanical properties. Rather, it is the shape of the voids and their orientation which proves essential. It is found that elongated voids, probably well oriented, are responsible for superior mechanical properties. This explains also improved textile properties of lyocell fibers of the NMMO type.
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  • 30
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    Angewandte Makromolekulare Chemie 230 (1995), S. 1-12 
    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: Die mit γ-Strahlen induzierte Polymerisation von Methacrylsäure (MA) und Acrylsäure (AA) mit Acrylamid (AAm) (M2) in Substanz wurde untersucht. Die nach Kelen-Tüdős berechneten Copolymerisationsparameter betragen r1 = 1.35 und r2 = 0.22 für MA-AAm bzw. r1 = 1.75 und r2 = 0.10 für AA-AAm. Die Polymerisationsgeschwindigkeit hängt sowohl von der Temperatur als auch von der Comonomerzusammensetzung ab. Die differentialkinetischen Kurven sind unimodal, was darauf hinweist, daß nur der Copolymerisationsprozeß abläuft. Ein zweites Maximum in diesen Kurven wird mit Vernetzung und der Bildung wasserunlöslicher Bestandteile erklärt. Die Copolymeren sind weiße Pulver; die wasserlöslichen Fraktionen sind im Gegensatz zu den wasserunlöslichen nicht giftig, aber als Immunmodulatoren weniger aktiv.
    Notes: A study was made of the γ-radiation-induced bulk copolymerization of the methacrylic acid-acrylamide (M2) (MA-AAm) and acrylic acid-acrylamide (M2) (AA-AAm) monomeric pairs. The copolymerization reactivity ratios deterined according to the Kelen-Tüdő method were: r1 = 1.35, r2 = 0.22 for the MA-AAm pair, and r1 = 1.75, r2 = 0.10 for the AA-AAm pair. It has been established that the polymerization rate depends both on the composition of the starting reaction mixture and on the reaction temperature. The differential kinetic curves obtained are unimodal ones, suggesting the occurrence of only one process, i.e. copolymerization. A second maximum in these curves, appearing at elevated temperature, is explained by crosslinking and formation of a water-insoluble fraction. The copolymers obtained are white powders; in contrast to their water-insoluble fractions, the water-soluble ones are not toxic but they are less active as immunomodulators.
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    Angewandte Makromolekulare Chemie 228 (1995), S. 201-219 
    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: Die Hydrolyse von Poly(ester-urethan-harnstoffen) (PURUs) wurde untersucht. Es handelt sich dabei um einen komplexen Vorgang, der die Analyse der Beziehung zwischen der Zusammensetzung der PURUs und ihrer Hydrolysebeständigkeit erschwert. Es wurde gefunden, daß die Hydrolysebeständigkeit mit Zunahme (i) der Polyol-Acidität, (ii) des Estergruppen-Gehaltes, (iii) der Beweglichkeit der Hauptketten und (iv) deren Hydrophilie abnimmt; die Molmasse des Polyols scheint keinen merklichen Einfluß darauf zu haben. Der negative Einfluß von Ethergruppen (obwohl hydrolysebeständiger als Estergruppen) ist möglicherweise auf eine Zunahme der Hauptkettenbeweglichkeit und den dadurch leichteren Zugang von Wassermolekülen zu Estergruppen zurückzuführen. Der positive Effekt von aromatischen Ringen in Polyolen kann einer erhöhten Steifigkeit der Hauptkette als auch einer ansteigenden Hydrolysebeständig-keit benachbarter Estergruppen durch Resonanzeffekte zugeschrieben werden. Insgesamt kann angenommen werden, daß die beschriebenen Effekte sich überlagern und gleichzeitig die resultierende Hydrolysebeständigkeit vorherbestimmen. Es sollte daher möglich sein, qualitative Vorhersagen bezüglich der Hydrolysebeständigkeit in Abhängigkeit von der Zusammensetzung der PURUs zu treffen.
    Notes: Hydrolysis of poly(ester urethane ureas) (PURUs) is a complex phenomenon which impedes the analysis of the relationships between their composition and hydrolytic stability. Hydrolytic stability of PURUs decreases due to rising (i) polyol acidity, (ii) content of ester groups, (iii) flexibility and (iv) hydrophilicity of the backbones; molar mass of polyols does not seem to have any appreciable effect on it. Negative influence of ether groups (which have better hydrolytic stability than ester groups) is probably linked to the increase in the backbone flexibility and, consequently, to easier access of water molecules to ester groups. Positive effect of aromatic rings in polyols can be ascribed to enhanced rigidity of the backbones as well as to increased hydrolytic stability of adjacent ester groups due to the resonance effect. It can be presumed that the mentioned effects will superpose and simultaneously predestine the resulting hydrolytic resistance. Considering the observed tendencies, it is possible to qualitatively predict the trends how the hydrolytic stability will respond to changes in PURUs composition.
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    Angewandte Makromolekulare Chemie 229 (1995), S. 63-72 
    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: Eine neuartige lichtempfindliche Naphthochinondiazid-Verbindung (NQD) wurde aus 2,6-Bis(hydroxymethyl)-3,4-dimethylphenol und Toluoldiisocyanat synthetisiert und mit IR-, NMR- und Elementaranalyse identifiziert. Die Bleicheigenschaften unter Lichteinwirkung wurden mit UV-Spektrophotometrie bestimmt. Die Anwendung von NQD in der Photolithographie als positiver Photoresist sowie einer wäßrigen Lösung von NQD, Novolak, Cellosolve-Acetat und DMF als lichtempfindliches Material wurde untersucht. Das hergestellte NQD erwies sich als effektive Komponente in positiven Photoresists. Die optimalen Bedingungen der UV-Dosis, Schichtdicke und Resistzusammensetzung wurden abgeschätzt. Die Auflösung des positiven Photoresists wurde durch Rasterelektronenmikroskopie bestimmt. Außerdem wurde der Einfluß von UV-Dosis und -Wellenlänge, Einwirkungsdauer und Entwicklungszeit auf die Empfindlichkeit und die Auflösung des Photoresists untersucht.
    Notes: A new photosensitive naphthoquinonediazide (NQD) was synthesized from 2,6-bis-(hydroxymethyl)-3,4-dimethylphenol and toluene diisocyante. NQD was identified by using IR, NMR and elemental analyses. Photobleachable characteristics were evaluated by UV spectrophotometry. Applications of the NQD on the photolithography as a positive working photoresist were investigated. The aqueous solution of NQD, novolak, cellosolve acetate, and DMF was used as a photosensitive material. It was found that NQD synthesized in this investigation can be used as an effective component in a positive photoresist. Optimal conditions of the UV dose, coating thickness, and development of the resist system were estimated. Resolution of the positive resist was evaluated by SEM technique. Effects of UV dose, exposure time, development time, and exposure UV wave length on the sensitivity and resolution of the photoresist were investigated.
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    Angewandte Makromolekulare Chemie 229 (1995), S. 123-132 
    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: Die radikalinduzierte Polymerisation von phenlysubstituierten 2-Methylen-1,3-dioxanen wurde untersucht. Es kann gezeigt werden, daß die grundlegende Polymerisationstendenz derartiger Ketenacetale darin besteht, über die Doppelbindung zu hochmolekularen Polyacetalen ohne eine nennenswerte Ringöffnung zu polymerisieren. Einflußfaktoren, wie z. B. resonanzstabilisierte Kettenenden oder sterische Hinderungen während des Wachstumsschrittes sind nicht in der Lage, die Polymerisation in die Richtung der gewünschten Ringöffnung zu lenken.Mittels Dichtemessungen wurden Informationen über das Schrumpfungsverhalten gewonnen. Es konnte gezeigt werden, daß raumerfüllende Substituenten am 2-Methylen-1,3-dioxansystem bei der Homopolymerisation grundsätzlich eine geringe Volumenschrumpfung bewirken und die Schrumpfung von herkömmlichen Monomeren bei der Copolymerisation herabsetzen können.
    Notes: We have investigated the free radical polymerization of phenyl-substituted 2-methylene-1,3-dioxanes. It was shown that there is a basic tendency of such ketenacetals to undergo exclusively a vinyl polymerization forming high-molecular polyacetals without any detectable ring opening. The polymerization with the desirable ring opening reaction cannot be controlled by factors like resonance stabilized chain ends or steric hindrance in the growing step.From densitometric measurements we got new information about the shrinkage behaviour. It was demonstrated that bulky substituents attached to the 2-methylene-1,3-dioxane system result in a significant low shrinkage in homopolymerization and the shrinkage of common comonomers can be decreased by copolymerization.
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  • 34
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    Angewandte Makromolekulare Chemie 229 (1995), S. 133-143 
    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: Die Polymerisation von Acrylamid (AAM) in einer konzentrierten bikontinuierlichen Mikroemulsion wurde studiert. Die Initiierungsstelle bei Verwendung von radikalischen Initiatoren mit verschiedener Wasserlöslichkeit wurde untersucht. Es wurde festgestellt, daß ein vollständig oder teilweise wasserlöslicher radikalischer Initiator die Acrylamidpolymerisation in der untersuchten Mikroemulsion effektiv initiieren kann. Die dadurch entstandenen Polymeren weisen eine Spezialstruktur auf, die von der Zusammensetzung der ursprünglichen Mikroemulsion abhängig ist.
    Notes: The polymerization of acrylamide (AAM) in concentrated bicontinuous microemulsion systems was studied. The locus of initiation using radical initiators with various water-solubility was investigated. It was found that water-soluble and partially water-soluble initiators initiate the AAM polymerization in the reaction systems under investigation very effectively. The polymers thus formed have special structures dependent on the composition of the original concentrated bicontinuous microemulsion.
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  • 35
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    Angewandte Makromolekulare Chemie 229 (1995), S. 209-209 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 36
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    Angewandte Makromolekulare Chemie 229 (1995), S. 185-198 
    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: Bacteriorhodopsin is a component of the purple membrane of Halobacterium halobium. It shows photochemical activity and undergoes a series of photocyclic-associated conformational changes. Incorporated in a matrix it is suitable as a light energy/electrical current transducer. Very important is an orientation of purple membrane fragments.The reaction between solutions of a polyelectrolyte and multivalent ions leads to a ionotropic gel, that is a gel with an ordered structure. If the gel formation was carried out in the presence of purple membrane fragments, the Bacteriorhodopsin is highly oriented and produces a photoelectrical signal. It consists a correlation between the light direction and the orientation of the purple membrane due to the gel formation.
    Notes: Bacteriorhodopsin ist Bestandteil der sogenannten Purpurmembran des Mikroorganismus Halobacterium halobium. Es zeigt photochemische Aktivität und kann als biologischer Lichtwandler fungieren. Voraussetzung hierfür ist eine orientierte Anordnung der Purpurmembran in einer Matrix.Das Prinzip der ionotropen Gelbildung, d. h. die geordnete Strukturbildung einer Polyelektrolytlösung infolge eines gerichteten Diffusionsstromes von mehrwertigen Ionen gestattet die orientierte Anordnung der Purpurmembran. Durch Lichteinwirkung werden elektrische Signale induziert. Es besteht ein Zusammenhang zwischen der Richtung des Strahlungseinfalls und der durch die Gelwachstumsrichtung festgelegten Orientierung der Purpurmembran.
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  • 37
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal oxidation of β ray-crosslinked polyethylene (XLPE) was studied in temperatures ranging from 90 to 180°C. Various analytical methods were used for determination of an end of the induction period on bulk samples: gravimetry, ultimate tensile properties, density and color change. On microtome slices of ∼30 μm thickness the depth distribution of oxidation products, phenolic antioxidant, density and tensile ultimate properties were followed as a function of exposure time by respectively IR and UV spectrophotometry, densitometry and Microfoil Tensile Testing.Depending on the testing method different durations of induction period (DIP) were obtained. They increase in following order:Phenol depletion 〈 Ultimate elongation 〈 Density 〈 Carbonyl build-up ≤ Color change 〈 Weight loss.The difference between phenol depletion DIP and carbonyl build-up DIP can be considered as negligible at temperatures higher than the melting point (about 30%) but it reachs more than 100% at T〈 Tm.Different kinetic regimes of phenol consumption were observed depending on the exposure temperature. A mechanistic interpretation is proposed explaining the role of the stabilizer system in initially homogeneous and later heterogeneous oxidation of the bulk material.The Arrhenius law was applied to different durations of induction period. A discontinuity appeared in the melting point region (120-130°C) which is tentatively interpreted in terms of different stabilizer concentration in amorphous phase of semicrystalline material (T 〈 Tm) and in melt material (T 〉 Tm). On the basis of the presented complex study of polyethylene thermo-oxidation, different aspects of lifetime predictions are discussed.
