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  • 1990-1994  (10,382)
  • 1920-1924
  • 1905-1909
  • 1992  (10,382)
  • Chemistry  (10,382)
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  • 1990-1994  (10,382)
  • 1920-1924
  • 1905-1909
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 139-150 
    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 makroporöser Glycidylmethacrylat-Ethylendimethacrylat-Copolymerer (GMA-co-EDMA) wurde durch Suspensionspolymerisation hergestellt; dabei wurden nach einer statistisch geplanten experimentellen Durchführung die Ethylendimethacrylatkonzentration und die Heizrate der Polymerisationstemperatur von 20 auf 70°C variiert. Die Porositätseigenschaften der hydrolysierten Copolymeren wurden mit Hilfe der Größenausschlußchromatographie unter Verwendung von Polystyrolstandards in Tetrahydrofuran charakterisiert. Das Porenvolumen, die spezifische Oberfläche und die Porengröße werden dabei durch die Konzentration des Vernetzungsmittels stärker beEinflußt als durch die Heizrate während der Polymerisation.
    Notes: A series of macroporous glycidyl methacrylate-ethylene dimethacrylate copolymers have been prepared by the suspension polymerization according to a statistical design of experimental approach in which concentration of ethylene dimethacrylate and time needed for raising the polymerization temperature from 20 to 70°C have been varied. The porous properties of hydrolyzed copolymers have been characterized by means of size exclusion chromatography using polystyrene standards in tetrahydrofuran. Pore volume, specific surface area, and pore size are affected by the crosslinking agent concentration rather than by the rate of temperature increase during the polymerization reaction.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 171-190 
    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: Copolymers of AN were prepared with variable molecular masses and with variable contents of methylacrylate (ASME) and sodiumallylsulfonate (NaAS), acrylamide (AA), itaconic acid (IS), polyethyleneglycol acrylate (600) (PEGA), vinylacetate (VA), 2-hydroxyethyl acrylate, (HEE) or sodium acrylamido-2-methylpropanesulfonate (NaAMPS), respectively, by using a mathematical model for the calculation of the polymerization conditions needed. Precipitation studies by light scattering showed the predominant influence of NaAS and NaAMPS on the precipitation properties. Acrylonitrile homopolymers show a hard precipitation behaviour. The originating particles have a density of between 0.2 and 0.4 g/cm3. An increasing content of NaAS or NaAMPS leads for example beginning from 0.8 wt.-% NaAS in the monomer composition to a soft precipitation behaviour and to highly swollen particles possessing a density of less than 1 · 10-2 g/cm3. The molar mass and the ASME-content show no significant influence. For the acrylonitrile/acrylamide system already 0.5 wt.-% allylsulfonate is sufficient to get a soft precipitation behaviour with formation of highly swollen particles. All samples with the other cocomponents and without NaAS- or NaAMPS-comonomer show a hard precipitation behaviour with little swollen particles.
    Notes: Copolymere des Acrylnitrils (AN) mit variabler Molmasse bzw. mit variablem Anteil von Acrylsäuremethylester (ASME) und Natriumallylsulfonat (NaAS), Acrylamid (AA), Itaconsäure (IS), Polyethylenglykolacrylat (600) (PEGA), Vinylacetat (VA), Acrylsäure-2-hydroxyethylester (HEE) oder Natrium-2-acrylamido-2-methylpropansulfonat (NaAMPS) wurden hergestellt, wobei die erforderlichen Polymerisations-bedingungen mit Hilfe eines mathematischen Polymerisationsmodells ermittelt wurden.Die Fällungsuntersuchungen mit der Methode der Lichtstreuung zeigten, daß NaAS und NaAMPS einen dominierenden Einfluß haben. Bei Acrylnitril-Homopolymeren tritt eine harte Fällung auf, und die entstehenden Partikel haben eine Dichte zwischen 0,2 und 0,4 g/cm3. Zunehmender NaAS-bzw. NaAMPS-Gehalt führt ab einem Gehalt von beispielsweise ca. 0,8 Gew.-% NaAS im Monomergemisch zu einer weichen Fällung, bei der hochgequollene Partikel mit einer Dichte in der Größenordnung von 〈 1.10-2 g/cm3 entstehen. Ein Einfluß der Molmassen und des ASME-Gehaltes Konnte nicht nachgewiesen werden. Beim Acrylnitril/Acrylamid-System genügen offensichtlich 0,5 Gew.-% Allylsulfonat im Monomeransatz, um eine stabile, weiche Fällung unter Bildung hochgequollener Strukturen zu gewährleisten. Alle Proben mit den übrigen hydrophilen Cokomponenten zeigen ohne NaAS bzw. NaAMPS-Comonomer ein hartes Fäungsverhalten mit wenig gequollenen Partikeln.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 213-213 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 191-204 
    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: Die Photovernetzung von Poly(p-hydroxystyrol) (PPHS) wird durch O2 beachtlich beschleunigt. Dies ergab sich aus der Bestimmung der Molmasse (mit Hilfe der Lichtstreumethode) und des Gelanteils nach kontinuierlicher Bestrahlung bei λinc = 254 nm. Aufgrund von Ergebnissen aus Blitzphotolyseversuchen wird der folgende Reaktionsmechanismus aufgestellt: Die Vernetzung sowohl in An-als auch Abwesenheit von O2 kommt im wesentlichen durch Kombination von Radikalen des Phenoxyltyps zustande. In Abwesenheit von O2 werden Phenoxylradikale ausschließlich durch Spaltung von O—H-Bindungen phenolischer Gruppen, die sich im angeregten Singulettzustand befinden, erzeugt. Triplett-angeregte phenolische Gruppen, die sich auch bilden, desaktivieren nicht durch Spaltung der O—H-Bindungen. Sie reagieren allerdings sehr effektiv, sofern vorhanden, mit O2. Bei dieser Reaktion entstehen HO·2- und zusätzliche Phenoxylradikale. Alle handelsüblichen und die meisten im Labor synthetisierten PPHS-Proben enthalten chemisch gebundene, chinoidartige Verunreinigungen. Durch Versuche mit niedermolekularen Modellverbindungen wurde nachgewiesen, daß triplett-angeregte chinoide Gruppen einerseits mit phenolischen Gruppen unter Bildung von Phenoxylradikalen reagieren und daß sie andererseits unreaktiv sind bezüglich der Abstraktion aliphatischer Wasserstoffatome. Die Bestrahlung von PPHS bei λinc = 254 nm bewirkt die Bildung chinoider Gruppen, die bei dieser Wellenlänge auch stark absorbieren. Die Lichtabsorption dieser Gruppen wird im Laufe der weiteren Bestrahlung zum bestimmenden Faktor hinsichtlich der photochemischen Veränderung des Polymeren.
    Notes: Light-induced crosslinking of poly(p-hydroxystyrene) (PPHS) is significantly enhanced by O2. This was evidenced by molar mass (light scattering measurements) and by gel content determinations which were performed on various polymer samples before and after continuous irradiation at λinc = 254 nm. The following mechanism was elucidated with the aid of flash photolysis studies: Crosslinking in the absence or presence of O2 is mainly due to the combination of phenoxyl type radicals. In the absence of O2 the latter are exclusively formed by O—H bond cleavage of singlet excited phenolic groups. Triplet excited phenolic groups which are also formed do not deactivate via O—H bond cleavage but react very effectively with O2. This reaction leads to the formation of HO2· and additional phenoxyl type radicals. All Commercial and most laboratory-prepared PPHS samples contain chemically bound impurities of quinoid nature. On the basis of results performed with model compounds of low molar mass, it is concluded that triplet excited quinoid groups react effectively with phenolic groups forming phenoxyl type radicals and that they are quite unreactive with respect to the abstraction of alphatic hydrogen atoms. Irradiation of PPHS at λinc = 254 nm causes the formation of quinoid groups which absorb strongly at this wavelength. Light absorption by these groups becomes a determining factor with respect to photochemical alteration in the course of further irradiation.
    Additional Material: 9 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), 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: Die verschiedenartigen Eigenschaften von Polymerlegierungen aus Polyoxymethylen (POM) und bis zu 20 Gew.-% chemische oberf;ächenbehandeltem Poly(tetrafluorethylen) (CPTFE) wurden untersucht und denen unbahandelter POM/PTFE- Blends gegenübergestellt. PTFE iwrd POM zugesetzt, um dessen Oberflächenabriebseigenschaften Anteil zunehmend verschlechtert. Durch die bessere Phasenanbindung in den oberflächenbehandelten POM/CPTFE- Blends konnten die doppelten Zugfestigkeiten und EModuli wie bei unbehandelten POM/PTEF- Blends erreicht werden. Mit Hilfe der Elektronenmikroskopie (SEM) konnte gezeigt werden, daß die PTEF-Agglomerate in der POM-Matrix eine Größe von 30 bis 100 μm haben, während die CPTFE-Teilchengrößbe unter 1 μum liegt.
    Notes: The various properties of the blends of polyacetal (POM) with up to 20 wt.-% chemically surface-treated poly(tetrafluoroethylene) (CPTFE) were investigated and compared with those of POM/PTFE blends. The PTFE is added to POM to improve the wear properties, however, the mechanical properties of POM/PTFE blends decrease with increasing PTFE content, but tensile strength and Young's modulus of POM/CPTFE blends are more than 2 times higher than that of the POM/PTFE blends. SEM shows that the size of inherent agglomerative PTFE is in the range of 30 to 100 μm. The particle size of major CPTFE dispersed in POM is smaller than 1 μm.
    Additional Material: 12 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 49-61 
    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: Hydrogele wurden aus methylmethacrylat (MMA) and N-Vinyl-2-pyrrolidon (NVP) mit 1,2,2-Trimethylolpropantrimethacrylat (TPTA) als Vernetzungsmittel hergestellt. Die Terplymerisation wurden mittels UV-strahlung (365 nm) initiiert, wobei kleine Mengen an Diethoxycetophenon (DEAP) als Photosensibilisator sowie Triethanolamin(TEA)als Beschleuniger und Verdünner verwendet wurden. Die Hydrogele wurden durch Messung des Wasserrückhaltevermögens, der Sauerstodiffusions- und permitionskoeffizienten, der mechanischen Eigenschaften und der Lichtdurchlässigkeit charakterisiert. Dabei zeigte sich, daß die Hydrogele bis zu 80 Gew.-% Wasser aufnehmen können, wobei mit steigendem Wassergtehalt deren mechanische Festigkeit drastisch sinkt. Der Ssuerstoffdiffusionskoeffizient der gequollenen Hydrogele beträgt 10-6 cm2s-1, der Sauerstoffpermeationskoeffizient 1013 cm2s-1Pa-1, und die Lichtdurchlässigkeit liegt im Bereich von 500 bis 700 nm bei über 90%.
    Notes: Hydrogels are synthesized from methyl methacrylate (MMA) and N-vinyl-2-pyrrolidone (NVP) with 1,1,1-trimethylol propane trimethacrylate (TPTA) as a crosslinking agent. It was polymerized under UV radiation (365nm) with a small amount of photosensitizer, diethoxy acetophenone (DEAP), acclerator and diluent, triethanol amine (TEA). The hydrogels were characterized by measuring the water retention, dissolved oxygen diffusivity and permeability, mechanical strength, and light transparency. The hydrogels can retain water up to 80 wt.-% and the mechanical strenght is weakened as the water content is increased in the gel. The dissolved oxygen diffusivity and permeability in the swelling hydrogels are determined to be 10-6 cm2/sec and 1013 cm2s-1 Pa-1, respectively. The light transparency is over 90% in the wave lenght ranging from 500 to 700 nm.
    Additional Material: 5 Ill.
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  • 7
    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: Ein Bisphenol-A-Epoxidharz wurde zunächst mit Toluylendiisocyanat, dessen eine Isocyanatgruppe mit 2-Ethylhexanol blockiert war, und dann mit unterschiedlichen Mischungen on Diethanolamin und Bis(2-methyl-isobutylketiminoethyl)amin (DKI)umgesetzt. Aus diesen Harzen mit Triethanolamin- und DKI-Endgruppen wurden durch Hydrolyse und Neutralisieren mit Essigsäure kationische Harze mit primären Amin-Endgruppen erhalten, aus denen mit geeigneten Lösungsmitteln und deionisiertem Wasser Emulsionen hergestellt wurden. Deren Eigenschaften und die Elektroabscheidung der Harze aus den Emulsionen wurden untrsucht. Der Effekt der Zugabe von hydrophoben Lösungsmitteln wie Toluol oder Hexylcellosolv (HCS) auf die Abscheidungseigenschaften wird diskutiert.
    Notes: A diglycidylether of bisphenol A epoxy resin (DGEBA) was first reacted with 2,4-toluene diisocyanate partially blocked with 2-ethylhexanol (2-EH P. B. TDI) to form modified epoxy resins, and subsequently reacted with different molar ratios of diethanolamine and bis(2-methylisobutylketiminoethyl)amine (DKI) (used as ring opening agents) to give diethanolamine/diketimine terminated resins. These resins were hydrolyzed and neutralized with acetic acid to give cationic resins containing various contents of primary amine groups in the terminal polymeric chain. These cationic resins can be dissolved in a suitable solvent and mixed with deionized water to obtain emulsions. The electrodeposition properties and characteristics of the resulting cationic resins were investigated in detail. The effects of hydrophobic solvents, such as hexyl cellosolve (HCS) and toluene, on the deposition properties of the emulsions are discussed.
    Additional Material: 11 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 107-111 
    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 radikalische Polymerisation von Acrylnitril in Gegonwart verschiedener ungesättigter optischer Aufheller (FB) (Derivate des 1,3,5-Triazins) wurde untersucht. Kolorimetrische Messungen ergaben, daß mehr als 80% des optischen Aufhellers in die Polymerkette eingebaut werden. Zur Erzielung eines intensiven optischen Effektes genügt eine FB-Anfangskonzentration von 0,1 Gew.-%, bezogen auf Acrylnitril.
    Notes: The polymerization of acrylonitrile in the presence of some unsaturated, triazinebased fluorescent brighteners (FB) has been investigated. It was found colourimetrically that more than 80% of the FB is incorporated in the polymer. The initial concentration of 0.1 wt.-% is sufficient to obtain a good bleaching effect without significant decrease of the molecular weight.
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  • 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: Les polyesters thermoplastiques (PBT et PET) sont des polymères fragiles avec une résistance au choc entaillée faible. Leur renforcement peut être obtenu par extrusion réactive avec dirrérents types de copolymères élastomères de l'éthylène, contenant des fonctons à réactivité potentielle avec extrémités de chaîne acide et hydroxyle des polyesters.Deux types de copolymères ont été étudiés: Ethylène(acrylate d'éthyle/méthacrylate de glycidyle (E/EA/GMA), et éthylène/acrylate d'éthyle/anhydride maléique (E/EA/MAH). Les alliages ont été obtenu par malaxage de 10 à 25% de coppolymères avec du PBT.Le PBT présente une transition fragile, ductile lorsqu'on passe de 10 à 20% de particules dispersées de copolymère au GMA. Les gains les plus importants en résistance au choc sont obtenus en réticulant partiellement la phase dispersée, par association de copolymères en GMA et de copolymères avec MAH et catalyseur de réaction.
    Notes: Poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) are brittle polymers with poor notched impact strength. Their toughening can be achieved by melt blending with different types of rubbery ethylene copolymers containing functions having potential reactivity with the hydroxy and carboxy end groups in polyesters.Two types of ethylene copolymers were investigated: ethylene/ethyle acrylate/glycidyl methacrylate (E/EA/GMA) and ethylene/ethyl acrylate/maleic anhydride (E/EA/MAH) copolymers. The blends were obtained by reactive extrusion of PBT with 10 to 25% of copolymers.PBT blends undergo a brittle to ductile transition by toughening with GMA copolymer between 10 and 20% of rubbery phase. The most effective toughening could be achieved by a partial crosslinking of the rubbery particles obtained by associating GMA and MAH copolymers and a reaction catalyst.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 101-106 
    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 Orientierung (Neigungswinkel ϕ) von thermotropen Flüssigkristallen (LC) an der Grenzfläche zu polymerbeschichteten Substraten wird nicht nur durch den numerischen Wert der Oberflächenspannung \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$\end{document} bestimmt. Das Verhältnis zwischenden dispersiven und polaren Anteilen an \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$\end{document} beeinflußt ebenfalls die Orientierung der LC-Moleküle an der Substratoberfläche. Als Polymere wurden ein Polyimid und ein Midgruppenhaltiges Styrol/Maleinsäureanhydrid-Copolymeres verwendet.
    Notes: The orientation (tilt angle ϕ) of thermotropic liquid crystals (LC) on the interface to a polymer-coated surface is not only determined by the numerical value \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$\end{document} of the substrate surface tension. However, the ratio between the dispersive and the polar part of \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm\gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$\end{document} also influences the LC orientation on the substrate surface. A polyimide and an amide-modified styrene/maleic anhydride copolymer were used as polymers.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 129-137 
    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: Epoxidharze aus Bisphenol A wurden mit neuen Diphenolen, die Imidgruppen enthalten, modifiziert, um die thermischen Eigenschaften zu verbessern. Die verwendeten Diimiddiphenole wurden aus Dianhydriden und Aminophenolen durch Kondensation hergestellt. Die Diimiddiphenole und die modifizierten Harze wurden durch IR- und NMR-spektroskopische Messungen charakterisiert. Das thermische Verhalten wurde anhand von DSC- und TGA-Messungen untersucht.
    Notes: Epoxy resins derived from Bisphenol A have been modified with new diphenols containing imide moieties in order to improve their thermal properties. The diphenols have been synthesized from dianhydrides and aminophenols by condensation reactions. Diphenols as well as modified resins have been characterized by IR and NMR spectroscopy. The thermal characteristics were evaluated by DSC and TGA.
    Additional Material: 3 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 165-170 
    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 structural transformation of a molecular complex (MC) of polyoxyethylene and urea on cooling from the molten state has been investigated by DSC and X-ray analysis. A high-temperature polymorphic from of the MC was found to be formed, which transforms into the known crystal form of the MC with a hexagonal crystal modification on cooling.
    Notes: Die Strukturveränderungen eines Molekülkomplexes (MK) aus Polyoxyethylen und Harnstoff beim Abkühlen aus dem geschmolzenen Zustand werden kalorimetrisch und röntgenographisch untersucht. Es wird festgestellt, daß eine polymorphe Hochtemperaturform des MK entsteht, die beim Abkühlen in die bekannte Kristallform des MK mit hexagonaler Kristallmodifikation übergeht.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 143-154 
    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: Das Anfangsstadium der Oxidation von Lactamen wurden im Temperaturbereich 70-120°C Cuntersucht. Es wurde festgestellt, daß Pyrrolidon und Piperidon bedeutend schneller oxidiert werden als die sieben-, acht- und dreizehngliedrigen Lactame sowie lineare N-Alkylamide. Die hohe Oxidierbarkeit der fünf- und sechsgliedrigen Lactame kann der leichteren homolytischen Spaltung der N- vicinalen C—H Bindung und der unterschiedlichen Reaktivität der Lactamradikale im Wachstuschritt der Kettenoxidation zugeschrieben werden.
    Notes: The initial stage of oxidation of lactams was studied in the temperature range 70-120°C. It was found that pyrrolidone and piperidone are oxidized essentially more easily than the seven-, eight-, nine- and thirteen-membered lactams as well as linear N-alkylamides. The high oxidizability of the five- and six-membered lactams may be attributed to the easier homolytic splitting of the N-vicinal C—H bond and to the different reactivity of lactam radicals in the propagation step of the chain oxidation.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 127-141 
    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: The relative chain transfer constant for sodium allylsulfonate (NaAS) in the copolymer system acrylonitrile (AN)/methylacrylate (MA) in dimethylformamide (DMF) was determined to be Cx = 0,04 ± 0.01, independent of the initiator used (azoisobutyronitrile, ammoniumperoxodisulfate).The chain transfer reaction explains the influence of NaAS on the polymerization degree, but not the concentration dependence of the copolymerization reactivity ratio r1 · r1 depends on the transfer reaction only in a range of 1 - 5%.The extended Debye-Hückel theory for dilute electrolytes has been successfully tested for a quantitative dependence of r1 from NaAS concentration. The resultant r10-value for infinite dilution of NaAS obviously depends on the acrylonitrile concentration, but only to a small extent (e.g. r10 = 0.32 for [AN] =- 4.26 mol/l). This theory provides comfortable access to resolve the nonideal AN/NaAS copolymerization. This approach may be generally applicable to copolymerizations of monomers with dissociated groups.