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  • 38
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Most plastics are produced from oil and have a high potential as hydrocarbon sources for the chemical industry. Pyrolysis is a practicable way to pyrolyze mixed plastics. The fluidized bed pyrolysis has turned out to be particularly advantageous. 25 to 45 percent of product gas with a high heating value and 30 to 50 percent of an oil rich in aromatics, could be recovered. The oil is comparable to that of a mixture of light benzene and bituminous coal tar. Up to 60 percent of ethene and propene are produced by using mixed polyolefins as feedstock. Under appropriate conditions the pyrolysis could be successful on the market.
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  • 39
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When poly(methyl methacrylate) films containing UV absorbers are exposed to UV light, the absorbers undergo photodegradation resulting in loss of absorbance. If the data extend for less than one half-life, both zero and first order kinetic treatment give fairly linear fits, but the rate constants so derived are dependent on the initial absorbance of the films. When the zero order rate constants are corrected to account for the higher rate of degradation near the surface compared with the bulk that occurs in highly absorbing films, consistent “infinite absorption” zero order rate constants are derived. The inhomogeneous degradation is due to only the highly absorbed, higher energy light contributing significantly to the degradation. For the benzophenone and benzotriazole classes of absorber, at least 65% of the degradation is due to light with wavelengths 〈 350 nm. Structural variations generally caused only small differences in the rates of degradation of these classes of absorbers unless the substitutions disrupted the intramolecular hydrogen bonds that are critical for stability. If the hydrogen bond is weakened, the absorber is less stable.
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  • 40
    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: Aus Cardanol, einem Bestandteil der Schale der Cashewnuß, wurde durch Kondensation mit Formaldehyd und substituierten aromatischen Verbindungen unter saurer oder basischer Katalyse eine Reihe von Harzen hergestellt und anhand ihrer IR-Spektren charakterisiert. Sie lassen sich als selektive Ionenaustauscher für bestimmte Ionen verwenden, was mittels einer Gleichgewichtsmethode geprüft wurde. Das thermische Verhalten der Harze wurde untersucht, und ein plausibler Abbaumechanismus wird vorgeschlagen.
    Notes: A large number of resins have been synthesized by reacting cardanol, a constituent of cashewnut shell liquid, with formaldehyde and substituted aromatic compounds in the presence of acidic and basic catalysts. The resins have been characterized by IR spectra. They were shown to be selective ion exchangers for certain metal ions. A batch equilibrium method was used for studying the selectivity of the metal ions. The thermal behaviour of the resins has been studied and a plausible degradation mechanism has been suggested.
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  • 41
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bisphenol A polycarbonate (BPA-PC) is an important high performance engineering thermoplastic well known for its outstanding combination of toughness, transparency and heat resistance. These properties make it an idel material for demanding applications where it is exposed to external stresses such as elevated temperatures, ultraviolet light and γ-ray sterilization. However, on extended exposure to these conditions, BPA-PC slowly degrades, turning progressively more yellow, eventually leading to a decrease in its physical properties. Over the years, there has been numerous studies made to understand these degradative processes so as to better design more stable BPA-PC formulations. In this paper, this chemistry is briefly reviewed along with more recent work in this area with a special emphasis on the efforts made to identifying the actual chemical species responsible for the observed yellow color and the chemistry responsible for their formation.
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  • 42
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hindered Amine Light Stabilizers (HALS) are know to inhibit the photo-oxidation of polymers. A key reaction in their stabilization mechanism is believed to be the conversion of a hindered aminoether into a nitroxyl radical. Several different possible mechanisms for this conversion were explored. One, the elimination of the aminoether to form an olefin and hydroxylamine (an intermediate in the formation of a nitroxyl), while possible at high temperatures, cannot account for the inhibitory activity we observed for secondary and primary aminoethers. Direct radical displacement by peroxy radicals was also considered. However, the products predicted by this reaction pathway were not observed. Finally, oxidation of the nitrogen by a peroxy radical, by either electron transfer or a radical attack on the nitrogen, was investigated. While electron transfer was shown to be unlikely, direct oxidation of the aminoether nitrogen was supported by our results. A detailed mechanism for the reaction of both alkyl- and acyl-peroxy radicals with aminoethers is proposed.
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  • 43
    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: Die thermischen und dynamisch-mechanischen Eigenschaften einiger linearer kautschukelastischer Polyurethane mit chemisch unterschiedlichen starren Segmenten wurden untersucht und zur chemischen Zusammensetzung in Beziehung gesetzt. Interessante Zusammenhänge wurden zwischen der Kristallinität der elastischen Polyurethanharnstoffe und der aromatischen oder cycloaliphatischen Natur der Diisocyanat-Komponenten gefunden. Darüber hinaus scheinen die Ergebnisse bei einem bestimmten Verhältnis zwischen starren und flexiblen Segmenten und bei gegebener Zusammensetzung der flexiblen Gruppen auf eine bessere Phasenseparation bei den Polyurethanharnstoffen mit cycloaliphatischen starren Segmenten als bei solchen mit aromatischen, starren Einheiten hinzuweisen.
    Notes: Experimental batches of linear rubber-like polyurethanes characterized by the presence of chemically different hard segments are studied and their thermal and dynamic-mechanical properties are related to the differences in chemical compositions. Interesting correlations are found between the development of crystallinity in such elastomeric poly(urethaneurea)s and the aromatic or alicyclic nature of the diisocyanate. Moreover, for a fixed ratio between hard and soft segments, and for a given composition of the soft segment, the results seem to indicate a better degree of phase separation in cycloaliphatic-based hard segment poly(urethaneurea)s than in aromatic-based hard segment poly(urethaneurea)s.
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  • 44
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    Angewandte Makromolekulare Chemie 231 (1995), S. 135-144 
    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: Makromonomere Polyethylenoxid-Azoinitiatoren (Makroinimere) MIM-400 und MIM-1500 wurden synthetisiert und IR- und NMR-spektroskopisch sowie mit Hilfe der DSC-Analyse charakterisiert. Die mit diesen Makroinimeren initiierte Dispersions-polymerisation von Styrol bzw. Methylmethacrylat (MMA) in Ethanol/Wasser bei 60°C wurde untersucht. Dabei wurde gefunden, daß die Polymerisationsgeschwindig-keit mit zunehmender MIM-Konzentration ansteigt, wobei der Anstieg im Styrolsystem ausgeprägter war. Im Bereich von mittleren Umsätzen konnte gezeigt werden, daß die Polymerisationsgeschwindigkeit von MMA proportional der Potenz 1,7 bzw. 1,6 von [MIM-400] bzw. [MIM-1500] ist, während für Styrol eine Potenz von 2,5 bezüglich [MIM-400] gefunden wurde.
    Notes: Macromonomeric poly(oxyethylene) azoinitiators (macroinimers) MIM-400 and MIM-1500 were synthesized and characterized by IR and NMR spectroscopy and DSC techniques. The dispersion polymerizations of styrene and methyl methacrylate (MMA) initiated by poly(oxyethylene) macroinimers (MIM-400 and MIM-1500) in water/ethanol were investigated at 60°C. The rate of polymerization was found to increase with increasing concentration of MIM and the increase was more pronounced in the styrene system. In the range of medium conversions the rate of polymerization was found to be proportional to the 1.7th and 1.6th power of [MIM-400] and [MIM-1500] for MMA and to the 2.5th power of [MIM-400] for styrene, respectively.
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  • 45
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    Angewandte Makromolekulare Chemie 231 (1995), S. 187-198 
    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: Glass transition temperatures of binary and ternary blends of chemically uniform poly(styrene-co-n-butyl methacrylate)s with a mean content of 30.8 wt.-% of n-butyl methacrylate and number-average molar masses in the range of 4900 and 67000 g/mol have been investigated in relation to their composition. The blends showed significant deviations from an ideal behaviour with reference to a linearity between glass transition temperature and composition.This phenomenon is described by a mathematical model where polynoms are particularly well suited to represent the glass transition temperatures of the blends, partly exceeding those of the pure components. Finally, various reasons of these deviations were discussed. Here, energetical interactions seem to be of considerable importance combined with a nonadditivity of volumes.
    Notes: Die Glasübergangstemperaturen binärer und ternärer Mischungen chemisch einheitlicher Poly(styrol-co-n-butylmethacrylat)e mit einem mittleren n-Butylmethacrylat-Anteil von 30,8 Gew.-% und unterschiedlichen zahlenmittleren Molmassen im Bereich von 4900 bis 67000 g/mol wurden in Abhängigkeit von der Zusammensetzung untersucht. Es wurden wesentliche Abweichungen vom idealen Verhalten bezüglich einer linearen Abhängigkeit zwischen Glasübergangstemperatur und Zusammensetzung festgestellt.Dieses Verhalten konnte mit einem mathematischen Modell dargestellt werden, wobei sich insbesondere Polynome zur Beschreibung der teilweise über den Werten der Ausgangskomponenten liegenden Glasübergangstemperaturen der Mischungen als geeignet erwiesen. Schließlich wurden verschiedene Ursachen für diese Abweichungen diskutiert, wobei offensichtlich energetische Wechselwirkungen verbunden mit einer Nichtadditivität der Volumina von wesentlicher Bedeutung sind.
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  • 46
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    Angewandte Makromolekulare Chemie 233 (1995), S. 133-148 
    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: ε-Caprolactam (CL) and phenyl glycidyl ether (PGE) were homopolymerized using the initiator/accelerator-systems Na-caprolactam/N-acetyl-caprolactam (NaCL/AcCL) and Na-caprolactam/N-acetyl imidazole (NaCL/AcImi). In a one-pot reaction both monomers gave different oligomeric reaction products depending on the reaction temperature (100°C to 140°C, max. 240°C) but no regular copolymers. Soluble products were separated by HPLC and identified by means of spectroscopic methods. In acetone insoluble products were investigated by IR- and NMR-spectroscopy, mass spectrometry and elemental analysis.
    Notes: Es wurden Versuche zur Homopolymerisation von ε-Caprolactam (CL) und Phenylglycidether (PGE) mit den Initiator/Beschleuniger-Systemen Na-Caprolactam/N-Acetylcaprolactam (NaCL/AcCL) und Na-Caprolactam/N-Acetylimidazol (NaCL/AcImi) durchgeführt, um die für eine mögliche Copolymerisation von CL und PGE geeigneten Reaktionsbedingungen zu ermitteln. CL und PGE wurden in unterschiedlichen molaren Verhältnissen (CL : PGE = 1 : 5 bis 1 : 0,05) und bei Temperaturen zwischen 100°C und 140°C (max. 240°C) in einer Eintopfreaktion polymerisiert.Die löslichen Produkte wurden mittels HPLC getrennt und spektroskopisch identifiziert. Die in Aceton unlöslichen Produkte wurden mit IR- und NMR-Spektroskopie, Massenspektrometrie (MS) und Elementaranalyse untersucht.
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  • 47
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    Angewandte Makromolekulare Chemie 231 (1995), S. 199-211 
    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: 2-Methylaziridin (MAz) wurde als nukleophiles Monomeres mit den elektrophilen Monomeren Acrylsäure (AA) bzw. Methacrylsäure (MA) in unterschiedlichen Verhältnissen ohne Initiator copolymerisiert. Die Copolymeren wurden mittels Elementaranalyse, FT-IR- und 1H-NMR-Spektroskopie charakterisiert. Die Copolymerisationsparameter wurden mit den Methoden nach Fineman-Ross bzw. Kelen-Tüdős bestimmt. Für r1 und r2 wurden die Copolymerpaare MAz-AA und MAz-MA jeweils Werte 〈 1 ermittelt, was auf statistische Copolymere mit einer Tendenz zu alternierenden Copolymeren hinweist. Thermische Zersetzung mit einem Gewichtsverlust von 10% tritt bei den Copolymeren erst oberhalb 430 K auf. Der thermische Abbau verläuft nach einer Reaktion nullter Ordnung. Die kinetischen Parameter der Zersetzung der Copolymeren wurden bestimmt.
    Notes: 2-Methylaziridine (MAz) as a nucleophilic monomer and acrylic acid (AA) and methacrylic acid (MA), respectively, as electrophilic monomers were copolymerized in the absence of initiator at various feed ratios. Copolymers were characterized by elemental analysis, FT-IR and 1H-NMR spectroscopy. The monomer reactivity ratios were determined by the Fineman-Ross and Kelen-Tüdős methods. Values of r1 and r2 were found to be less than unity for MAz-AA, and MAz-MA, corresponding to random copolymers with the tendency to the alternance. For all the copolymers the thermal decomposition with 10% weight loss is higher than 430 K. The reaction order for degradation of all copolymers was zero. The kinetic parameters of the decomposition were determined for all copolymers.
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  • 48
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of the solid state oxidation of isotactic polypropylene films and the the mechanism of inhibition by HALS have been investigated by kinetic-ESR and kinetic modelling with derivation of the rate constants for the sensitive steps in the reaction scheme. The results have shown the inadequacy of the Denisov cycle to account for the observed experimental kinetics of the intermediate nitroxyl radicals. The molecular dynamics associated with the oxidation inhibited by HALS in the polypropylene matrix has been investigated by applying the Liouville stochastic method to the analysis of the temperature effects of the ESR spectra of the intermediate nitroxyl radicals used as spin probes. The investigation on the nature and characteristics of the molecular motions available at the oxidation sites has also been carried out with nitroxyl spin labels bound to the PP chains. For this application a novel method of spin labelling was developed based on reactions with some of the oxidation products, namely the terminal and intrachain ketones (keana method), alcohols, peroxides and macroalkyl radicals.
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  • 49
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As plastics are being used in a variety of applications, demands on a greater level of processing stability are increasing. Phosphites are noteworthy as effective processing stabilizer and the performance of phosphite antioxidants can be correlated to the chemical structure of phosphites. Cyclic phosphite esters derived from 2, 2′ methylene bis-2, 4-di-tert-butylphenol and some commercially available phosphites were submitted to comparative studies. Decomposition of cumene hydroperoxide, melt flow of polypropylene and consumption of additives after multiple extrusions were investigated to understand the activity of phosphites as process stabilizers in polypropylene.This study suggests that phosphites play an important role in process stabilization when used in combination with sterically hindered phenols, and that the activity of phosphites may be predicted by their reactivity on hydroperoxide.
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  • 50
    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: Durch redoxinitiierte radikalische Polymerisation von Methylmethacrylat (MMA) und Acrylamid (AAm) mit Polyethylenglykol (PEG) und Mn(III) als Reduktionsmittel wurden PMMA-PEG-PMMA- und AAm-PEG-AAm-Triblockcopolymere hergestellt. Der EinfluR der Konzentration der Reaktanden und der Temperatur auf den Umsatz und die Grenzviskositat der Copolymeren wurde untersucht. Die Blockcopolymeren wurden mittels 'H-NMR- und IR-Spektroskopie charakterisiert.
    Notes: Redox-initiated free-radical polymerization of methyl methacrylate (MMA) and acrylamide (AAm) with poly(ethy1ene glycol) (PEG) using Mn(III) as reduction agent was carried out to yield PMMA-block-PEG-block-PMMA and AAm-block-PEG-block-AAm triblock copolymers. The principal parameters (concentration of the reactants, temperature) affecting the synthesis were examined. Block copolymers were characterized by 'H-NMR and infrared spectroscopy.
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  • 51
    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: Durch redoxinitiierte radikalische Polymerisation von Methylmethacrylat (MMA) mit Azogruppen enthaltendem Polyethylenglykol (PEG) und Mn(III) als Reduktionsmittel wurden PMMA-PEG-PMMA-Triblockcopolymere mit Azogruppen in der Polymerkette hergestellt. Mit diesen Prepolymeren wurde durch thermischen Zerfall der Azogruppen die radikalische Polymerisation von Styrol initiiert, wobei Multiblockcopolymere gebildet wurden, die durch fraktionierte Fällung, eine starke Zunahme des Molekulargewichts sowie 1H-NMR- und IR-Spektroskopie nachgewiesen wurden.
    Notes: Redox polymerization of methyl methacrylate using Mn(III) with poly(ethylene glycol) having azo and hydroxy functions was carried out to yield ethylene glycolmethyl methacrylate block copolymers with labile azo linkages in the main chain. These prepolymers were used to initiate free-radical polymerization of styrene through thermal decomposition of the azo groups, resulting in the formation of multiblock copolymers. Successful blocking has been confirmed by fractional precipitation, a strong change in the molecular weight, and spectral measurements.
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  • 52
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    Angewandte Makromolekulare Chemie 224 (1995), S. 61-71 
    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: By addition of a stabilizer (4-benzyloxyphenol) the oxidative thermal decomposition of benzylcellulose during melt processing was reduced. The minimum stabilizer concentration was 5 wt.-%. Plastification with diethyl phthalate reduced the glass transition temperature and the processing temperature and imparted softness and flexibility of the inherently brittle benzylcellulose. The required plasticiser concentration (5-10 wt.-%) is lower than that required for other cellulose ethers like ethylcellulose (10-20 wt.-%) or cellulose acetates (20-30 wt.-%).
    Notes: Durch Zusatz eines Stabilisators (4-Benzyloxyphenol) kann die oxidative thermische Schädigung von Benzylcellulose bei deren Verarbeitung aus der Schmelze vermindert werden. Die notwendige Mindestkonzentration an Stabilisator beträgt 5 Gew.-%. Durch äßere Weichmachung mit Diethylphthalat können die Glas- und die Verarbeitungstemperatur herabgesetzt und eine zufriedenstellende Weichheit und Flexibilität der ansonsten hart-spröden reinen Benzylcellulose erzielt werden. Die erforderliche Weichmacherkonzentration liegt bei 5 bis 10 Gew.-% und ist damit wesentlich niedriger als für andere Cellulosederivate wie z. B. Ethylcellulose (10-20 Gew.-%) oder Celluloseacetate (20-30 Gew.-%).
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  • 53
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    Angewandte Makromolekulare Chemie 224 (1995), S. 73-88 
    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: Because of their properties, flax fibres can be used as reinforcing material in composites, e. g. as substitute for glass fibres in composites with polypropylene. A major drawback of this application is the high water adsorption of the natural fibre and its low adhesion to the hydrophobic polymer.Therefore, improvement of adhesion to the polypropylene matrix by application of bifunctional silanes was investigated. While silanes with alkyl groups did not significantly improve the fibre-matrix adhesion, it was found that silanes which carry functional groups capable of reacting by formation of free radicals under processing conditions lead to a remarkable improvement. For silanes with vinylic and methacrylic groups, the dependence of adhesion on the nature of hydrolysis catalyst, on the compound which initiates the free-radical reaction, and on the degree of fibre silylation was investigated. The degree of silylation was varied under optimum concentration conditions.
    Notes: Flachsfasern können auf Grund ihres Eigenschaftsprofils als Verstärkungsmaterial in Verbundwerkstoffen genutzt werden. Als wichtiger Anwendungsfall bietet sich die Substitution von Glasfasern in Compounds aus Glasfasern und dem Standardkunststoff Polypropylen an. Problematisch für diesen Einsatz sind die hohe Wasseraufnahme der Naturfaser und deren geringe Haftung zum hydrophoben Polymeren.Es wurde daher versucht, die Adhäsion zur Polypropylenmatrix durch Applikation von bifunktionellen Silanen zu erhöhen. Während alkylgruppenfunktionalisierte Silane nur eine unbedeutende Verbesserung der Faser-Matrix-Haftung bewirken, konnte jedoch eine deutliche Steigerung mit solchen Silanen erzielt werden, deren funktionelle Gruppe unter Verarbeitungsbedingungen des Verbundwerkstoffes radikalisch reagiert. Für vinyl- und methacrylgruppenfunktionalisierte Silane wurde die Abhängigkeit zwischen dem Hydrolysekatalysator, der die Radikal-Reaktion initiierenden Verbindung, der Silanauflage und dem Adhäsionsniveau untersucht und unter optimalen Konzentrationsverhältnissen die Silanauflage variiert.
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  • 54
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    Angewandte Makromolekulare Chemie 224 (1995), S. 145-151 
    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: In einer zweistufigen radikalischen Polymerisation, initiiert mit einem Initiator mit Azo- und Acyloximgruppen (AOE), wurden Blockcopolymere aus Styrol und Methylmethacrylat (MMA) erhalten. In der ersten Stufe mit dem AOE-Initiator hergestellte photosensitive Styrol-Prepolymere wurden in der zweiten Stufe als Photoinitiatoren für die Polymerisation von MMA eingesetzt, wobei Blockcopolymere gebildet wurden. Diese wurden mit geeigneten Lösungsmitteln extrahiert und mittels GPC sowie IR- und NMR-Spektroskopie charakterisiert.
    Notes: Block copolymers of styrene and methyl methacrylate (MMA) were prepared in a two-stage free-radical polymerization by means of an azo-acyloxime ester (AOE) initiator. In the first stage, photosensitive styrene prepolymers were synthesized by using AOE initiator. These polymers were photolysed in the presence of MMA in the second stage to form block copolymers. The block copolymer structure was elucidated by means of extraction by appropriate solvents, GPC analysis and IR and NMR spectral measurements.
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  • 55
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    Angewandte Makromolekulare Chemie 224 (1995), S. 191-200 
    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: The melting points of liquid-crystalline main chain polyesters made from hydroquinone derivatives and substituted terephthalic acids can be lowered strongly by attaching flexible side chains or voluminous side groups. The solid state of poly(2′-phenyl-1′,4′-phenylene-2,5-dihexyloxyterephthalate) is even amorphous with a glass transition at 47°C and a phase transition to isotropic melt at 184°C. Beside the low phase transition temperatures, this polyester is readily soluble in toluene and tetrahydrofuran. Up to 40 mol-% of 2,5-dihexyloxyterephthalic acid may be replaced by unsubstituted terephthalic acid without a strong influence on the phase transition temperatures and the solubility of the polyester. The E-modulus of the copolyester with 40 mol-% of terephthalic acid reaches 7700 MPa.
    Notes: Bei flüssigkristallinen Hauptkettenpolyestern aus Hydrochinon- und Terephthalsäurederivaten lassen sich die Schmelztemperaturen durch “Anheften” von flexiblen Seitenketten und raumfüllenden Gruppen stark absenken. Poly(2′-phenyl-1′,4′-phenylen-2,5-dihexyloxyterephthalat) liegt im festen Zustand sogar amorph vor; die Glasübergangstemperatur beträgt 47°C, der Phasenübergang zur isotropen Schmelze erfolgt bei 184°C. Neben tiefen Phasenübergangstemperaturen zeichnet sich dieser Polyester durch eine gute Löslichkeit in Toluol und THF aus. Bis zu 40 mol-% der 2,5-Dihexyloxyterephthalsäre lassen sich durch unsubstituierte Terephthalsäure ersetzen, ohne die Phasenübergangstemperaturen und die Löslichkeit des Polyesters wesentlich zu beeinflussen. Der Copolyester mit 40 mol-% Terephthalsäure zeigt im Zugversuch nach DIN 53455 einen E-Modul von 7700 MPa.
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  • 56
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    Angewandte Makromolekulare Chemie 225 (1995), S. 1-9 
    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: Acrylnitril wurde unter Verwendung des Redoxinitiatorpaares Peroxodisulfat-Eisen(II)-ammoniumsulfat auf Jutefasern gepfropft. Der Einfluß der Reaktionszeit, Temperatur, Menge an Jutefaser, Monomer-, Initiator- und Schwefelsäurekonzentration sowie verschiedener Lösungsmittel und Salze auf die Pfropfausbeute wurde untersucht. Die gepfropfte Jute wurde mittels IR-Spektroskopie charakterisiert. Die Pfropfung verbessert die Lichtechtheit von mit Rhodamin B gefärbter Jute.