    Notes: Im Copolymerisationssystem Acrylnitril (AN)/Methylacrylat(MA) mit Natriumallylsulfonat (NaAS) in Dimethylformamid wurde die relative Übertragunskonstante zum NaAS Cx = 0,04 ± 0,01 unabhängig vom verwendeten Initiator (Azoisobuttyronitril, Ammoniumperoxodisulfat) ermittelt. Die Übertragunsreaktion beschreibt den Einfluß des NaAS auf den Polymerisationsgrad, sie beeinflußt jedoch den Copolymerisationsparameter r1 nur in der Größenordung von 1 bis 5% und kann damit die Konzentrationsabhängigkeit von r1 nicht erklären.Mit Hilfe der erweiterten Debye-Hückel-Theorie für verdünnte Elektrolyte wird die Abhängigkiet des r1-Wertes von der NaAS- Konzentration beschrieben. Der sich daraus für unendliche Verünnung des NaAS ergebende r10-Wert ist offensichtlich noch gerinfügig von der Acrylnitrilkonzentration abhägig. Er liegt beispielsweise für [AN] = 4, 26 mol/1 bei r10 = 0, 32. Damit wurde zum ersten Mal das nichtideale Copolymerisationsverhalten im untersuchten System erkärl. Das Vorgehen sollte verallemeinerungsfähig sein und generell auf das Copolymerisationsverhalten von Monomeren mitdissoziierten Gruppen angewendet werden können.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 196 (1992), S. 169-177 
    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: Katalase wurde durch photoinduzeirte Propfpolymerisation auf mikroporöse polymere Trägermembranen immobilisiert. Die katalytische Aktivität für Zersetzung von Wasserstoffperoxid unter Ultrafitrationsbedingungen wurde mittels eines Rezirkulationsapparates untersucht. Die Membranen zeigten ein sehr gutes katalytisches Verhalten; die Enzymreaktion fand ausschließlich in der Membranstruktur statt. Anfangsreaktionsgeschwindigkeiten, gemessen in einem Temperaturbereich von 5-35°C als Funkation der Substratkonzentration und der Menge des immobilisierten Enzyms pro Einheit Membranoberfäche zeigten, daß sich der Reaktionsmechanismus der Katalase durch die Immobilisierung nicht verädert.
    Notes: Catalase has been immobilized in membranes prepared by photoinduced grafting onto microporous polymeric supports and its catalytic activity on hydrogen peroxide decomposition has been studied under ultrafiltration conditions by means of a recirculation apparatus. The membranes showed a very good catalytic performance and the enzyme reaction took place exclusively within the membrane structure. Initial reaction rates measured in the temperature range 5 - 35°C as a function of both substrate concentration and enzyme amount immobilized per unit membrane surface indicate that the mechanism of action of catalase is not altered after immobilization.
    Additional Material: 2 Ill.
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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: The network formation process of bisphenol A-diglycidylether and 4,4′-diaminodiphenylmethane was investigated by measuring the torque, the conductivity and the soluble part of the crosslinking system. The activation energy for the curing process was estimated from gel time. The volume shrinkage during network formation was measured. The influence of N,N-dimethylbenzylamine as accelerator was discussed.
    Notes: Der Aufbau von Netwerken aus Bisphenol A-Diglycidylether und 4,4′-Diaminodiphenylmethan wurde durch Messung des Drehmomentes, der Leitfähigkeit und durch Bestimmung der löslichen Anteile des vernetzenden System untersucht. Aus den Gelzeiten wurden die Aktivierungsenergie für den Vernetzungsprozeß bestimmt. Außerdem wurde die während der Vernetzung aufretende Volumenschwindung gemessen. Der Einfluß von N, N-Dimethylbenzylamin als Beschleuniger auf den Vernetzungsprozeß wird diskutiert.
    Additional Material: 6 Ill.
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  • 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: The UV-laser induced surface modification of various types of high-performance fibers is investigated. Due to the high UV-absorption coefficients, the well-known effect of UV-laser induced etching (ablation) is observed with all fiber types. Furthermore, the relaxation of orientated macromolecules leads to a characteristic structuring of the fiber surface. For a possible controlled use of this physical surface modification, exact conditions for the treatment in view of textile applications are determined. Useful constants like threshold of ablation, etching rate and structuring constants are measured for all fiber types.
    Notes: Die Oberflächenbehandlung von unterschiedlichen Hochleistungsfasertypen mit gepulstem UV- Laserlicht wird untersucht. Bedingt durch die hohen UV-Absorptionskoeffizienten dieser Materialien wird der bekannte Effekt des UV-laserinduzierten Abtrags (Ablation) bei allen Fasern beobachtet. Zusätzlich werden durch die Relaxation der orientierten Makromoleküle charakteristische Strukturierungen auf der Faseroberfläche ausgebildet. Für einen möglichen kontrollierten und gezielten Einsatz dieser physikalischen Oberflächenmodifizierung in textilen Anwendungen werden die gnaunen Bedingungen der Laserbestrahlung ermittelt und beschieben. Darüber hinaus werden geeignete Konstanten der Laserbearbeitung wie Ablationsschwellenenergie, Ätzraten und Strukturierungskonstanten für verschiedene Fasertypen bestimmt.
    Additional Material: 8 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 165-178 
    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: Die Polymerisation von Dimethyl-diallyl-ammoniumchlorid in konzentrierter wäßriger Lösung mit Persulfat als Initiator kann bis zu hohen Umsätzen mit einem Modell beschrieben werden, in dem folgende Teilreaktionen berücksichtigt werden: a)Primärradikalbildung durch aktivierten Initiatorzerfall sowie Redoxreaktion von S2O2-8 und Cl-b)Kettenwachstum über Monomerkationassoziate undc)Kettenabbruch durch Kombination von cyclisierten Polymerradikalen untereinan der und mit Chloratomen.Für die Polymerisationsgeschwindigkeit wird ein Zeitgesetz hergeleitet, für dessen Konstanten und Parameter numerische Werte ermittelt wurden.
    Notes: The polymerization of dimethyl diallyl ammonium chloride in concentrated aqueous solution with persulfate as an initiator can be described up to high conversion by a kinetic model including a)formation of primary radicals by activated initiator decomposition as well as by redox reaction of S2O82- and Cl-,b)chain propagation via monomer cation associates andc)termination by combination of cyclized polymer radicals between each other or with chlorine atoms.A kinetic expression for the rate of polymerization is presented; rate constants and model parameters have been determined.
    Additional Material: 5 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 199-199 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 179-190 
    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: Polymere mit über eine C—C-Verknüpfung an hochvernetztem Polystyrol kovalent gebundenen, makrocyclischen Amiden wurden durch die Reaktion polymergebundener Malonsäureester-Gruppen mit offenkettigen Diaminen dargestellt. Die Reaktion von vernetztem, chlormethyliertem Polystyrol mit makrocyclischen und offenkettigen Aminen führt zu Polymeren mit kovalenter Bindung über eine C—N-Verknüpfung. Die erhaltenen funktionalisierten Polymeren wurden hinsichtlich der Adsorption von Cu(II)-, Ni(II)- und Co(II)-Ionen aus wäßriger Lösung untersucht.
    Notes: Polymers containing moieties of amides covalently bound to highly crosslinked polystyrene by C—C connections were prepared via a polymer-bound malonic ester group in the reaction with open-chain diamines. The reaction of crosslinked, chloromethylated polystyrene with macrocyclic and open-chain amines results in covalent binding by C—N-connection. The synthesized functionalized polymers were investigated for uptake of Cu(II), Ni(II) and Co(II) ions from aqueous solutions.
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  • 21
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 1-6 
    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: Poly(phenylphosphindiylterephthaloyl), ein neues phosphorhaltiges Polymeres, wurde durch Lösungspolykondensation von Dilithium(phenyl)phosphin mit Terephthaloylchlorid bei niedriger Temperatur hergestellt. Es ist in polaren aprotischen Lösungsmitteln löslich; die inhärente Viskosität in DMF bei 30°C beträgt 19 ml/g. Das Polymere wurde mittels Elementaranalyse sowie IR- und 1H-NMR-Spektroskopie charakterisiert. TGA-Messungen ergeben, daß das Polymere in Luft bis 250°C stabil ist; es ist selbstverlöschend.
    Notes: Poly(phenylphosphinediylterephthaloyl), a novel phosphorus-containing polymer, was synthesized by low-temperature solution polycondensation of dilithio(phenyl)-phosphine with terephthaloyl chloride. The resulting polymer is soluble in polar aprotic solvents, having inherent viscosity of 19 ml/g in DMF at 30°C. The polymer was characterized by elemental analysis, IR and 1H-NMR spectroscopy. TGA data show that the polymer is stable up to 250°C in air. The polymer was found to be self-extinguishing.
    Additional Material: 3 Ill.
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  • 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: Es wird eine neue Methode für die Erweiterung des Meßbereiches der Ausschlußchromatographie, gekoppelt mit Lichtstreuung (SEC/LALLS), zu höherer molarer Masse, vorgestellt. Diese Methode nützt den Effekt, daß das Lichtstreusignal oft schon bei wesentlich kleineren Werten des Elutionsvolumens, also hoheren Werten der molaren Masse erfaßbar ist als das Konzentrationssignal und berücksichtigt dabei die Peakverbreiterung in der SEC. Das betreffende Rechenverfahren wird für den Fall einer logarithmischen Normalverteiung und einer wahrscheinlichsten Verteilung getestet. Im Falle von Polypropylen mit logarithmischer Normalverteilung (M̄W = 420 000 und M̄n = 99 000) kann der durch SEC/LALLS erfaßte Bereich der molaren Masse um einen Faktor von ca. 10 erweitert werden; bei einer wahrscheinlichsten Verteilung (M̄n = 100 000) liegt die erreichbare Erweiterung des Meßbereiches der molaren Masse beieinem Faktor von ca. 2.
    Notes: A new method for the extension of the measuring range of size exclusion chromatography coupled with light scattering (SEC/LALLS) to higher molar mass is presented. This method uses the fact that the light scattering signal can often be detected already at considerable smaller values of the elution volume (i. e. higher values of molar mass) than the concentration signal; furthermore, it takes into account the peak broadening effect in SEC. This procedure is tested for the case of a logarithmic normal distribution and a most probable distribution of molar mass. In the case of polypropylene with a logarithmic normal distribution (M̄w = 420 000, M̄n = 99 000), the range of molar mass covered by SEC/LALLS can be extended by a factor of about 10; with a most probable distribution (M̄n = 100 000), the attainable extension in molar mass assumes a factor of about 2.
    Additional Material: 2 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 45-63 
    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 the interest in their possible application as biologically degradable polymers, the isotherms of sorption of water vapour by native and thermoplastic starch were measured. The thermomechanical treatment of starch and the insertion of glycerol as softener lead to the disappearance of the hysteresis and to the transition from a Type II to Type III isotherm. A theory, describing the sorption behaviour of swellable sorbents, is introduced and its statements are discussed by means of experimental results. The theory allows to draw conclusions on the molecular behaviour during sorption.
    Notes: Es wurden Wasserdampf-Sorptionsisothermen von nativer und thermoplastischer Stärke gemessen. Die thermisch-mechanische Behandlung der Stärke und das Einfähren von Glyzerin als Weichmacher fährt zum Verschwinden der Hysterese und zum Übergang von der Typ II in eine Typ III Isotherme. Eine Theorie, welche das Sorptionsverhalten von quellbaren Sorbentien gut beschreibt, wird kurz eingeführt und anhand der experimentellen Daten ihre Aussagen diskutiert. Die vorgestellte Theorie erlaubt wegen der physikalischen Bedeutung der Parameter Rückschlüsse auf die molekularen Vorgänge während der Sorption. Die Motivation zur Untersuchung des Sorptionsverhaltens von thermoplastischer Stärke ist deren möglicher Einsatz als biologisch abbaubarer Kunststoff.