    Notes: The graft polymerization of acrylonitrile (AN) onto chemically modified bleached jute fibers has been studied using potassium peroxydisulfate-ferrous ammonium sulfate redox initiating system. The effects of time of reaction, variation in concentration of monomer, peroxydisulfate, ferrous ammonium sulfate and sulfuric acid on graft yield have been studied. The effects of temperature, amount of jute fibers, some inorganic salts and organic solvents on graft yield have also been investigated. Grafted jute has been characterized by IR spectra. Grafting has improved the light fastness of jute dyed with Rhodamine B dye.
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  • 57
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    Angewandte Makromolekulare Chemie 225 (1995), S. 21-35 
    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: Dielektrische Messungen an Silikon, EPDM und einem Blend aus gleichen Gewichtsteilen beider Polymerer wurden im Frequenzbereich 1-105 Hz zwischen 25 und 200°C vor und nach Alterung in Wasser, Wasserdampf und Luft durchgeführt. Für das unpolare und nahezu verlustfreie EPDM werden niedrige Werte der Dielektrizitätskonstante und des Verlustfaktors gemessen. Die für EPDM beobachtete thermische Depolarisation ist bei in Luft gealtertem EPDM aufgrund von Dipolorientierung etwas ausgeprägter. Silikon wird in zwei Stufen polarisiert. Veränderungen der dielektrischen Eigenschaften und des spezifischen Gleichstromwiderstands nach Alterung belegen, daß Ladungsträger bei niedriger Temperatur und polare Silanolgruppen bei hoher Temperatur zur Polarisation beitragen. Die Eigenschaften des Blends hängen vom Alte-rungsmedium ab. Hydrothermische Alterung bewirkt eine qualitative Verbesserung des Dielektrikums Silikon durch Entfernung von Ladungsträgern und der Unterdrückung der Silikonhydrolyse durch EPDM. Durch Alterung des Blends in Luft nimmt dessen Polarisation zu, bedingt durch die Bildung von Ladungsträgern und Dipolen sowie die zusätzliche Grenzchicht. Aus Aktivierungsenergien wird gefolgert, daß die bei niedriger Temperatur stattfindende Polarisation mit der Beweglichkeit der Ladungsträger und der Orientierung von Seitengruppen zusammenhängt. rungsmedium ab. Hydrothermische Alterung bewirkt eine qualitative Verbesserung des Dielektrikums Silikon durch Entfernung von Ladungsträgern und der Unterdrückung der Silikonhydrolyse durch EPDM. Durch Alterung des Blends in Luft nimmt dessen Polarisation zu, bedingt durch die Bildung von Ladungsträgern und Dipolen sowie die zusätzliche Grenzchicht. Aus Aktivierungsenergien wird gefolgert, daß die bei niedriger Temperatur stattfindende Polarisation mit der Beweglichkeit der Ladungsträger und der Orientierung von Seitengruppen zusammenhängt.
    Notes: Dielectric measurements in the frequency (1-105 Hz) and temperature (25-200°C) domains have been carried out for silicone, EPDM, and their 50/50 (by weight) blend before and after ageing in water, steam and air. Low values of permittivity and loss tangent for EPDM reflect its non-polar and loss-free nature. Thermal depolarisation is also observed with EPDM and the air-aged specimen shows little rising trend due to dipole orientation. Silicone is found to be polarised in two steps. Changes in dielectric properties and DC resistivity on hydrothermal weathering and air ageing confirms that charge carriers contribute in the low-temperature step and polar silanol groups contribute in the high-temperature region. The properties of the 50:50 blend are very much sensitive to the medium of ageing. Hydrothermal ageing improves the quality of the dielectric of silicone due to removal of charge carriers and the suppression of silicone hydrolysis by EPDM. Ageing of the blend in air increases the polarisation to a very high level owing to the charge carriers, the additional interface and the dipoles formed during ageing. Activation energies suggest that the low temperature polarisation step is associated with charge carrier mobility and orientation of pendent groups.
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  • 58
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    Angewandte Makromolekulare Chemie 225 (1995), S. 73-81 
    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: The rheological properties of polypropene containing various amounts of wood-flour, of polypropene elastified with 1,4-poly-cis-isoprene and of the ternary composite material based on polypropene, elastified polypropene and wood-flour were studied. The flow curves (viscosity curves) of the melts were obtained by means of a capillary viscosimeter, and the melt flow index, the consistency index and the melt flow rate through the capillary were determined from these curves. A pseudo-plastic nature of the flow was established, the compositions containing 7 to 15 wt.-% of elastomer showing the best flowability. The activation energy of viscous flow was calculated from the shear viscosity using the Frenkel-Eyring equation. The elastified polypropene was characterized by an enhanced impact strength, timber outlook and higher outdoor durability, as compared to elastomer-free, wood-flour-filled polypropene.
    Notes: Die rheologischen Eigenschaften von mit unterschiedlichen Mengen Holzmehl gefülltem Polypropylen, von mit 1,4-cis-PolyisoprenSystematischer Name: Poly(1-methyl-cis-1-butenylen). elastifiziertem Polypropylen und von ternären Blends aus Polypropylen, Polyisopren und Holzmehl wurden untersucht. Die Fließkurven der Schmelzen wurden mit einem Kapillarviskosimeter erhalten, und daraus wurden der Fließindex, der Konsistenzkoeffizient und die Strömungsgeschwindigkeit durch die Kapillare bestimmt. Die Schmelzen zeigen einen pseudoplastischen Strömungscharakter, wobei am leichtesten die Blends mit 7 bis 15 Gew.-% Elastomeranteil strömen. Aus der Scherviskosität wurde mit der Gleichung von Frenkel-Eyring die Aktivierungsenergie der viskosen Strömung berechnet. Das elastifizierte Polypropylen zeigt eine erhöhte Schlagfestigkeit, ein holzartiges Aussehen und eine größere Wetterbeständigkeit als das mit Holzmehl gefüllte Polypropylen ohne Elastomeranteil.
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  • 59
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    Angewandte Makromolekulare Chemie 225 (1995), S. 109-122 
    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: Poly(ethylenterephthalat)-(PET)-Rezyklat aus gebrauchten Getränkeflaschen wurde bei 150-220°C im Vakuum behandelt oder bei mehreren Temperaturen mit zwei unterschiedlichen Durchsatzgeschwindigkeiten extrudiert. Nach anschließender Extraktion wurden die erhaltenen niedermolekularen Verbindungen mittels Hochleistungs-Flüs-sigchromatographie (HPLC), Größenausschlußchromatographie (SEC) und Massenspektrometrie mit chemischer Ionisierung (DCI/MS) untersucht. Die Verteilung von cyclischen und linearen Oligomeren mit Polymerisationsgraden von 2 bis 6 im Extrakt wurde bestimmt. Als Folge der Vakuumbehandlung des PET nimmt der Oligomergehalt mit steigenden Temperaturen ab. Umgekehrt führt die Extrusion bei ansteigenden Temperaturen (ebenso bei längeren Aufbewahrungszeiten) zu höheren Oligomerkon-zentrationen. Außerdem wurden bei zunehmenden Aufbewahrungstemperaturen und -zeiten breitere Molekulargewichtsverteilungen beobachtet, d. h. es wurden in zunehmendem Maße größere Ringe und längere Ketten gebildet. Eine bedeutende Menge an Oligomeren mit mittlerem Molekulargewicht wurde ebenfalls nachgewiesen.
    Notes: Low-molecular-weight compounds extracted from recycled poly(ethylene terephthalate) (PET) from post-consumer soft-drink bottles, treated at 150-220°C in vacuo or extruded at several temperatures and two different mass flow rates, were characterized by high performance liquid chromatography (HPLC), size exclusion chromatography (SEC) and desorption chemical ionization/mass spectrometry (DCI/MS). Among these products, cyclic and linear oligomers (polymerization degree 2-6) were identified, and their distribution was determined.As a consequence of vacuum treatment of PET, the overall oligomer content decreases with increasing temperatures. Conversely, the extrusion at crescent temperatures causes an increase of the oligomer concentration; the same effect was observed by increasing the residence time. A further effect was represented by the enlargement of molecular weight distributions, i.e. larger rings and longer chains were formed in greater amounts at higher temperatures and residence times; a significant fraction of medium-molecular-weight oligomers (M̄n = 1400-1900) was also formed.
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  • 60
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    Angewandte Makromolekulare Chemie 225 (1995), S. 123-130 
    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: Dextran wurde mit 4-Nitrophenylchloroformat und Pyridin als Katalysator umgesetzt. Die Struktur der modifizierten Dextrane wurde mittels IR-, 1H- und 13C-NMR-Spektroskopie bestimmt. Unter den gewählten Reaktionsbedingungen entstehen nur acyclische Carbonate. Vorversuche zeigten, daß die Reaktion der 4-Nitrophenyl-chloroformat-Gruppen mit verschiedenen Amin-Modellverbindungen stark von der Basizität des Amins abhängt. Die Anbindung der Modellamine Phenethylamin und Tyramin an das modifizierte Dextran war befriedigend. Die Dextran-Phenethylamin-und Dextran-Tyramin-Verbindungen sind gegen heterogene Hydrolyse bei 37°C (pH 9 und pH 1) weitgehend beständig.
    Notes: The modification reaction of dextran with 4-nitrophenyl chloroformate using pyridine as catalyst was studied. The structure of the resulting polymers was determined by means of IR, 1H and 13C NMR spectroscopy as well as by chemical analysis. Under the used experimental conditions only acyclic carbonate groups have been detected. Preliminary experiments have shown that the reaction of 4-nitrophenyl carbonate groups with several model amines is greatly dependent on the basic character of the amine. Model amino-type drugs (phenethylamine and tyramine) were satisfactorily bound to activated dextran with 4-nitrophenyl carbonate groups. The heterogeneous hydrolysis of dextran-phenethylamine or dextran-tyramine adducts showed that no significant hydrolysis takes place under the applied conditions (pH 1 and pH 9, 37°C).
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  • 61
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    Angewandte Makromolekulare Chemie 226 (1995), S. 89-99 
    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: Die Strangaufweitung und die Scherviskosität von lyotrop flüssigkristallinen Lösungen von Hydroxypropylcellulose in N,N-Dimethylacetamid wurden in einem relativ breiten Scherspannungs- und Konzentrationsbereich bei 30°C mit einer langen Kapillardüse mit einem Achsenverhältnis von 114 gemessen. Die Strangaufweitung hängt in ähnlicher Weise von der Konzentration ab wie die Scherviskosität; sie zeigt ein Maximum bei einer kritischen Konzentration Ca und ein Minimum bei einer weiteren kritischen Konzentration Cb, wobei Ca 〈 Cb. Die Abhängigkeit der Strangaufweitung von der Scherspannung wird stark von der Zahl der Phasen der Lösung bestimmt: Im isotropen Bereich unterhalb Ca nimmt die Strangaufweitung mit der Scherspannung monoton zu; nahe Ca durchläft sie ein Maximum; in einem zweiphasigen Bereich zwischen Ca und Cb nimmt sie wieder ab und durchläuft im einphasig-isotropen Bereich oberhalb Cb ein Minimum, wobei eine oberhalb Cb auftretende Distorsion des Extrudats im Bereich des Minimums verschwindet.
    Notes: The die swell and shear viscosity of lyotropic liquid crystal-forming hydroxypropyl cellulose solutions in N,N-dimethylacetamide were determined over a relatively wide range of shear stress or polymer concentration at 30°C by using a long capillary die with an aspect ratio of 114. The dependence of die swell on the concentration was similar to that of shear viscosity: a maximum at a critical concentration Ca and a minimum at another critical concentration Cb (Ca 〈 Cb). The dependence of the swell on shear stress is greatly affected by the solution phase: in an isotropic range (below Ca), the die swell increased monotonously with shear; in the vicinity of Ca, the die swell exhibited a maximum; in a biphasic range (between Ca and Cb), the die swell decreased monotonously; in a single-phase anisotropic range (above Cb), the die swell exhibited a minimum. Above Cb, extrudate distortion was observed and disappeared around the shear where the die swell exhibited a minimum.
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    Angewandte Makromolekulare Chemie 226 (1995), S. 47-52 
    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: Filme aus Cellulosetriacetat wurden mit oligomeren 2-Hydroxy-4-alkoxybenzophenon-Derivaten stabilisiert und thermisch gealtert. Die oxidationshemmende Wirkung der oligomeren Stabilisatoren wurde durch Messung des Gewichtsverlusts, der Änderung von Carbonyl- und Hydroxy-Index sowie der Änderung der Bruchspannung und -dehnung ermittelt. Es wurde festgestellt, daß die Stabilisatorwirkung der oligomeren Benzophenone im allgemeinen besser ist als die der monomeren Vorstufen.
    Notes: Cellulose triacetate films stabilized with oligomeric 2-hydroxybenzophenone derivatives were subjected to oven ageing. The antioxidant efficiency of the oligomeric stabilizers was determined by carrying out measurements of percentage weight loss, change in carbonyl index and hydroxy index, and change in tensile strength and elongation at break. In general, the oligomeric benzophenones show better performance than their monomeric precursors in stabilizing cellulose triacetate.
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  • 63
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    Angewandte Makromolekulare Chemie 226 (1995), S. 59-69 
    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: Mit Hilfe der Spannungsrelaxationskurven von Phenolphthalein-Poly(etherketon) (PEK-C) bei unterschiedlichen Temperaturen und dem Prinzip der Zeit-Temperatur-Äquivalenz wurden Masterkurven von PEK-C bei beliebigen Referenztemperaturen ermittelt. Mit dem Kopplungsmodell nach Kohlrausch-Williams-Watts wird die Temperaturabhängigkeit der Spannungsrelaxation quantitativ erklärt und eine Beziehung zwischen der Spannungsrelaxation und dem Fließverhalten vorgeschlagen.
    Notes: According to stress relaxation curves of phenolphthalein poly(ether ketone) (PEK-C) at different temperatures and the principle of time-temperature equivalence, the master curves of PEK-C at arbitrary reference temperatures are obtained. A coupling model (Kohlrausch-Williams-Watts) is applied to explain quantitatively the different temperature dependence of stress relaxation behavior and the relationship between stress relaxation and yield phenomenon is established through the coupling model.
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    Angewandte Makromolekulare Chemie 226 (1995), S. 205-212 
    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: Polyurethane and Polyetherurethane vom Elastomer-Typ mit nitroaromatischen Gruppen wurden hergestellt und mit UV-Licht in Lösung bestrahlt. Der Einfluß der UV-Strahlung auf die UV-Absorptionseigenschaften wurde untersucht und mit dem einer Modellsubstanz verglichen. Die UV-Bestrahlung bewirkt eine Intensitätsabnahme der charakteristischen UV-Absorptionsbanden und eine Verringerung des Molekulargewichts.
    Notes: Elastomer-type polyether urethanes and polyether urethane cationomers with nitroaromatic groups were prepared and the effect of UV irradiation on their characteristics was evaluated comparatively with a model compound. The photobehavior by UV irradiation with a high-pressure Hg lamp was studied in solution, following the change of absorption bands characteristic for nitro structures as a function of irradiation time. UV irradiation causes diminution of the intensity of characteristic UV absorption bands and a decrease of molecular weight.
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    Angewandte Makromolekulare Chemie 226 (1995), S. 197-204 
    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: Vergleichende Untersuchungen über die chromatographische Reinigung von Trypsin-Inhibitoren aus Sojabohnen (STI) wurden mit verschiedenen Polymermatrizes durchgeführt. Dazu wurden ein Copolymeres aus Butylacrylat und Ethylenglykoldimethacrylat sowie ein Terpolymeres aus Acrylnitril, Butylacrylat und Divinylbenzol als Vernetzer eingesetzt. Die Untersuchungen zeigten, daß sowohl mit der Affinitätschromatographie mit beiden Trypsin-modifizierten Copolymermatrizes als auch mit der Ionenaustauschchromatographie im Fall der mit Ethylendiamin aminierten Matrizes vergleichbare Reinigungswirkungen erzielt wurden. Mit den beiden nicht modifizierten Matrizes waren die Reinigungserfolge weniger groß und im Fall der mit Tris(hydroxymethyl)aminomethan hydrophilierten Matrizes fast vernachlässigbar.
    Notes: The paper presents comparative studies on chromatographic purification of soybean trypsin inhibitors (STI) applying various polymer matrices. Two types of copolymers were tested: a copolymer of butyl acrylate with ethylene glycol dimethacrylate, and a terpolymer of acrylonitrile and butyl acrylate crosslinked with divinylbenzene. The investigations revealed that a similar purification extent is achieved in affinity chromatography with trypsin attached to both copolymers and in ion exchange chromatography when the matrices are aminated with ethylene diamine. The purification phenomenon was not so high for both unmodified matrices, and quite negligible for matrices hydrophilized by end-capping with tris(hydroxymethyl)aminomethane.
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    Angewandte Makromolekulare Chemie 226 (1995), S. 213-217 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Diazopropane and 1-diazo-1-phenylethane were reacted with meso-tetraphenyl-porphin cobalt(III) bromide (Co(III)TPPBr), and the resulting vinyl Co(III)TPP derivatives were copolymerized with MMA to give alkyl Co(III)TPP complexes, covalently bound to macromolecules.
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    Angewandte Makromolekulare Chemie 226 (1995), S. 129-141 
    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: Der Einfluß der Verstärkung von Polyethylen niedriger Dichte (LDPE) und Polypropylen (PP) sowie deren Blends mit kurzen Polyamid-66-Fasern (PA) auf das Zug-, Biege- und Schlagzähverhalten der Matrix wurde untersucht. Die Moduli der Composite nehmen mit steigendem Faser- und PP-Gehalt zu, insbesondere bei LDPE/PP-Verhältnissen größer als 1. Der Einfluß der Fasern auf die Zug- und Biegefestigkeit hängt jedoch von der Zusammensetzung der Matrix ab. Während die Fasern bei LDPE/PP-Verhältnissen größer als 1 verstärkend wirken, zeigt sich bei Compositen mit PP als kontinuierlicher Phase eine Abnahme der Zugfestigkeit. In allen Fällen nimmt die Festigkeit der Composite, bei gleichem Faseranteil, mit steigendem PP-Gehalt zu. Das Einmischen von PA-Fasern bewirkt eine Zunahme der Zugfestigkeit bei Compositen mit einem PP-Anteil über 50% in der Matrix. Aus den Ergebnissen wird geschlossen, daß die PA-Fasern vornehmlich in der LDPE-Phase verstärkend wirken, verursacht durch eine höhere Affinität zwischen PA und LDPE.
    Notes: The effect of short polyamide 66 (PA) fibers on the tensile, flexural, and impact behaviour of low density polyethylene (LDPE), polypropylene (PP), and their blends has been investigated. The moduli of the composites increase as fiber and PP contents increase, and this effect is more noticeable at LDPE/PP ratios above 1. However, the effect of the fibers on the tensile and flexural strength of these materials depends on matrix composition. So, the polyamide fibers act as a reinforcing agent for polymer matrices with LDPE/PP ratios above 1, but with PP as the continuous phase a decrease in the tensile strength is observed. In all cases, at the same fiber content, the strength of the composites increases as PP percentage increases. On the other hand, the addition of PA fibers gives rise to an increase of the tenacity of the composites with PP percentages above 50% in the matrix composition. From the observed results a higher reinforcing effect and a better affinity between the polyamide fibers and the LDPE are suggested.
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    Angewandte Makromolekulare Chemie 227 (1995), S. 11-17 
    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: Ausgehend von 4,4′-Diaminodiphenylmethan-3,3′-dicarbonsäure und Estergruppen enthaltenden aromatischen Dicarbonsäuredichloriden wurden in einer zweistufigen Reaktion über Polyamidsäuren als Zwischenstufe Poly(esterbenzoxazinone) hergestellt. Diese sind lediglich in konzentrierter Schwefelsäure löslich und zersetzen sich thermisch zwischen 400 und 500°C.
    Notes: Poly(esterbenzoxazinone)s were prepared in two successive steps from 4,4′-diaminodiphenylmethane-3,3′-dicarboxylic acid and aromatic diacid dichlorides which contained preformed ester groups, via polyamic acids as intermediates. The poly(esterbenzoxazinone)s are soluble only in concentrated sulfuric acid. They thermally decompose in a single step between 400 and 500°C.
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  • 69
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    Angewandte Makromolekulare Chemie 227 (1995), S. 35-42 
    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: Adsorptionsmittel zur Entfernung von Polymerisationsinhibitoren aus Styrol wurden untersucht. Die ausgewählten Adsorptionsmittel besitzen ein weites Struktur- und Eigenschaftsspektrum. Die wichtigsten Inhibitoren für Labor- und Industrieverwendung wurden untersucht. Die Leistung der Adsorptionsmittel wurde durch Bestimmung der Inhibitorabnahme im Gleichgewicht bewertet. Aktivkohle erwies sich als das wirksamste Adsorptionsmittel. Die Polaritäten des Adsorptionsmittels und des Adsorbants sind die wichtigsten Faktoren des Adsorptionsprozesses. Die Entfernung des Inhibitors vor der Polymerisation kann von Bedeutung für industrielle Polymerisationen sein.
    Notes: Use of adsorptive materials for the removal of polymerization inhibitors from styrene is studied. The adsorptive materials selected cover a wide range of properties and structure. The most important inhibitors that are used in laboratory and industrial scale were studied. The effectiveness of the adsorptive materials was assessed by determining the inhibitor uptake at equilibrium. It was found that activated carbons are the most effective adsorbents for the removal of inhibitors from styrene and that the factor most affecting adsorption is the polarity of the adsorbent and the adsorbate. The possible importance of removing the inhibitor before industrial-scale polymerization is demonstrated.
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    Angewandte Makromolekulare Chemie 230 (1995), S. 47-71 
    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: Die Glykolyse von Poly(ethylenterephthalat) mit Bisphenol A wurde bei hohen Temperaturen zwischen 190°C und 230°C in einem Autoklaven durchgeführt und die Kinetik der Depolymerisation wurde untersucht. Die Reaktionstemperatur und das Verhältnis von Poly(ethylenterephthalat) und Bisphenol A erwiesen sich als bestimmend für die Reaktionsgeschwindigkeit und den Glykolysegrad. Zur exakten Beschreibung der Kinetik wurde ein aus sechs Gleichgewichtsreaktionen bestehender Reaktionsmechanismus vorgeschlagen, mit dem durch numerische Integration nach Runge-Kutta die kinetischen Parameter berechnet wurden. Die sehr gute Übereinstimmung zwischen den berechneten und den experimentellen Werten bestätigte die Richtigkeit des Mechanismus.
    Notes: Glycolysis of poly(ethylene terephthalate) with bisphenol A at high temperature (190°C-230°C) was carried out in an autoclave reactor. Kinetic study on depolymerization of glycolysis was conducted. The reaction temperature and the ratio of bisphenol A to poly(ethylene terephthalate) played the key roles on the reaction rate and the extent of glycolysis. For describing the kinetic behavior properly, a mechanism consisting of six principle equilibrium reactions was proposed. Based on this mechanism, the kinetic parameters were obtained through the Runge-Kutta numerical integration. Excellent agreements between the calculated values and the experimental data were achieved, thus verified the appropriateness of the proposed mechanism.
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    Angewandte Makromolekulare Chemie 230 (1995), S. 89-98 
    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: Durch radikalische Polymerisation wurden Harze mit Amid- und 4-Vinylpyridin-Gruppen synthetisiert. Die hergestellten wasserunlöslichen Polymeren Poly(4-vinylpyridin) (1), Poly(4-vinylpyridin-co-N,N-dimethylacrylamid) (2) und Poly(N,N-dimethylacrylamid) (3) wurden mit FT-IR-Spektroskopie, Elementaranalyse und Thermoanalyse charakterisiert. Die Fähigkeit der Harze, Cu(II)-, Fe(II)-, Fe(III)- und U(VI)-Ionen zu binden, wurde mit der Batch-Gleichgewichts-Methode bei verschiedenen pH-Werten untersucht. Die Harze 1 und 2 adsorbierten bei pH 1 mehr als 50% U(VI). Die Selektivität von U(VI) gegenüber Cu(II) bei pH 1,0 betrug 2,11. Durch Behandlung mit Schwefelsäure und Natriumcarbonat konnte das mit Uran beladene Polymere 2 teilweise regeneriert werden.