    Additional Material: 7 Ill.
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  • 24
    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 order to solve the problem of polymer swelling which limits the resolution of negative resists, we have developed new resists where the swelling does not appear. For our study, we developed resists including polymers containing the tetrathiafulvalenylcarbonyloxymethyl radical and dibromotetrachloroethane. In order to study the influence of the nature of the radical bearing the tetrathiafulvalene unit in the polymers on the microlithographic properties of these resists, we also studied polymers containing the tetrathiafulvalenylphenoxymethyl radical. The resists have been tested under UV irradiation. The dependence of resist sensitivity on molecular weight is reported.
    Notes: Pour résoudre le phéomène de gonflement qui limite la résolution des résines microlithographiques classiques, nous nous sommes intéressés à de nouvelles résines avec lesquelles ce phénomène n'apparait pas. Nous avons retenu pour notre étude les résines R qui renferment en mélange un polymère porteur de radicaux tétrathiafulvalénylcarbonyloxyméthyles et le dibromotétrachloroéthane. Afin de voir l'influence de la nature du radical porteur de l'unité tétrathiafulvalène dans le polymtrè sur les propriétés microlithographiques des résines R, nous nous sommes également intéressés aux polymères renfermant des radicaux tétrathiafulvalénylphénoxymethyles. Les résines R ont été testées sous irradiation UV. Leurs sensibilités dépendent en outre de la valeur de la masse molaire du polymèr.
    Additional Material: 4 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 33-44 
    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: Hochfeste Polyethylen- (HSPE), Polypropylen- (PP), Polyethylenterephthalat-(PET) und Polyvinylalkohol-(PVA) Textilgarne wurden unter Anwendung des entwickelten kontinuierlichen Einweichprozesses mit verschiedenen funktionellen Monomeren, wie beispielsweise Acrylsäure (AA), Acrylamid (AM), Glycidylacrylat (GA) und 4-Vinylpyridin (VP) oberflächenfotogepfropft. Die Einfärbbarkeit der oberflächenmodifizierten Garne mit verschiedenen Textilfarbstoffen wurde untersucht. Im allgemeinen wurde eine erhebliche Verbesserung der Einfärbbarkeit beobachtet. Die Farbstoffaufnahme der oberflächenfotogepfropften Fasern wird von vielen Faktoren beeinflußt, beispielsweise von der Art der Faser, der Menge und den Eigenschaften des auf die Oberfläche der Fasern gepfropften funktionellen Monomeren, der Art des Textilfarbstoffs usw. Die Faseroberflächen, auf die ein Monomeres mit basischen Gruppen wie Acrylamid und 4-Vinylpyridin gepfropft wurde, lassen sich mit einem sauren Farbstoff wirkungsvoll einfärben. Dagegen läßt sich eine Faseroberfläche, auf die ein saures funktionelles Monomeres gepfropft wurde, leicht mit basischen Farbstoffen in tiefen Farbtönen einfärben. Die Farbstoffaufnahme steigt stetig mit zunehmender Pfropfung, in ESCA-Spectren als relative Intensitaten relevanter Linien gemessen. Die nicht gepfropften HSPE-, PP-, und PET-Fasern können mit bestimmten Farbstoffen in gewissem Maße eingefärbt werden. Bei der vorliegenden Arbeit erhöhte sich die Farbstoffaufnahme bei HSPE-Fasern, die mit GA gepfropft und mit dem Metallkomplexfarbstoff IO eingefärbt wurden, um das 3,4fache, bei PP-Fasern, die mit AA gepfropft und mit dem basischen Farbstoff MB eingefärbt wurden, um das 7,9fache, bei PET mit AM und dem Direktfarbstoff SL um das 6,1fache, bei PVA mit VP und dem sauren Farbstoff TE um das 15,3fache.
    Notes: High-strength polyethylene (HSPE), polypropylene (PP), poly(ethylene terephthalate) (PET), and poly(vinyl alcohol) (PVA) textile yarns have been surface-photografted with various functional monomers, such as acrylic acid (AA), acrylamide (AM), glycidyl acrylate (GA) and 4-vinyl pyridine (VP), by means of the continuous presoaking process developed. The dyeing of these surface-modified yarns with various textile dyes has been investigated. In general, considerable improvements of dyeability have been observed. The dye adsorption of the surface-photografted fibers is influenced by many factors, such as type of fiber, amount and properties of the functional monomer grafted on the surface of the fibers, type of textile dye, etc. The fibers surface-grafted with a monomer containing basic groups, such as acrylamide and 4-vinyl pyridine, are efficiently dyed with an acid dye. Conversely, a fiber surface-grafted with acidic functional monomer is easily dyed to deep shades with basic dyes. The dye adsorption increases monotonically with increasing grafting measured in ESCA spectra as relative intensities of relevant lines. The ungrafted HSPE, PP and PET fibers can be dyed to some extent with certain dyes. In the present work, the dye adsorption increased by 3.4 times for HSPE fiber grafted with GA and dyed with the metal complex dye IO, by 7.9 times for PP fiber grafted with AA and dyed with the basic dye MB, by 6.1 times for PET with AM and with the direct dye SL, and by about 15.3 times for PVA with VP and with the acid dye TE.
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 65-74 
    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 thermische Stabilität von Acrylnitril-Copolymeren wurde mittels DSC untersucht, um den Einfluß von halogenierten Comonomeren mit Carboxygruppen auf die Stabilisierung von PAN zu präfen. Es wird gezeigt, daß die Aktivierungsenergie fär die Cyclisierung des AN/Bromacrylsäure(BrAA)-Copolymeren (86,2 kJ/mol) deutlich niedriger als die der Copolymeren mit Chloracrylsäure (ClAA, 158 kJ/mol), Acrylsäure (AA, 128 kJ/mol) und Itaconsäure (IA, 102 kJ/mol) ist. Das erlaubt eine Stabilisierung bei häherer Temperatur und eine Verkürzung der Stabilisierungszeit. ClAA ist BrAA bezäglich der Stabilisierungseffektivität nicht überlegen. Der Mechanismus der Cyclisierung von AN-Copolymeren mit halogenierten, carboxygruppenhaltigen Comonomeren wird diskutiert.
    Notes: The thermal stability of AN copolymers was studied by DSC technique in order to get information on the influence of comonomers containing halogenated carboxylic acid on the stabilization of PAN. It is shown that the activation energy of cyclization is reduced in the case of the copolymer with bromoacrylic acid (BrAA, 86.2 kJ/mol) compared with chloroacrylic acid (ClAA, 158 kJ/mol), acrylic acid (AA, 128 kJ/mol) and itaconic acid (IA, 102 kJ/mol). Copolymer AN/BrAA permits the stabilization at higher temperature than AN/IA and AN/AA, helping to shorten the stabilization time. It is proved that comonomer ClAA is not superior to BrAA in the effectiveness of thermal stabilization. The mechanism of the cyclization reaction of AN copolymer containing halogenated carboxylic acid is discussed.
    Additional Material: 3 Ill.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 75-85 
    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: Es wurden neue unsymmetrische cycloaliphatische Bisepoxyderivative hergestellt. Die unterschiedliche Reaktionsfahigkeit der zwei Oxiranringe (cycloaliphatisch und glycidylisch) gegenüber Carbonsäure wurde untersucht, wobei eine normale und anomale Ringöffnung der Glycidylgruppen beobachtet wurde. Eine Homopolymerisation des Oxirans wurde ebenfalls beobachtet. Mit Hilfe der 13C-NMR-Spektroskopie wurde die Struktur der Polymeren ermittelt. Die neuen Epoxidharze zeigen gute thermische Eigenschaften.
    Notes: New bisepoxy unsymmetrical cycloaliphatic derivatives have been synthesized. The different reactivity of both oxirane rings (cycloaliphatic and glycidylic) has been tested against carboxylic acids giving rise to normal and abnormal opening to the glycidyl group. Homopolymerization reaction was also observed. Polymer structures were identified by 13C-NMR spectroscopy. Thermal analysis carried out allowed to confirm their good thermal properties.
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  • 28
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), S. 119-131 
    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: N,N′-4,4′-Diphenylmethane-bismaleimide (BMI) was oligomerized in semisolid phenolnovolak epoxide-resin (EP) up to P̄n = 10. The morphology of the novolakcured EP-BMI solid resins is a two-phase structure. It consists in a homogeneous EP-BMI phase of an interpenetrating polymer network (IPN) and a BMI phase. The dynamic-mechanical properties depend on the overall weight fraction w2 of BMI and on the degree of oligomerization (P̄)n of BMI. The relative shear modulus of the EP-EMI resin in the rubber state shows that both phases can be coherent. The glass transition temperature (Tg) can be correlated with the degree of oligomerization of the BMI, for instance Δ P̄n ≡ 10 corresponds to Δ Tg ≡ 35 K and Δ wx2 ≡ 0,25 (weight fraction of BMI in the homogeneous EP-BMI phase). Surprisingly, the breaking strength remains constant.
    Notes: N,N′-4,4′-Diphenylmethan-bismaleimid (BMI) wurde in halbfesten Phenolnovolak-Epoxidharzen (EP) bis P̄, = 10 oligomerisiert. Die novolakgehärteten EP-BMI-Festharze bilden eine Zweiphasenstruktur, bestehend aus einer EP-BMI-Mischphase der beiden sich durchdringenden Netzwerke (interpenetrating polymer network, IPN) und einer BMI-Phase. Die dynamisch-mechanischen Eigenschaften hängen vom Gesamt-BMI-Anteil w2 und vom Oligomerisierungsgrad P̄n des BMI ab. Der relative Schubmodul des EP-BMI-Harzes im kautschukelastischen Zustand zeigt, daß beide Phasen kohärent sein können. Die Glastemperatur Tg korreliert mit dem Oligomerisierungsgrad, z. B. entspricht ΔPn ≡ 10 einem ΔTg ≡ 35 K und einem BMI-Anteil Δ wx2 ≡ 0,25 in der Mischphase. Die Bruchzahigkeit bleibt unerwartet konstant.
    Additional Material: 8 Ill.
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  • 29
    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: Handelsübliche Araldit™-Polymere wurden mit Zimtsäure- bzw. Furanacrylsäurechlorid modifiziert und über [2 + 2]-Cycloaddition photochemisch vernetzt. Die Glasübergangstemperaturen der entstandenen Polymeren betragen bis zu 130°C bei Dielektrizitätskonstanten von ∊r = 3.0. Daher können diese Polymeren in Mehrlagenmikroverdrahtungen verwendet werden. Zahlreiche wohldefinierte, multifunktionelle Modifikatoren wurden synthetisiert und deren Einfluß auf die Polymerisation und die Eigenschaften der Araldit™-Polymeren eingehend untersucht.
    Notes: Commercially available Araldite™-type polymers have been modified with cinnamic and furan acrylic acid chlorides. The polymers were photochemically crosslinked via a [2 + 2] cycloaddition. The resulting polymers show glass transition temperatures up to 130°C and dielectrical constants of ∊r = 3.0. Therefore, these polymers can be applied as permanent resists in multi-layered wiring structures. Numerous well-defined multifunctional modifiers have been synthesized. The effect of those modifiers on the polymerization and properties of the araldite-type polymers has been studied in some detail.
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  • 30
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 200 (1992), S. 61-76 
    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 photoinduced free radical crosslinking of silicone containing pendent acrylate or methacrylate groups was investigated by swelling measurements. A modified swelling test was applied to observe the network formation as a function of several parameters. The results show that the network density of the crosslinked polymers is a function of the light intensity, the exposure time, the acrylate content, the molecular weight of the uncrosslinked silicone acrylate and also of the length of the spacer group between the acrylate unit and the silicone backbone. Oxygen has only an influence on the polymerization kinetics, but it does not influence the network density.From the δB, -values of crosslinked silicone acrylates and silicone containing vinyl groups it is possible to analyze the structure of the network as a function of the olefinic group. The χ-parameters of both silicone types are of the same magnitude in the same concentration range.Kinetics investigations demonstrate that the order of the network formation is nearly unity. This result agrees with the polymerization kinetics.By means of swelling measurements it is also possible to study the influence of hydrogen siloxane additives as hydrogen transfer reagents.
    Notes: Die photoinduzierte radikalische Vernetzung von Siliconacrylaten bzw. -methacrylaten wurde mit Hilfe von Quellungsmessungen untersucht, wobei ein modifizierter Quellungstest erlaubt, die Netzwerkbildung als Funktion verschiedener Parameter zu betrachten. Die Ergebnisse zeigen, daß die Netzwerkdichte eine Funktion der Lichtintensität, der Bestrahlungszeit, des Acrylatgehalts, der Molmasse des unvernetzten Silicons und auch der Länge der Spacergruppe zwischen Acrylateinheit und dem Siliconrückgrat ist. Sauerstoff besitzt dagegen nur einen Einfluß auf die Polymerisationskinetik, nicht aber auf die Netzwerkdichte.Aus dem Vergleich der δB, -Werte der vernetzten Siliconacrylate und der vernetzten Vinylsilicone kann geschlossen werden, daß die Netzwerkstruktur auch vom Typ der olefinischen Gruppen abhängt. Die χ-Parameter besitzen jedoch im gleichen Konzentrationsbereich die gleiche Größe.Kinetische Untersuchungen zeigen, daß die Netzwerkbildung nach einem Zeitgesetz erster Ordnung verläuft. Dieses Ergebnis steht im Einklang mit der Polymerisationskinetik.Mit Hilfe der Quellexperimente ist es auch moglich, den Einfluß von H-Siloxanzusätzen als Wasserstoffüberträger zu untersuchen.
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  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), 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: The copolymerization of butadiene with a technical divinylbenzene fraction was investigated to study the modification of cis-1,4 polybutadiene. Beside the Ziegler-Natta-catalyst nickeloctanoate/bortrifluoride/aluminiumtriethyl, another catalytic system consisting of nickeloctanoate/titaniumtetrachloride/aluminiumtriethyl was used, which allows to polymerize more divinylbenzene because of its higher activity toward vinylaromates. With the help of spectroscopical, pyrolysis-gaschromatographical and thermoanalytical methods one can obtain relations between glass-, crystallization- and melting temperature and the microstructure of the polymer. It can be shown that not only the divinylbenzene but also the trans-1,4- and the 1,2-vinyl units are statistically distributed in the polymer. By this, beside the pyrolysis-gaschromatography, particularly the differential scanning calorimetry is a useful tool to characterize the structure of partially crosslinked polymers obtained from polymerization of technical fractions.
    Notes: Im Rahmen von Arbeiten zur Modifizierung des cis-1,6Polybutadiens wurde die Copolymerisation von Butadien und einer Divinylbenzolfraktion, insbesondere der Bereich mit kleinen Divinylbenzolgehalten, untersucht. Neben dem Ziegler-Natta-Katalysator Nickeloctanoat/Bortrifluoridetherat/Aluminiumtriethyl kam auch ein Nickeloctanoat/Titantetrachlorid/Aluminiumtriethyl-System zur Anwendung, welches es durch seine höhere Aktivität gegenüber Vinylaromaten ermöglicht, großere Mengen der Divinylbenzolfraktion zu polymerisieren. Durch die Anwendung von spektroskopischen, pyrolysegaschromatographischen und thermoanalytischen Charakterisierungsmethoden können Beziehungen zwischen den erhaltenen Glas-, Kristallisations- und Schmelztemperaturen und der Mikrostruktur des Polymeren hergestellt werden. Es zeigt sich, daß sowohl das Divinylbenzol als auch die trans-1,4 bzw. die 1,2-Vinyl-Einheiten statistisch in das Polymere eingebaut werden. Damit eignet sich neben der Pyrolysegaschromatographie besonders die Differential Scanning Calorimetry als eine einfache Methode zur Charakterisierung der Struktur von aus technischen Fraktionen erhaltenen und teilweise vernetzten Polymerproben.
    Additional Material: 10 Ill.
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  • 32
    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: Optisch hochreine Gläser wurden aus Polystyrol (PS), Polymethylmethacrylat (PMMA) und statistischen Styrol-Methylmethacrylat-Copolymeren (S-MMA) hergestellt. Die an diesen Gläsern gemessene Lichtstreuung hängt von der chemischen Zusammensetzung des Polymeren und dem Brechungsindex des zugesetzten Weichmachers ab. Ein isorefraktiver Weichmacher verringert die Streuwerte der S-MMA-Copolymeren, hat aber keinen signifikanten Einfluß auf das Streuverhalten von PMMA. Ein Weichmacher mit einem vom Polymeren verschiedenen Brechungsindex verschlechtert die Streuwerte in allen untersuchten Fällen. Es wird gezeigt, daß ein isorefraktiver Weichmacher die Dämpfungseigenschaften von aus dem Copolymeren S-MMA 2/1 gezogenen polymeren Lichtleitern verbessert.
    Notes: High optical purity polystyrene (PS), poly(methyl methacrylate) (PMMA) and styrene-methyl methacrylate statistical copolymers (S-MMA) were prepared. Light scattering measured on polymeric glasses depends on the chemical composition of the polymer and on the refractive index of the plastifier added. An isorefractive plastifier reduces considerably the scattering values for the copolymers S-MMA, while having no significant effect on the scattering of PMMA. A plastifier with a refractive index different from that of the polymer raises distinctly the light scattering values in all cases. It has been shown that the isorefractive plastifier has a favourable effect on attenuation loss of polymeric optical fibers (POF) obtained from the copolymer S-MMA 2/1.
    Additional Material: 4 Ill.
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  • 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: ABS/TPU- und SAN/TPU-blends were investigated on the basis of the analysis of viscoelastic behaviour of the components for characterization of the formation of morphology in melt mixing processes. Blends mixed in a laboratory kneeder and extruded from a high pressure capillary viscosimeter under definite conditions were characterized concerning their phase morphology by transmission electron microscopy. The types of morphology predicted by the help of rheological analysis could be confirmed by electron micrographs and quantitative analysis of morphology. It becomes evident, that the ratio of viscosity of the components has the primary influence on the formation of morphology in the blends. But also thermomechanically induced molecular destruction processes and thermodynamic interactions as well as connecting crystallisation conditions for the TPU-phase are not negligible with regard to resulting phase morphology.
    Notes: An ABS/TPU- bzw. SAN/TPU-Blends wurden Untersuchungen zur Morphologiebildung beim Schmelzemischen auf der Basis der Analyse des viskoelastischen Verhaltens der Komponenten angestellt. Unter definierten Bedingungen im Laborkneter gemischte und unter definierten Bedingungen mittels Hochdruckkapillarviskosimeter extrudierte Blendproben wurden hinsichtlich ihrer Phasenmorphologie elektronenmikroskopisch charakterisiert. Die mittels der rheologischen Analyse prognostizierten Morphologietypen und Morphologiebildungsmechanismen konnten anhand der elektronenmikroskopischen Aufnahmen und der quantitativen Morphologieanalyse bestätigt werden. Es zeigte sich, daß das Viskositätsverhältnis der Komponenten primären Einfluß auf die Morphologiebildung ausübt. Darüber hinaus sind auch thermomechanisch induzierte molekulare Abbauvorgänge und thermodynamische Wechselwirkungen sowie damit im Zusammenhang stehende Kristallisationsbedingungen für die TPU-Phase hinsichtlich der resultierenden Phasenmorphologie nicht zu vernachlässigen.
    Additional Material: 14 Ill.
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  • 34
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 194 (1992), S. 189-200 
    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: Die Stabilität von Verbindungen von Polypropylen (PP) und Polycarbonat (PC) mit einem Acryl-Kleber wurde mit einer thermodynamischen, auf der Messung von Oberflächenspannungen beruhenden Methode bestimmt.Die Charakterisierung der Oberflächen zeigte, daß eine Plasmabehandlung die Bildung einer sauerstoffreichen Oberflächenschicht bewirkt. Eine Lagerung in Wasser führt bei PP zu keiner Veränderung dieser Schicht, während bei PC niedermolekulare, oxidierte Verbindungen ausgewaschen werden.Sowohl unbehandelte als auch mit Plasma behandelte PP-Verbindungen wiesen bei Lagerung in Wasser eine annehmbare Stabilität auf. Zwar wurde eine geringe Abnahme der Scherfestigkeit gemessen, aber unbehandeltes und plasmabehandeltes PP zeigten weiterhin adhäsives bzw. kohäsives Bruchverhalten.Im Falle von PC blieben nur die aus unbehandeltem PC hergestellten Verbindungen ausreichend stabil, während die aus plasmabehandeltem PC hergestellten Verbindungen stark abgebaut wurden. Bei den letzteren wanderte der Versagensort an die Polymer/Kleber-Grenzfläche, was auf die Ausbildung einer sehr hydrophilen, niedermolekularen Schicht zurückgeführt wird.