    Notes: Resins containing amide and 4-vinylpyridine moieties were synthesized by radical polymerization. All the resins were completely insoluble in water and characterized by FT-IR spectroscopy, elemental analysis and thermal analyses. The ability to bind Cu(II), Fe(II), Fe(III) and U(VI) ions at different pHs was studied by batch equilibrium procedure. Uranium(VI) was adsorbed at pH 1 above 50% by the resins 1 and 2. The selectivity of uranium(VI) respect to copper(II) at pH 1.0 was 2.11. The uraniumloaded resin 2 could be partially recovered by treatment with H2SO4 and Na2CO3.
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    Angewandte Makromolekulare Chemie 230 (1995), S. 99-104 
    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: Eine Reihe von Harzen des Novolak-Typs wurden durch Reaktion von Formaldehyd mit verschiedenen Phenoxy-Essigsäuren hergestellt, indem HCl als Katalysator eingesetzt wurde. Alle synthetisierten Harze wurden IR-spektroskopisch und viskosimetrisch untersucht; das zahlenmittlere Molekulargewicht wurde mit Hilfe der Dampfdruckosmometrie bestimmt. Zwei der Harzproben wurden zum Vernetzen von Epoxidharzen eingesetzt, um die Kinetik der Vernetzung mittels DSC-Untersuchungen zu studieren. Die vernetzten Epoxide wurden hinsichtlich ihrer thermischen Stabilität geprüft. Die hergestellten Harze verleihen dem Epoxidsystem eine sehr gute Hitzebeständigkeit.
    Notes: A series of novolak type resins were prepared by reacting formaldehyde with various phenoxy acetic acids using HCl as catalyst. All the synthesized resins were characterized by spectral studies (IR), viscometric measurements and by estimating the numberaverage molecular weight by vapour-pressure osmometry. Two of these resin samples were used as curing agents for epoxy resins for studying the kinetics of curing by DSC technique. The cured epoxies were tested for thermal stability. These resins impart very good heat resistance to epoxy systems.
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    Angewandte Makromolekulare Chemie 230 (1995), S. 179-187 
    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: Poly(trimethylenterephthalat) wurde durch Umesterung von Dimethylterephthalat und Polykondensation im halbtechnischen Maßstab hergestellt. Als Katalysator für beide Reaktionsschritte wurde Titantetrabutylat eingesetzt. Die erhaltenen Polymeren mit gewichtsmittleren Molekulargewichten von bis zu 70000 können aus der Schmelze versponnen werden und zeigen, im Gegensatz zu mit Titanverbindungen hergestelltem Poly(ethylenterephthalat), einen bemerkenswerten Weißheitsgrad. Die Mark-Houwink-Parameter in 1,1,2,2-Tetrachlorethan/Phenol-Lösung (1 : 1, w/w) wurden mit Kalibrierung durch statische Lichtstreuung bestimmt. Die MVI-Werte (235°C, 1,2 kg) lagen typischerweise zwischen 20 und 30 mL/10 min bei Polymeren mit einer gewichtsmittleren Molmasse von 50000-60000 g mol-1.
    Notes: Poly(trimethylene terephthalate) was synthesized on a semi-technical scale following the trans-esterification route. Ester exchange as well as polycondensation were catalyzed by titanium tetrabutylate. The polymer formed shows a remarkable degree of whiteness, contrary to poly(ethylene terephthalate) when synthesized with the aid of titanium compounds. Polymers having molar masses up to 70000 (weight average) were obtained suitable for melt spinning. The Mark-Houwink parameters for solutions in 1,1,2,2-tetrachloroethane/phenol (1 : 1, w/w) were determined using static light scattering as a calibration. The melt volume index (235°C, 1.2 kg) was typically in the range 20-30 mL/10 min for a polymer having a weight-average molar mass of 50000-60000 g mol-1.
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    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: Mit dem Monoester Ethylbenzoat als internem Elektronendonor komplexierte Titan-Magnesium-Katalysatoren (TMC) können mit TiCl4 und Dibutylphthalat zum Diester-Komplex umgesetzt werden. Aktivität und Stereospezifität der direkt mit dem Diester hergestellten und der modifizierten TMC sind bei der Polymerisation von Propylen annähernd gleich. Die Oberfläche und Porenstruktur beider TMC-Typen und deren Zusammenhang mit der jeweiligen Katalysatoraktivität wurde untersucht.
    Notes: Titanium-magnesium catalysts (TMC), containing monoester (ethyl benzoate) as internal donor, can be transferred to the diester TMC by the treatment with TiCl4 and dibutyl phthalate. The activity and the stereospecificity of the transferred TMC in propylene polymerization are close to those of TMC prepared directly in the presence of diester. The surface area and the porous structure of both types of TMC were studied and the correlation with the activity of these catalysts is discussed.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 123-133 
    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: Makrophotoinitiatoren aus Poly(ethylenglykol) (PEG) mit Benzoylxanthat-Segmenten wurden durch Reaktion der PEG-Xanthate mit Benzoylchlorid hergestellt. Diese Makrophotoinitiatoren mit PEGs unterschiedlicher Molekulargewichte wurden eingesetzt, um durch lichtinduzierte radikalische Polymerisation von Styrol und Methyl-methacrylat Blockcopolymere mit inneren PEG-Segmenten zu synthetisieren. Der Ein-fluß der Konzentration der Reaktanden und der Polymerisationszeit auf die Ausbeute und die Viskosität der Blockcopolymeren wurde untersucht. Die Blockcopolymeren wurden durch fraktionierte Fällung und IR-, UV- und 1H-NMR-Spektroskopie charakterisiert.
    Notes: Macro photoinitiators based on poly(ethylene glycol)s (PEG) bearing benzoyl xanthate moieties were synthesized by the reaction of PEG xanthates with benzoyl chloride. These macro photoinitiators possessing PEGs of different molecular weights were used in the photoinduced radical polymerization of styrene (S) and methyl methacrylate (MMA) to yield block copolymers having an inner-PEG segment. The influence of the concentration of reactants and polymerization time on the yield and intrinsic viscosities of block copolymers were also investigated. Characterization of block copolymers was carried out by fractional precipitation and IR, UV and 1H NMR spectroscopic methods.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 109-121 
    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: Die Flüssigkristalle 4-Butyl-N-(4-methoxybenzyliden)anilin (MBBA) und 4-Butyl-N-(4-ethoxybenzyliden)anilin (EBBA) wurden synthetisiert. Die hydrophilen Monomeren 2-Hydroxyethylmethacrylat (HEMA) und Acrylsäure (Aa) wurden eingesetzt, um die polymere Matrix für Flüssigkristalle zu bilden, die dispergieren und einen Polymer-Flüssigkristall-Film (PDLC) bilden, Um solche PDLC-Filme herzustellen, wurden MBBA, EBBA oder die kommerziellen Flüssigkristalle ZLI-2444, 2452, 2459 und BDH-E7 mit HEMA, Aa und photoempfindlichen Stoffen gemischt und mit UV-Licht bestrahlt. Das elektrooptische Verhalten und die Mikrostruktur der PDLC-Filme wurden mit einem He-Ne-Laser bzw. mit der Rasterelektronenmikroskopie (SEM) untersucht. Die Effekte der UV-Bestrahlung und des Monomerverhältnisses auf das Verhalten der PDLC-Filme wurden ebenso untersucht wie die Reproduzierbarkeit und die Speicherstabilität der Filme.
    Notes: 4-Butyl-N-(4-methoxybenzylidene)aniline (MBBA) and 4-butyl-N-(4-ethoxybenzylidene)aniline (EBBA) liquid crystals were synthesized. To investigate the applications of hydrophilic monomers and polymers on the field of polymer dispersed liquid crystal (PDLC) films, 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (Aa) were selected as monomers for the polymer matrix. To prepare the PDLC films, MBBA, EBBA, and commercial liquid crystals ZLI-2444, 2452, 2459 and BDH-E7 were mixed with HEMA, Aa and photosensitive materials and then irradiated by UV light. The electrooptical behavior and the microstructure of the PDLC films were investigated by He-Ne laser and scanning electron microscopy (SEM), respectively. The effects of UV-light irradiation and monomer ratio on the electrooptical behavior of PDLC films, and the reproducibility and storage stability of the PDLC films were investigated.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 91-108 
    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: Mit einem schnellen und einfachen Vorversuch wurde die Fähigkeit von unterschiedlich zusammengesetzten Grundierungen zur Reduzierung der “pink-ring”-Defekte in mehrschichtigen gedruckten Leiterplatten untersucht. Mischungen von Silanen mit multifunktionellen Silanol-Gruppen (Vernetzer) und 3-Glycidoxypropyl-trimethoxysilan (Silan A) oder N-(2-Aminoethyl)-3-aminopropyl-trimethoxysilan (Silan B) erwiesen sich als wirksam zur Reduzierung der “pink-rings”. Die Mischungen von Silan A mit aromatischen Vernetzern zeigten bessere Ergebnisse als andere Grundierungsformulierungen, was teilweise dem geringeren Anteil an hydrophilen Gruppen und der besseren Verteilung in den Filmen zugeschrieben wurde. Die besten Resultate wurden mit einer Grundierung mit Siloxan-Verbindungen erhalten. On-line Untersuchungen bestätigten die Ergebnisse der Vorversuche und demonstrierten die Durchführbarkeit des entwickelten Vortests zur Bewertung der Wirkung der Grundierungen. FT-IR-Spek-troskopie und Thermogravimetrie-untersuchungen zeigten, daß die auf die Kupfero-xide aufgebrachten Grundierungen sowohl die Vernetzungsreaktion fördern als auch die thermooxidative Stabilität der Epoxy/CuO-Systeme verbessern.
    Notes: A rapid and easy screening test was applied to assess the capability of various formulated primers to reduce the defect of pink rings in multilayer printed circuit boards. The mixtures of silanes with multifunctional silanol groups (crosslinkers) and 3-glycidoxypropyl-trimethoxysilaneSystematic name: 3-(2,3-Epoxypropoxy)propyl-trimethoxysilane. (referred to as silane C) or N-(2-aminoethyl)-3-aminopropyl-trimethoxysilaneSystematic name: 3-[N-2-aminoethyl]aminopropyl-trimethoxysilane. (silane B) were proved to be effective in reducing the pink rings. The performance of the mixed silanes using silane A and crosslinkers with aromatic groups were better than other formulated primers which was partly attributed to less amounts of hydrophilic groups and better integrity in the primer films. A developed primer consisting of siloxane compounds had the best performance. The online test confirmed the results from the screening test and demonstrated the feasibility of the designed screening test in assessing the performance of primers. The results of FTIR spectroscopy and thermogravimetric analyses confirmed that the effective primers coated on the copper oxides could improve the curing reaction and the thermal oxidative stability of the epoxy/CuO system.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 161-169 
    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: In the amorphous region (chlorine ≥ 30 wt.-%), chlorinated polyethylene (PE-C) which was prepared by chlorination in solution shows a continuous rise of the glass temperature Tg with increasing chlorine content. This Tg-percent chlorine function was compared with the Tg-percent chlorine function of PVC-C. It could be shown that the Δcp data as a function of the chlorine content measured at Tg has a maximum at 50 wt.-% chlorine in the case of PE-C and at 60 wt.-% chlorine in the case of PVC-C.
    Notes: Durch Chlorieren in Lösung hergestelltes Polyethylen (PE-C) zeigt im amorphen Bereich (Chlorgehalt ≥ 30 Gew.-%) eine kontinuierliche Erhöhung der Glastemperatur Tg mit steigendem Chlorgehalt. Diese Tg-Chlorgehalt-Funktion wurde verglichen mit der Tg-Chlorgehalt-Funktion des PVC-C. Es wurde festgestellt, daß die Δcp-Werte, gemessen bei Tg, in Abhängigkeit vom Chlorgehalt ein Maximum aufweisen, und zwar bei 50 Gew.-% Chlor für PE-C und bei 60 Gew.-% Chlor für PVC-C.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 213-213 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Angewandte Makromolekulare Chemie 230 (1995), S. 205-205 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
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    Angewandte Makromolekulare Chemie 231 (1995), S. 25-33 
    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: Die Viskosität verdünnter Lösungen in Wasser oder DMF von Polyurethan-Ionomeren mit Natriumsulfopropylgruppen an den Urethan-Stickstoffatomen wurde untersucht. Bei Temperaturen zwischen 25 und 60°C zeigte sich ein Polyelektrolyteffekt, der auch nach Zugabe von Natriumchlorid erhalten blieb. Dies läßt sich durch Coulombsche Wechselwirkungen zwischen den Ladungsträgern und eine Tendenz zur Aggregation in separierten Domänen (begünstigt durch die spezifische molekulare Architektur der Polymeren) erklären.
    Notes: Aqueous and DMF-diluted solutions of polyurethane ionomers with sodium propanesulfonated groups at urethanic nitrogen atoms were studied by viscometry. A polyelectrolyte effect was evidenced at temperatures between 25 and 60°C, and it was preserved when NaCl was added to solutions.The coulombic interactions between charged groups and a tendency to aggregation in separated domains (favoured by specific molecular architecture of polymers) explain the observed solution properties.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 69-77 
    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: Es wurde der Einfluß der Oberflächenbehandlung auf die Hydrophilie und die freie Oberflächenenergie (FSE) von isotaktischem Polypropylen (iPP) untersucht. Es wurde festgestellt, daß bereits ein- bis zweiminütige UV-Bestrahlung ausreicht, um die FSE zu erhöhen. Unter dem zusätzlichen Einfluß von PCl3 auf die Polymeroberfläche wird die FSE um 29% im Vergleich mit unmodifiziertem iPP erhöht. Die Adhäsionsarbeit steigt dabei um den Faktor sechs. Die FSE wächst durch die Anwendung von starken Oxidationsmitteln in wäßriger Lösung. Die FSE des iPP ändert sich mit der Zeit nach der Oberflächenbehandlung nur unwesentlich.
    Notes: The applied surface modification methods aim at an increase of the hydrophilicity and the free surface energy (FSE) of isotactic poly(propylene) (iPP).It was shown that for this purpose it is possible to use UV irradiation during 1-2 min, depending on the distance of the source of irradiation from the polymer surface [50, resp. 100 mm]. By the simultaneous effect of phosphorus trichloride (PCl3) and UV irradiation on the polymer surface the FSE was increased by 29% compared to the unmodified polymer and the mechanical work of adhesion was six times the original value. It was found that the application of strong oxidizing agents, such as potassium permanganate (PPM) and ammonium peroxodisulfate (APS), resulted in an increase of the FSE of iPP by 16 to 19%. The efficiency of the modification depends on the time of the modification by aqueous solutions of the oxidizers, as well as on the concentration of the solution. The FSE of iPP modified by UV irradiation does not change with the time after the modification.
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    Angewandte Makromolekulare Chemie 231 (1995), S. 171-186 
    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: Durch Polyaddition von Diphenylmethan-4,4′-diisocyanat oder Dicyclohexylmethan-4,4′-diisocyanat mit 2-Methyl-2-(4-pyridyl)propan-1,3-diol (MPyP) wurden neue reaktive Polyurethane hergestellt, deren Struktureinheiten mit Pyridinringen substituiert sind. Copolyurethane aus diesem Diol wurden in einem Ein- bzw. Zweistufenprozeß in Substanz oder in Diglyme-Lösung hergestellt, wobei als Comonomere Hexan-1,6-diol (HD), α,ω- Dihydroxypoly(oxyethylen)e mit verschiedenen Molekulargewichten (POE 400,1000 und 2000) oder α,ω-Dihydroxypoly(oxypropylen) (PPO 400) eingesetzt wurden. Die erhaltenen Pyridin-substituierten Polyurethane und Copolyurethane wurden durch 1H-NMR- und 13C-NMR-Spektroskopie und durch die Grenzviskosität [λ] charakterisiert. Die Pyridineinheiten wurden acidometrisch (HClO4) bestimmt. Die Reaktivität der OH-Gruppen in MPyP bezüglich der Isocyanat-Gruppe wurde charakterisiert, indem die Geschwindigkeitskonstante der Reaktion von MPyP mit Phenylisocyanat bestimmt wurde. Der erhaltene Wert von 2,45 · 10-3 dm3 mol-1 s-1 (25°C) liegt um eine Größenordnung höher als die Geschwindigkeits-konstante für die Addition von Hexan-1,6-diol. Diese Differenz wurde mit einem katalytischen Mechanismus bei der Addition von MPyP interpretiert.
    Notes: New reactive polyurethanes with structure units substituted with pyridine rings were prepared by the polyaddition reaction of diphenylmethane-4,4′-diisocyanate or dicyclohexylmethane-4,4′-diisocyanate with 2-methyl-2-(4-pyridyl)propane-1,3-diol (MPyP). Copolyurethanes based on this diol were synthesized by a one- or two-step procedure carried out in bulk or diglyme solution using hexane-1,6-diol (HD), α,ω-dihydroxypoly(oxyethylene)s of various molecular weights (POE 400, 1000 and 2000) or α,ω-dihydroxypoly(oxypropylene) (PPO 400) as comonomers.Pyridyl-substituted polyurethanes and copolyurethanes were characterized by their 1H and 13C NMR spectra and limiting viscosity numbers [η]. The pyridine units were determined acidimetrically (HClO4). The reactivity of the OH groups of the pyridine diol towards NCO groups was characterized by determining the rate constants of its reaction with phenyl isocyanate. The obtained value of 2.45 × 10-3 dm3 mol-1 s-1 (25°C) was by an order of magnitude greater than the rate constant for the addition of hexane-1,6-diol. This difference was interpreted in terms of a catalytic mechanism for the addition of MPyP.
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  • 84
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We consider the possibility of stabilising a polymer by using a low-molecular-weight, mobile and soluble antioxidant, trapped in a small volume fraction of encapsulating material so that it is released into the surrounding polymer to compensate for consumption or loss. Two models are discussed. In the “matrix” model, the additive is dissolved in an encapsulant and its release is controlled entirely by the diffusion coefficient in the encapsulant. In the “balloon” model, the pure additive is surrounded by a wall of encapsulant, through which it permeates into the surrounding polymer. Modelling of the two cases allows the required diffusion or permeation coefficients to be calculated for any chosen loss time. It is found that purely diffusion-controlled loss would require improbably low diffusion coefficients, whereas the required permeabilities for balloon models are accessible. It is difficult to imagine a system for which the temperature coefficient of loss rate would be low enough to allow elevated temperature processing without loss of the additive.
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  • 85
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    Angewandte Makromolekulare Chemie 233 (1995), S. 47-58 
    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: Thin, plane plates of a defined thickness were cast from two types of gelcoat resins (isophthalic acid neopentylglycol (UP) and vinylester resin (PHA) based on bisphenol A) as a model for a gelcoat or topcoat layer of a glass fibre-reinforced laminate. The effect of undercuring as well as of resin dilution with styrene on the water vapor permeation through these plates was examined. In both cases the dilution of the resin results in an obvious increase of permeability. Undercuring (curing degrees of about 97%) and subsequent extraction of residual styrene monomer increases the water vapor permeability in the UP, on the other hand a light drop of the permeation coefficient was registered in the case of PHA. The results are discussed in connection with the different kinetics of the curing reactions in both resin types.
    Notes: Als Modell für die Gelcoat- oder Topcoatschicht eines glasfaserverstärkten Laminates wurden dünne, planparallele Platten definierter Dicke aus zwei Gelcoatharztypen (Isophthalsäure-Neopentylglykol- (UP) und Phenacrylat-Harz (PHA) auf Basis von Bisphenol A) gegossen, und es wurde der Einfluß der Unterhärtung sowie der Harzverdünnung mit Styrol auf die Wasserdampfdurchlässigkeit dieser Platten untersucht. Die Harzverdünnung führt in beiden Fällen zu einem evidenten Anstieg der Permeationskoeffizienten P. Die Unterhärtung (Aushärtungsgrade um 97%) und anschließende Extraktion des nicht auspolymerisierten Styrols läßt beim UP die Permeabilität von Wasserdampf ebenfalls ansteigen, beim PHA wurde dagegen ein leichtes Sinken des Permeationskoeffizienten verzeichnet. Die Ergebnisse werden im Zusammenhang mit den Unterschieden in der Kinetik der Aushärtungsreaktion beider Harztypen diskutiert.
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  • 86
    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: Blends aus Polystyrol (PS) und Polyvinylchlorid (PVC) sind aus thermodynamischen Gründen unverträglich und weisen deshalb nur schlechte mechanische Eigenschaften wie mangelnde Schlagzähigkeits- und Reißdehnungswerte auf. Der Grund hierfür liegt in der Natur der Grenzfläche solcher unverträglicher, heterogener Polymer-Blends. Hohe Grenzflächenspannungen und eine geringe Phasenadhäsion führen zu groben Phasenmorphologien, die kinetisch und thermodynamisch instabil sind. Jedoch gelingt es mit maßgeschneiderten Block-Pfropfcopolymeren P(S-b-(B-g-CHMA, MMA)) auf Basis von Styrol/Butadien-Blockcopolymeren P(S-b-B), auf die Polycyclohexylmethacrylat (PCHMA) oder Polymethylmethacrylat (PMMA) radikalisch ge-pfropft wurden, die Phasenmorphologien drastisch zu verfeinern, was zu einem duktilen Verhalten der modifizierten Blends führt. So steigt die Schlagzähigkeit von modifizierten gegenüber nicht modifizierten PS/PVC-Blends um den Faktor 10 und bewegt sich damit im Bereich von zähmodifiziertem PS.Elektronenmikroskopische Untersuchungen (TEM, REM) beweisen, daß die drastisch verbesserten Eigenschaften der modifizierten PS/PVC-Blends auf einer Grenzflächenselektivität der Block-Pfropfcopolymeren und einer ausgezeichneten Phasenanbindung beruhen.
    Notes: Blends composed of polystyrene (PS) and polyvinylchloride (PVC) are incompatible due to unfavourable interactions. Consequently, their mechanical properties such as impact strength and elongation at break are only very poor. The key to successfully influence the properties of such heterogeneous blends lies in the control of the interface. High interface tensions and an insufficient phase adhesion often lead to coarse phase morphologies which are thermodynamically and kinetically unstable. However, with radically synthesized, tailor made block-graft copolymers P(S-b-(B-g-CHMA, MMA)) based on a styrene/butadiene two-block copolymer P(S-b-B) which are grafted with poly(cyclohexylmethacrylate) (PCHMA) or poly(methylmethacrylate) (PMMA), the phase morphology can be markedly refined and the blends surprisingly show ductile behaviour. Thus, the impact strength of so modified PS/PVC 1 : 1 blends is about ten times higher than in the unmodified case and is thereby similar to impact modified PS.Electron microscopy (SEM, TEM) reveals that the modified PS/PVC blends owe their improved mechanical properties to the interface selectivity of the block-graft copolymers and therefore to a superior phase adhesion.
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  • 87
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    Angewandte Makromolekulare Chemie 233 (1995), S. 121-131 
    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: Eine Serie von 16 Polyaminen auf Triazinbasis wurde mittels Grenzflächenpolykondensation synthetisiert. Als Monomere wurden verschiedene Dichlortriazinderivate sowie Diaminverbindungen verwendet. Der Einfluß von Temperatur, Reaktionszeit, Monomerkonzentration, Art des organischen Lösungsmittels sowie Art der Base auf die reduzierte spezifische Viskosität und die Ausbeute an Polyamin wurde untersucht. Löslichkeiten, Glastemperaturen und thermogravimetrische Daten der Produkte wurden bestimmt. Über die dynamisch-mechanische Thermoanalyse von zwei Polyaminen wird berichtet.
    Notes: A series of 16 triazine-based polymines was synthesized by interfacial polycondensation, using various dichlorotriazine derivatives and diamines as monomers. The effect of the reaction parameters temperature, reaction time, concentration of monomers, type of organic solvent and type of base on the reduced specific viscosity and yield of polyamines was investigated. Solubilities, glass transition temperatures and thermogravimetric data were determined. Dynamic-mechanical thermal analyses of two polyamines are reported.