    Notes: The stability of PP and PC/acrylic adhesive joints has been assessed using a thermodynamic method based on surface tension components.Surface characterization showed that plasma treatment induces the formation of an oxygen-rich layer on treated surfaces. In the case of PP this layer does not change its composition upon immersion in water, while for PC leaching of oxidized species with low molecular weight was observed.Both untreated and plasma treated PP joints showed reasonable stability against immersion in water. A small reduction of shear strength was observed, but the fracture remained adhesive for untreated PP and cohesive for plasma treated PP.In the case of PC, only joints made from untreated PC showed fair sensitivity against immersion in water, while those made from plasma treated specimens degraded dramatically. In the latter case the locus of failure moved to the adhesive/adherend interface, the presence of a very hydrophilic, low molecular weight layer being suggested as responsible for this behavior.
    Additional Material: 2 Ill.
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  • 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: The chloromethylated polystyrenes bearing tetrathiafulvalenylcarbonyloxymethyl groups can be oxidized. We have shown that ion radical salts are obtained from these polymers and carbon tetrabromide after irradiation with UV light. Charge transfer complexes were prepared by mixing these polymers and 2,3-dichloro-5,6-dicyanobenzoquinone. The possible presence of sulfoxides as a result of oxidation of some tetrathiafulvalene units could explain the difficulties we have observed to filter solutions of these polymers.
    Notes: Les polystyrènes chlorométhylés renfermant des radicaux tétrathiafulvalénylcarbonyloxyméthyles peuvent être oxydés. Ainsi la formation de sels d'ions radicaux obtenus à partir de ces polymères et de tétrabromure de carbone, irradiés sous UV, a été mise en évidence. Des complexes de transfert de charge ont été préparés en mettant en présence ces polymères et de la 2,3-dichloro-5,6-dicyanobenzoquinone. La présence de sulfoxydes non décelés et résultant de l'oxydation de certaines unités de tetrathiafulvalène contenus dans ces polymères pourrait expliquer les problèmes rencontrés lors de la filtration de leurs solutions.
    Additional Material: 4 Ill.
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  • 36
    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 Metallkomplexierung von wasserloslichem Poly[1-(2-hydroxyethyl)aziridin-co-2-methyl-2-oxazolin] mit Co(II), Zn(II), Ni(II), Cu(II), Cr(III), Fe(III), Cd(II), Pb(II) und Sr(II)-Ionen wurde in wäßriger Phase mit der Methode der Liquid-Phase Polymer-Based Retention (LPR) untersucht. Die Studie zeigt, daß alle Metallionen, außer Co(II) und Zn(II), bei pH 5 komplexiert wurden. Im Gegensatz zu Sr(II), das nur eine schwache Wechselwirkung in einem pH-Bereich von 3 bis 7 zeigte, wurden bei pH 7 94% Co(II) und 88% Zn(II) retentiert. Bei pH 3 zeigten nur Cu(II) und Cr(III) eine Wechselwirkung mit dem Polymeren, wobei die Retentionswerte 76% für Cu(II) und 52% für Cr(III) betrugen. Viskositätsmessungen des Copolymeren in Gegenwart von Metallionen wurden bei verschiedenen pH-Werten durchgeführt.
    Notes: The metal complexation of water-soluble poly[1-(2-hydroxyethyl)aziridine-co-2-methyl-2-oxazoline] with Co(II), Zn(II), Ni(II), Cu(II), Cr(III), Fe(III), Cd(II), Pb(II), and Sr(II) ions was investigated in aqueous phase using Liquid-Phase Polymer-Based Retention (LPR). The study shows that all metal ions are complexed at pH 5, except Co(II) and Zn(II). In contrast to Sr(II), which showed only a slight interaction over a pH range of 3 to 7, 94% of Co(II) and 88% of Zn(II) were retained at pH 7. At pH 3, only Cu(II) and Cr(III) ions interacted with the copolymer with retention values of 76% for Cu(II) and 52% for Cr(III). Viscosimetric measurements of the copolymer were performed in the presence of metal ions at different pH values.
    Additional Material: 4 Ill.
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  • 37
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 117-129 
    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: Makroretikulare Copolymerperlen wurden durch Suspensionspolymerisation von Styrol, Bis(2-chlorethyl)vinylphosphonat (CEVP) und Divinylbenzol (DVB) in Gegenwart von Toluol als Verdünnungsmittel hergestellt. Die auf der Perlenoberfläche vorhandenen 2-Chlorethylphosphonat-Gruppen wurden durch Hydrolyse mit verdünnter Salpetersäure in Phosphon-Gruppen transformiert. Für die Einführung zusätzlicher Phosphon-Gruppen wurden die Copolymeren in Gegenwart von Aluminiumchlorid-Katalysator mit Phosphortrichlorid phosphoryliert, und die dabei entstandenen Dichlorphosphingruppen wurden mit verdünnter Salpetersäure verseift und oxidiert. Die Untersuchungen zur Chelatbildung der Copolymeren mit Metallionen zeigten, daß sie ein hohes Adsorptionsvermögen für Uranylionen und gute Stabilität gegen Chemikalien wie Säuren und Alkalien aufweisen. Es wurde auch gefunden, daß die Phosphongruppen enthaltenden Copolymeren recht effektive Adsorbentien für eine Vielzahl von Schwermetalionen wie Pb2+, Hg2+, Cd2+ und Cu2+ sind.
    Notes: Macroreticular copolymer beads were prepared by suspension polymerization of styrene, bis(2-chloroethyl) vinyl phosphonate (CEVP) and divinylbenzene (DVB) in the presence of toluene as diluent. The bis(2-chloroethyl) phosphonate groups on the bead surface were converted into phosphono groups by hydrolysis with dilute nitric acid. For the additional enrichment of phosphono groups, the copolymers were phosphorylated at the phenyl rings with phosphorus trichloride in the presence of aluminum chloride and hydrolyzed and oxidized with dilute nitrics acid. The investigations on metal ion chelation characteristics of the bead-type copolymers revealed that they have very high adsorptivity toward uranyl ions and good chemical resistance under acidic and alkaline media. It was also found that the phosphono group-containing copolymer beads are effective adsorbents for other heavy metal ions such as Pb2+, Hg2+, Cd2+, and Cu2+.
    Additional Material: 4 Ill.
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  • 38
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 131-139 
    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: Lösungen von Phenylisocyanat (I) in DMF wurden sowohl bei verschiedenen Temperaturen als auch in Gegenwart von Polyurethankatalysatoren und/oder 1,3-Diphenylharnstoff (II) gelagert. Die Reaktionsprodukte wurden mit Hilfe der HPLC quantifiziert. Neben der Hydrolyse von I zu II wird bei 20°C eine signifikante Reaktion von I mit II zu 1,3,5-Triphenylbiuret (III) beobachtet.Oberhalb 60°C reagiert I mit dem Lösungsmittel zu N,N-Dimethyl-N′-phenylformamidin (V). In DMF dissoziiert III bereits bei Temperaturen 〉 40°C zu I und II.
    Notes: Solutions of phenylisocyanate (I) in DMF were stored at different temperatures in the presence of both polyurethane catalysts and 1,3-diphenylurea (II). The reaction products were determined by HPLC. Beside the hydrolysis of I to II, a significant reaction of I with II to 1,3,5-triphenylbiuret (III) was observed at 20°C. Above 60°C, I reacted with the solvent to form N,N-dimethyl-N′-phenylformamidine (V). In DMF, III dissociated to I and II already at temperatures 〉40°C.
    Additional Material: 3 Ill.
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  • 39
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 141-147 
    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: Glasfaserverstärkte Epoxidlaminate wurden aus den Matrixharzen Tetraglycidyldiaminodiphenylmethan (TGDDM) und Tetraglycidylbis(o-toluidino)methan (TGMBT) unter Verwendung von Härtern wie 4,4′-Diaminodiphenylmethan (DDM), 4,4′-Diaminodiphenylsulfon (DDS) und Diethylentriamin (DETA) hergestellt. Die mechanischen und dielektrischen Eigenschaften sowie die Chemikalienresistenz der Laminate wurden untersucht. Die Zugabe eines Epoxyverstärkers (20 Gew.-%, bezogen auf das Matrixharz) ergab eine Verbesserung der mechanischen Eigenschaften.
    Notes: Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethaneSystematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane. (TGDDM) and tetraglycidyl bis(o-toluidino)-methaneSystematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane. (TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.
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  • 40
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 149-157 
    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 1 μm layers of different polymers containing 10 wt.-% 4,4′-diazidobiphenyl, the network formation under the influence of UV-irradiation was estimated by solvent treatment. The high activity of poly(glycidyl methacrylate) against the nitrenes formed is caused by its 1,2-epoxypropyl groups. As confirmed by IR-spectroscopy, the oxirane ring itself is not affected; NMR spectroscopic results indicate reactions between nitrenes and exocyclic CH2-groups.
    Notes: Die UV-Vernetzung in 1 μm-Schichten aus Polymeren verschiedener Konstitution, die 10 Gew.-% 4,4′-Diazidobiphenyl (DABP) enthalten, wird zeitabhängig anhand der reduzierten Schichtdicke nach Lösungsmittelbehandlung verglichen. Für die hohe Vernetzungsgeschwindigkeit von Polyglycidylmethacrylat mit den photolytisch gebildeten Bisnitrenen sind die 1,2-Epoxypropylgruppen verantwortlich. Der Oxiranring bleibt erhalten (IR-Spektroskopie). Wahrscheinlicher Reaktionsort ist die exocyclische CH2-Gruppe (13C-Festkörper-NMR-Spektroskopie).
    Additional Material: 4 Ill.
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  • 41
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 159-173 
    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 10 unterschiedlich 4′-substituierten 4-[N,N-dihydroxyethyl]aminoazobenzolen wurden durch Umsetzung mit Hexamethylendiisocyanat polymere Azofarbstoffe (M̄n 4200-10200) synthetisiert und die Substituentenabhängigkeit der spektralen Eigenschaften, der Redoxpotentiale und des Ausbleichverhaltens mit entsprechenden monomeren und dimeren Modellverbindungen verglichen. Die Ausbleichung erfolgt durch einen photooxidativen Prozeß. In der Reihenfolge monomerer 〉 dimerer 〉 polymerer Azofarbstoff sinkt die Lichtstabilität durch die Verringerung thermischer Desaktivierungsprozesse sowie durch einen möglichen intramolekularen Energietransfer.
    Notes: Starting from 10 different 4′-substituted 4-[N,N-dihydroxyethyl]aminoazobenzenes, polymeric urethane-azo dyes (M̄n 42000-10200) were prepared by reacting those with hexamethylene diisocyanate. The dependence of spectral properties, redox potentials and photofading behaviour on the kind of substitutents was determined and then compared with corresponding monomer and dimer model compounds. Photofading is caused by a photooxidative process. In the sequence of monomeric 〉 dimeric 〉 polymeric azo dyes, light stability decreases due to a diminution in thermal disactivation processes and in a possible intramolecular energy transfer.
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  • 42
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 207-208 
    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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  • 43
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 201-206 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bead cellulose, particle diameter 0.1 - 2.7 mm, was prepared from dispersions of viscose in chlorobenzene by applying the thermal sol-gel transition. Technical viscose containing modifiers Berol Visco 32, Berol Glyco 1540 and Kordamin V was used. The size of cellulose beads can be controlled by means of the amount of oleic acid in the dispersion medium. The optimal result was reached at 5 - 6 mg oleic acid in 90 ml chlorobenzene.
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  • 44
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), S. 185-199 
    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: PET- und PA 66-Textilien wurden unter normalen Bedingungen mit verschiedenen Dispersionsfarbstoffen gefärbt. Die gefärbten Textilien wurden mit 180 kV Elektronenstrahlung bestrahlt. Es wurde beobachtet, daß, verglichen mit den unbestrahlten Materialien, zunehmende Strahlungsdosen zu einer Zunahme des Gesamtfarbabstandes dE führten. Diese Farbunterschiede werden hauptsächlich von zwei Reaktionen verursacht: Erstens von der reversiblen Bildung von Farbstoffradikalen, die (an Luft) wieder zu den Ausgangsfarbstoffen reoxidiert werden können und zweitens durch die irreversible Reaktion von Farbstoffmolekülen mit dem Faserpolymeren. Die zweite Reaktion ruft eine permanente Farbänderung des Textils hervor, die bei entsprechenden Bestrahlungsbedingungen klein gehalten werden kann. Die Entscheidung, ob diese Veränderung toleriert werden kann, hängt von der weiteren Verwendung des Textils ab.
    Notes: PET and PA 66 fabrics were dyed with different disperse dyes under regular conditions. The dyed fabrics were irradiated with 180 kV electron radiation. It was observed that increasing radiation doses led to increasing total color differences dE if compared to the unirradiated materials.These color differences are mainly caused by two types of reactions. First by the reversible formation of dye radicals, which can be reoxidized (in air) to the original dye molecules, and second by the irreversible reaction of dye molecules with the fiber polymer. The latter reaction causes a permanent change of the color of the fabric, which can be kept low with the proper irradiation conditions. The decision whether or not this change can be tolerated depends on the further use of the textile.
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  • 45
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 197 (1992), 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: Unterschiedlich 4′-substituierte 4-[N-Ethyl-N-(2-acryloyloxy)ethyl]aminoazobenzole dienten als Ausgangsmonomere für Homopolymerisationen und Copolymerisationen mit Styrol und Methylmethacrylat. Die Photobleichung der erhaltenen polymeren Azofarbstoffe (M̄ 4200-9000) wurde mittels einer Xenotest-Apparatur untersucht und mit den entsprechenden Monomeren verglichen. Es wird angenommen, daß die in der Reihenfolge monomerer  -  copolymerisierter  -  homopolymerisierter Azofarbstoff sinkende Photostabilität durch zunehmenden Energietransfer in der Matrix verursacht wird.
    Notes: Different 4′-substituted 4-[N-ethyl-N-(2-acryloyloxy)ethyl]aminoazobenzenes were used as starting monomers for homopolymerization and copolymerization reactions with styrene and methyl methacrylate. The photofading behaviour of the obtained polymeric azo dyes (M̄n 4200 - 9000) was investigated by means of a Xenotest device and compared with that of the corresponding monomers. The decreased photostability in the order monomer  -  copolymer  -  homopolymer was assumed to be caused by an increasing energy transfer in the matrix.
    Additional Material: 2 Ill.
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  • 46
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 31-38 
    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: N-Methacryloyloxyphthalimid und N-Methacryloyloxytetrabromphthalimid wurden durch Reaktion von Methacrylsäure bzw. Methacryloylchlorid mit N-Hydroxyphthalimid bzw. N-Hydroxytetrabromphthalimid hergestellt und homopolymerisiert. Die Austauschreaktionen der Polymeren mit Hydroxy- und Amin-Verbindungen wurden untersucht.
    Notes: N-Methacryloyloxyphthalimide (NMPI) and N-methacryloyloxytetrabromophthalimide (NMTPI) were prepared by the reaction of methacrylic acid with N-hydroxy-phthalimide and N-hydroxytetrabromophthalimide, respectively. The resulting monomers were polymerized. The reactions of the resulting polymers with hydroxy and amine compounds have been studied.
    Additional Material: 4 Tab.
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  • 47
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    Angewandte Makromolekulare Chemie 198 (1992), S. 15-29 
    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: Das Tempern von Poly(etheretherketonketon) zwischen Glasübergangs- und Schmelztemperatur erzeugt normalerweise einen ausgeprägten Doppelschmelzpeak in der DSC-Kurve dieses Polymeren. Die eingehende Untersuchung dieses Doppelschmelzverhaltens in Abhängigkeit von Temperbedingungen und experimentellen Parametern zeigt, daß die Kristallisation als ein in zwei Stufen mit unterschiedlichen Zeitskalen ablaufender Prozeß beschrieben werden kann. Eine Rekristallisation als Ursache des Doppelpeaks kann widerlegt werden.
    Notes: Annealing poly(ether ether ketone ketone) (PEEKK) between glass transition and melting temperature generally results in a pronounced double peak melting behavior as obtained by DSC. Detailed investigations of the dependence of this double peak melting behavior on annealing conditions and experimental parameters clearly reveal that the crystallization can be described by a two-stage process occurring on different time scales. A recrystallization model as origin for the double peak melting curves can be disproved.
    Additional Material: 9 Ill.
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  • 48
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 1-14 
    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: Nitrilkautschuk (NBR) wurde mit trans-Chlorcarbonylbis(tripheny1phosphin)rhodium(1) [trans-RhCI(CO)(PPh3)2] und Hydridocarbonyltris(triphenylphosphin)rhodium(1) [RhH (CO)(PPh3)3] als Katalysatoren in homogener Lösung selektiv hydroformyliert. Bei der Hydroformylierung von NBR mit 40 mol-% Acrylnitril bei 363 K, 5,6 MPa Gasdruck (CO:H2 = 1:1) und mit 0,43 mmol Katalysator werden mit trans-RhCl(CO)(PPh3)2 25% und mit RhH (CO)(PPh3)3 30% Umsatz erreicht. Beide Reaktionen sind bezüglich der Olefin- und Katalysatorkonzentration pseudo-erster Ordnung. Mit RhH (CO)(PPh3)3 wird eine höhere Reaktionsgeschwindigkeit erhalten. Die IR- und NMR-spektroskopische Charakterisierung der Produkte zeigt, daß sowohl die 1,4- als auch die 1,2-Butadieneinheiten hydroformyliert werden. Mit steigendem Aldehydgruppengehalt sinkt die Grenzviskositatszahl [q] und steigt die Glastemperatur. Bei hoheren Hydroformylierungsgraden wird Gelbildung beobachtet.
    Notes: Selective homogeneous catalytic hydroformylation of nitrile rubber (NBR) has been carried out in presence of trans-chlorocarbonylbis(triphenylphosphine)rhodium(I) [trans-RhCl(CO)(PPh3)3] and hydridocarbonyltris(triphenylphosphine)rhodium(I) [RhH(CO)(PPh3)3] as catalysts. At 363 K, under 5.6 MPa pressure (CO:H2 = 1:1) in presence of 0.43 mmol/l catalyst, the amount of hydroformylation is 25% in the case of trans-RhCl(CO)(PPh3)2 and 30% in the case of RhH (CO)(PPh3)3 for NBR with 40 mol-% acrylonitrile. Reaction kinetics suggest that both the reactions are pseudo-first order with respect to olefinic substrate and catalyst concentration. The rate of the reaction is higher in the case of RhH(CO)(PPh3)3. The characterization of the products by IR and NMR spectroscopy shows the formation of internal aldehyde groups from 1,4-units and terminal branched aldehyde groups from 1,2-units of the copolymer. Measurements on intrinsic viscosity [η] and glass transition temperature (Tg) suggest a decrease in [η] and an increase in Tg with the degree of formyl functionalization. Gel formation has been observed at higher degree of hydroformylation.
    Additional Material: 7 Ill.
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  • 49
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    Angewandte Makromolekulare Chemie 198 (1992), S. 61-70 
    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 Komplexierung von Rhenium in einer polymeren Methacrylat-Matrix mit funktionellen Diethylentriaminpentaessigsäure-Gruppen wurde untersucht. Es werden diamagnetische Komplexe gebildet, wobei Rhenium in einer heterogenen Koordinationssphäre gebunden wird, bestehend aus Chlor und mehrfach gebundenem Sauerstoffsowie Carboxygruppen, die als einzige funktionelle Gruppe des polymeren Trägers als Ligand des Metallatoms wirken. Die Rhenium-Komplexe wurden durch IR- und UV-VIS-Spektroskopie sowie durch Messung ihrer magnetischen Momente charakterisiert.
    Notes: The bonding of rhenium to diethylenetriaminepentaacetic acid functional groups of a polymeric methacrylate matrix was studied. Diamagnetic complexes were formed of Re(V) with the heterogeneous coordination sphere containing atoms of chlorine and multiply bonded oxygen in addition to carboxylic groups, which are the only groups of the polymeric support functioning as ligands in the bonding to the metal. The rhenium complexes were examined by IR and UV-VIS spectroscopy and by magnetic moment measurements.
    Additional Material: 1 Ill.
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  • 50
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    Angewandte Makromolekulare Chemie 198 (1992), S. 51-60 
    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: Meta-halogenierte Phenole sind bekanntermaßen chemisch und thermisch stabiler als ihre ortho- oder para-halogenierten Analoga. Die Verwendung eines reaktiven Zwischenproduktes, hergestellt durch Bromierung von 2,4,6-Trimethylphenol, als Alkylierungsmittel für den Einbau der stabilen m-Bromphenol-Einheit in verschiedene organische Substanzen und Polymere wird beschrieben. Bei der Anwendung als Verkapselungsmaterialien für elektronische Bauteile zeigten sich Epoxid-Derivate von Novolaken mit m-Bromphenol-Einheiten bezüglich hydrolytischer und thermischer Stabilität den konventionellen Tetrabrombisphenol-A-Epoxidharzen, die ortho- und para-bromiert sind, überlegen. Die m-Bromphenolgruppe verbessert die Bauteilzuverlässigkeit bei gleichzeitiger Erfüllung der Anforderungen an das Brandverhalten.
    Notes: Meta-halogenated phenols are generally known to be more chemically and thermally stable than their ortho- or para-halogenated counterparts. A reactive intermediate, produced by the bromination of 2,4,6-trimethylphenol is being used as an alkylating agent to incorporate this stable m-bromophenol moiety into varieties of organic compounds and polymers. In electronic encapsulation applications, epoxy derivatives of novolacs containing m-bromophenol have exhibited superior hydrolytic and thermal stability as compared with the conventional tetrabromo bisphenol-A epoxies which are ortho-brominated phenolics. The m-bromophenol moiety contributes to the extended device reliability while meeting flame retardency requirements as well.