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  • 88
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    Angewandte Makromolekulare Chemie 231 (1995), S. 47-60 
    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: Es wurden sechs oligomere Polyole synthetisiert und charakterisiert. Die Oligomeren waren aus strukturell gleichen Perfluorpolyether-Ketten, aber mit unterschiedlichen Endgruppen aus Hydroxygruppen enthaltenden hydrogenierten Segmenten aufgebaut. Zur Synthese der Polyole wurde der Fluorpolyetherdiol-Precursor (ZDOL) mit Epoxiden oder Dibromalkanen verethert. Die Reaktion mit Epoxiden führte direkt zu den Polyolen, während mit Dibromalkanen zunächst die fluorierten Dibromderivate erhalten wurden, die mit Malonat und durch anschließende Reduktion in die Polyole umagewandelt wurden. Die Viskosität der Oligomeren wurde bestimmt, und der Einfluß von Temperatur, Lösungsmittelkonzentration sowie Gehalt an Hydroxyendgruppen auf die Viskosität wurde ermittelt. Die außergewöhnlich niedrige Glastemperatur und Viskosität sowie die gute Mischbarkeit mit gängigen Lösungsmitteln machen diese Polyole als Harze für hochfeste Beschichtungen interessant.
    Notes: Six oligomeric polyols having a common perfluoropolyether chain end-capped by different hydrogenated segments containing hydroxylic groups were synthesized and their properties described. The general scheme for the synthesis of these polyols involved the etherification of the fluoropolyether diol precursor (ZDOL) with epoxides or dibromoalkanes. The former reaction gave directly the polyolic derivatives, while the latter yielded the fluorinated dibromoderivative which could be converted to polyols through the reaction with malonate and final reduction.The viscosity of these oligomers was measured and its dependence on temperature, solvent concentration and hydroxylic end-groups content was established. The exceptionally low Tg and viscosity together with the good miscibility with common solvents make these polyols very interesting as “resins” suitable for high-solid coatings.
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  • 89
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    Polymer Engineering and Science 35 (1995), S. 1807-1810 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Blends prepared from poly(ethylene 2,6-naphthalate) (PEN) and poly(butylene 2,6-naphthalate) (PBN) show only partial miscibility judged from their glass transition temperatures. Two distinct mechanical behaviors are observed: brittle for the blends 〈 20 wt% of PBN, while ductile 〉 20 wt% of PBN. The experimental modulus and strength values of the blends are within the predicted values according to Kleiner and Paul models, respectively. This means that PEN/PBN blends are somewhat compatible based on their tensile properties. Especially for 20 wt% of PBN blend, the high modulus and strength are observed. The viscosity of the blend is high, which may imply a somewhat entangled morphology in the amorphous state.
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  • 90
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 91
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1821-1833 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The paper consides the effects of compatibilization with maleic anhydride grafted polypropylene (PP-g-MAH) on the propertie of immiscible blends of polypropylene (PP) and nylon 6 (N6). We prepared the blends by three different mixing processes; single-step blending, two-step blending with reactive premixing, and two-step blending with nonreactive premixing, to determine the effective mixiing process for fine morphological structure thermal stability, and mechanical properties. Dynamic melt reheological properties were measured to examine the modification of elastic properties by the compatibilizer. In addtion, thermal analysis was also carried out to detect the change in crystallization and thereby to probe the degree of compatibilizaton. The results show that compatibilized blends prepared by teh single-step process exhibit improved phase morphology, thermal stability, and mechanical properties for dried conditions, compared with other blend types. Finally, the water absorption test indicates that the added compatibilizer yields enhanced water resistance in spite of the strong intrinsic hydrophilicity of N6. In particular, two-step blending with reactive premixing is most effective in improving water resistance and reducing degradation of mechanical properties after moisture absorption.
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  • 92
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    Polymer Engineering and Science 35 (1995), S. 1834-1851 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A hybrid two-/three-dimensional solution technique is presentedto model 3-D flow fields in resin transfer moeling using Darcy's low. The 3-D flow field is only solved for regions where all three velocity components are significant, thus largely reducing the number of unknowns. Elsewhere, the commonly used 2-D approximation for flow in thin gaps between plates is employe.d The method is applied to regions where the flow splits, such as T-joints. Because of the uncertainties associated with an accurate determination of the permeability in these regions, a simplified decompled procedure is procesed, which reduces the computational complexity. In this procedure, the flow front is advanced using the 2-D formulation. The 2-D formulation also provides the boundary conditions for the subsequent computation of the 3-D flow field without feedback of flow field information to the 2-d model. The governing equations are solved using boundary fitted coordinate systems (BFCS) together with the finite difference method (FDM). Numerical as well as algebraic grid generation and domain decomposition are employe dto generate grids that always concide with the continuously deforming and enlarging flow domain. Results that include the trackingof numerical tracer particles to visualize the three-dimensionality of the flow field are presented for isothermal flow of a Newtonian fluid through a T-joint. This detailed flow field description is expected to form the basis for a rather accurate simulation of quantitities that largely depend on the fluid particle pathlines, such as the degree of cure. The method is also extendable to shear-thinning fluids as well as to 3-D flow in the vicinity of the flow front.
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  • 93
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    Polymer Engineering and Science 35 (1995), S. 1872-1877 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The Smoluchowski equation for the breakup and coalescence of dispersed droplets has been solved for flowing polymer blends. A scaling form for the distribution of droplet sized derived and published for a system of clusters with fragmentation and coagualation was used in our dervation. Equations are developed here for the average droplet size and for the characteristic time of transition to steady state flow of blends with a high content of the dispersed phase. Expressions reasonably describing the average size of droplets for all concentrations were obtained by a theory modification. Measured dependences of droplet size on the blend composition can be matched only if simultaneous collisions of three and more droplets are considered. The results of the theory indicate that the mechanism of droplet breakup (formation of pieces with the same or different volumes) has only a small effect on their average size in concentrated systems. The dependence of droplet size on the shear rate in flow is determined by properties of the blend components, and is generally nonmonotonic.
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  • 94
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1878-1883 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Multilayer LDPE/nylon-6 films with an overall content of 71 wt% LDPE, 24 wt% nylon-6, and 5 wt% PE-based tie-layer adhesive were reprocessed under both minimal and extensive mixing conditions. Thermal and mechanical properties, oxygen and water vapor permeability, and morphology of the reprocessed samples were determined. The modulus and yield stress of the reprocessed films fell between those of the pure homopolymers, whereas percent elongation at break and energy-to-break for all reprocessed films were less than those of the homopolymers. In minimally reprocessed film, layering of LDPE (low-density polyethylene) and nylon-6 was retained, whereas in extensively mixed samples, nylon-6 domains were spherical and ranged from 0.2 to 7 μm. Minimally reprocessed film exhibited good O2 and H2O vapor barrier properties, whereas extensively-mixed samples had poor barrier properties. Properties of well-mixed blends prepared both with and without adhesive showed that 5 wt% adhesive did not compatibilize the LDPE and nylon-6 components.
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  • 95
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    Polymer Engineering and Science 35 (1995), S. 1895-1898 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new stress monitoring technique, a stress-tracking device, is described here. It has been used to study some important properties of epoxy resin. Residual stresses, including a curing shrinkage stress and a cooling shrinkage stress, were measured automatically and continuously during curing and cooling. Simultaneously, information such as an apparent gelation time and glass transition temperature were obtained directly during the experiment. These epoxy resin properties were related to the extent of cure. Varying cure temperature produced changes of cure behavior, which resulted in different residual stresses.
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  • 96
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    Polymer Engineering and Science 35 (1995), S. 1899-1906 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Processing of microcellular foam was investigated for the feasibility of production of tough and lightweight polyurethanes. To increase the nucleation rate in a gas-supersaturated resin, ultrasonic excitation was applied to the mixture of polyol(polyether-based polyol) and isocyanate(diphenyl methane diisocyanate). A microcellular structure was produced by two sequential steps, i.e., supersaturationof the polyol resin with nitrogen gas at elevated pressure and ultrasonic bubble nucleation right after the impingement mixing of two components of the polyurethane system. Theoretical analyses based on nucleation theories were employed to predict the rate of nucleation in the gas-supersaturated polyurethane. The rate of nucleatio in the resin was predicted by classical nucleation and cluster theories. In the experimental investigation, ultrasonic excitation was applied to increase the nucleation rate in the resin that had been saturated by nitrogen at a saturation pressure 〈 2.0 MPa.
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  • 97
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    Polymer Engineering and Science 35 (1995), S. 1917-1922 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polypropylene/Polyamide-6 (PP.PA) blends containing maleic anhydride grafted elastomers were prepared by reactive blending. Three different types of core shell morphologies were obtained and characterized by transmission electron microscopy (TEM). The midulus of these elastomer midified PP/PA (70/30) blends with core shell type morphology is compared to predictions derived from the Kerner model. The multiphase morphology of these blends could be modeled by sequential application of the Kerner equation to two-phase subinclusions. Using morphological data ontained by TEM, good agreement between experimental and calculated values was ontained. The results are used to tailor PP/Pa-6 blends combining stiffness and toughness.
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  • 98
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    Polymer Engineering and Science 35 (1995), S. 1931-1937 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: One of the major factors limiting the use of thermoplastics in engineeing applications is the inadequacy of existing design data. Much of the data do not span appropriate ranges of stress, strain, time, or temperature. This study addresses the need to develop an accelerated method for generating long-time design data to support the innovative use of engineering thermoplastics. In particular, stress relaxation tests (SRT) were performed on polycarbonate (PC) and midified poly(phenylene oxide)(PPO), and used to generate time-dependent design data through the short-time measurement of the material's current state without dependence on elastic modulus. The test results and analyses reported here indicate the SRT method to be an efficeint means of generating accurate and repeatable creep and secant modulus data which may be directly used in design. Therefore, SRT shows great potential both as a design parameter development tool, and as a quality control instrumetn for assessing batch-to-batch variability.
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  • 99
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    Biotechnology and Bioengineering 48 (1995), S. 631-638 
    ISSN: 0006-3592
    Keywords: Saccharomyces cerevisiae ; fermentation ; on-line simulation ; state estimation ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In order to study and control fermentation processes, indirect on-tine measurements and mathematical models can be used. In this article we present a mathematical on-line model for fermentation processes. The model is based on atom and partial mass balances as well as on equations describing the acid-base system. The model is brought into an adaptive form by including transport equations for mass transfer and unstructured expressions for the fermentation kinetics. The state of the process, i.e., the concentrations of biomass, substrate, and products, can be estimated on-line using the balance part of the model completed with measurement equations for the input and output flows of the process. Adaptivity is realized by means of on-line estimation of parameters in the transport and kinetic expressions using recursive regression analysis. These expressions can thus be used in the model as valid equations enabling prediction of the process. This makes model-based automation of the process and testing of the validity of the measurement variables possible. The model and the on-line principles are applied to a 3.5-L laboratory tormentor in which Saccharomyces cerevisiae is cultivated. The experimental results show that the model-based estimation of the state and the predictions of the process correlate closely with high-performance liquid chromatography (HPLC) analyses. © 1995 John Wiley & Sons, Inc.
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  • 100
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    Biotechnology and Bioengineering 48 (1995), S. 659-666 
    ISSN: 0006-3592
    Keywords: methanogenic activity ; ethylene ; dechlorination ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Kinetics were determined for methanogenic activity and chlorinated ethylene dehalogenation by a methanol-enriched, anaerobic sediment consortium. The culture reductively dechlorinated perchloroethylene (PCE) to trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinylchloride (VC), and ethylene and ethane. The absence : of methanol or the addition of 2-bromoethanesulfonic. acid in the presence of methanol suppressed both methanogenic activity and dechlorination. In contrast, acetate production continued in the presence of 2-bromoethanesulfonic acid. These results suggest that dechlorination was strongly linked to methane formation and not to acetate production. A kinetic model, developed to describe both methanogenesis and dechlorination, successfully predicted experimentally measured concentrations of biomass, methane, substrate, and chlorinated ethylenes. The average maximum specific dehalogenation rates for PCE, TCE, 1,1-DCE, and VC were 0.9 ± 0.6, 0.4 ± 0.1, 12 ± 0.1, and 2.5 ± 1.7 μmol contaminant/ g. DW/day, respectively. This pattern for dechlorination rates is distinctly different than that reported for transition metal cofactors, where rates drop by approximately one order of magnitude as each successive chlorine is removed. The experimental results and kinetic analysis suggest that it will be impractical to targeting methanol consuming methanogenic organisms for in situ ground-water restoration. © 1995 John Wiley & Sons, Inc.
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