    Additional Material: 5 Tab.
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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: Additionspolymere aus Bisphenol-A und Epichlorhydrin lassen sich mit Arylacryloylchloriden verestern. Die gebildeten Photoresists können mit UV-Licht (λ ≥ 280 nm) gehärtet werden. Aus FT-IR Messungen ergibt sich, daß die Netzwerkbildungsreaktion einem Zeitgesetz zweiter Ordnung gehorcht. DSC- und TGA-Messungen wurden durchgeführt. Die photovernetzten Polymeren weisen Glastemperaturen bis zu 171 °C auf und sind bis mindestens 350 °C thermisch stabil. Spektroskopische Daten werden aufgeführt.
    Notes: Addition polymers of bisphenol-A and epichlorohydrin can easily be esterified with aryl acryloyl chlorides to yield photosensitive polymers. The photoresists are curable with UV-irradiation (λ ≥ 280 nm). FT-IR measurements indicate that the network formation fonforms to second order kinetics. DSC and TGA measurements were carried out. The glass transition temperature of irradiated material is up to 171oC; the material is thermally stable up to 350oC. Spectral data are given.
    Additional Material: 2 Ill.
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  • 52
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    Angewandte Makromolekulare Chemie 198 (1992), S. 39-49 
    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 wird eine Ultraschall-Meßmethode vorgestellt, mit der sich fünf voneinander unäbhangige Elästizitatskonstanten von uniaxial symmetrischem Material bestimmen lassen. Für die Messung werden nur fünf Ultraschallausbreitungsgeschwindigkeiten benötigt. Vermessen wurden spritzgegossene Composite aus Polyphenylensulfid, Polyarylethersulfon mit Cardo-Seitengruppen, kurzen Kohlefasern und RUB. Die Ergebnisse zeigen eine enge Beziehung zwischen den elastischen Eigenschaften und der Struktur der Materialien auf.
    Notes: The paper makes an approach to the determination of the five independent elastic constants of uniaxial symmetric material with the ultrasonic immersion technique. Only five ultrasonic wave velocities are required during measurement. The elastic constants of the moulded composites comprised of poly(phenylene sulfide), poly(aryl ether sulfone) with cardo side groups, short carbon fiber and carbon black are measured by using the suggested treatment. The results exhibit a close relationship between the elastic properties and the structure of the materials.
    Additional Material: 6 Ill.
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  • 53
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    Angewandte Makromolekulare Chemie 198 (1992), S. 83-89 
    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: Membranen aus interpenetrierenden Netzwerken (IPN) wurden auf ihre Eignung für die Anwendung als Piezodialyse-Membranen untersucht. Bei diesen IPN-Membrane? handelt es sich nicht um Mosaik-Membranen. Bei zwei der IPN-Membranen enthielten die Permeate eine höhere NaCl-Konzentration als die Ausgangslösung (differentialrefraktometrisch bestimmt). Für eine dieser Membranen wurden die Salzgehalte auchtitrimetrisch mit AgNO3 ermittelt; die Ergebnisse belegen den positiven Piezodialyse-Effekt.
    Notes: In the present study, interpenetrating polymer network (IPN) membranes were investigated for their potential application as piezodialysis membranes. These IPN membranes are not mosaic membranes. It was found that some of these membranes did show piezodialysis effects. Two of the membranes tested under high pressure gave permeates which were found to be more concentrated in sodium chloride than the initial feed solution, when analyzed by differential refractometry. The permeates from one membrane were double checked by titrating the chloride ion with silver nitrate solution. The results of the titration also indicated a positive effect.
    Additional Material: 1 Ill.
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  • 54
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    Angewandte Makromolekulare Chemie 198 (1992), S. 91-110 
    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 Untersuchungen zum Flüssig-Dampf- und Flüssig-Fliissig-Gleichgewicht in Mischungen aus den Monomeren Ethen, 1-Buten, 4-Methyl-1 -penten und einem Polyethylenwachs bei mittleren Drücken durchgeführt. Auf der Basis der Chain-of-Rotators (COR) Zustandsgleichung, die mit einem Gruppenbeitragsmodell modifiziert wurde, wurden die Phasendiagramme der binaren und ternären Subsysteme sowie für das quaternare Gesamtsystem berechnet. Die Berechnungen ergeben eine zufriedenstellende Beschreibung des Flussig-Dampf-Gleichgewichtes und dessen Überlappung mit einem Flüssig-Flussig-Gleichgewicht bei höheren Drücken und Temperaturen. Die Mischungslücken in den beiden Systemen aus dem Polyethylenwachs mit 1 -Buten bzw. 4-Methyl-1 -penten werden auch nach Zugabe von Ethen zu den binären Mischungen beobachtet. Die Berechnungen zeigen ein kleines Dreiphasengebiet in allen entsprechenden ternären Mischungen. Eine Flüssig-Flüssig-Mischungslücke, die das Flüssig-Dampf-Gebiet schneidet, wird auch im quäternaren Gesamtsystem durch die Berechnungen mit dem modifizierten COR-Model1 gefunden. Diese doch überraschend komplizierten Phasenverhältnisse rnüssen bei der Abscheidung der Monomeren nach dem Syntheseschritt ausreichend beachtet werden.
    Notes: Some measurements of the vapour-liquid and/or the demixing equilibrium at moderate pressures were carried out in systems containing the monomers ethene, 1-butene, 4-methyl-1-pentene and a polyethylene wax. A group-contribution-modified chain-of-rotators (COR) equation of state was used to calculate the phase diagrams in all binary and ternary subsystems and in the whole quarternary mixture. The calculations lead to a satisfying description of the vapour-liquid equilibrium and its intersection by a liquid-liquid region at higher pressures and temperatures. The miscibility gaps in both mixtures of the polyethylene wax with 1-butene and 4-methyl-1-pentene, respectively, were observed again after adding ethene to these binary mixtures. The calculations indicate a small three phase triangle in all corresponding ternary mixtures. A liquid-liquid demixing region intersecting the vapour-liquid surface could also be found in the whole quaternary system by calculation with the modified COR model. This surprisingly complicated phase behaviour has properly to be taken into account during the separation of the monomers after the co- or terpolymerization process.
    Additional Material: 13 Ill.
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  • 55
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    Angewandte Makromolekulare Chemie 198 (1992), S. 111-122 
    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: Optisch aktives (+)-2-endo-Acetoxy-5-endo-bornylmethacrylat (ABMA) wurde aus (+)-Campher hergestellt und in Benzol radikalisch homo- bzw. mit achiralem Methyl-methacrylat (MMA) bzw. Styrol (St) copolymerisiert. Der EinfluB von Temperatur und Reaktionszeit auf den Polymerisationsverlauf wird diskutiert. Die Copolymerisations-parameter (r1 und r2, nach Fineman-Ross) für Poly(ABMA-co-MMA) und Poly(ABMA-co-St) sowie die Q- und e-Werte für ABMA wurden berechnet.Der Absolutwert der spezifischen Drehung von Poly(ABMA-co-MMA) nimmt mit steigendem ABMA-Gehalt im Copolymeren zu. Eine geringe Abweichung von der Linearität deutet darauf hin, daß die Copolymerhauptkette nicht asymmetrisch ist. Aus der Temperatur- und Löjsungsmittelabhangigkeit der spezifischen Drehung der beschriebenen Homo- und Copolymeren laßt sich schlierjen, daß diese nicht in einer speziellen helikalen Konformation vorliegen. Die Eignung der chiralen Polymeren als Katalysatoren für die asymmetrische Addition von Butyllithium an verschiedene Aldehyde in Abhängigkeit von der Temperatur wurde untersucht.
    Notes: Optically active (+)-2-endo-acetoxy-5-endo-bornyl methacrylate (ABMA) was prepared from (+)-camphor. The free-radical homopolymerization of ABMA and its copolymerization with achiral methyl methacrylate (MMA) or styrene (St) were carried out with 2,2′-azoisobutyronitrile in benzene. Effects of temperature and reaction time on the copolymerization were discussed. The monomer reactivity ratios (r1, r2) for poly(ABMA-co-MMA) and poly(ABMA-co-St) as well as Q and e values for the chiral ABMA in the copolymerization systems were evaluated by the Fineman-Ross method. It was found that the absolute value of the specific rotation of poly(ABMA-co-MMA) increased with increasing ABMA unit content. A small deviation from linearity was observed, which suggests that asymmetry is not introduced into the copolymer main chain. Temperature and solvent effects on the specific rotation of the chiral homopolymer and copolymers were investigated. The results suggest that the chiral polymers synthesized in this investigation did not show a strong preference for a particular helical conformation. Applications of the chiral polymers on the asymmetric addition of n-butyllithium to aldehydes were investigated. The effect of temperature and aldehydes on the asymmetric addition were also discussed.
    Additional Material: 6 Ill.
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  • 56
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Verschiedene α-oxoethylierte und α-hydroxyethylierte Styrol-Divinylbenzol-Copolymere (St-DVB) mit Unterschieden in Vernetzungsgrad und Porosität wurden hergestellt und auf ihre Eignung als Adsorbentien für ein nichtionisches Detergens (Nonaethylenglycol-mono-nonylphenylether) untersucht. Die durch Einführung der α-Hydroxy-ethylgruppen erreichte Verbesserung der Adsorptionskapazität war in den wenig vernetzten Harzen beträchtlich. Die mit 10 Vo1.-% DVB in Gegenwart von 100-120 Vo1.-% 2,2,4-Trimethylpentan hergestellten α-hydroxyethylierten Harze wiesen das höchste Adsorptionsvermögen auf, das sowohl von der Makroporosität als auch der Gelporosität abhängt. Die Anwendung der Harze als Säulenmaterial wurde geprüft und ihre Adsorptionseigenschaft als “Durchbruch”-Kapazität ermittelt.
    Notes: Several α-oxoethylated and α-hydroxyethylated styrene-divinylbenzene (St-DVB) resins having different degrees of crosslinking and porosity were prepared and their adsorption behaviour toward a nonionic surfactant, decaethyleneglycol nonylphenyl monoether, was investigated. The increment of the adsorption capacity caused by the introduction of the α-hydroxyethyl groups was remarkable in the less crosslinked resin. The α-hydroxyethylated resin derived from the St-DVB resin synthesized with 10 vol.-% DVB and 100 - 120 vol.-% of 2,2,4-trimethylpentane showed the highest capacity among the resins tested. The significance of both macroporosity and gel porosity in the effective adsorption of the nonionic surfactant was elucidated. A column operation using proposed resins was carried out and versatility was evaluated in terms of the breakthrough capacity.
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  • 57
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    Angewandte Makromolekulare Chemie 201 (1992), S. 1-10 
    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 Pigmentdispersion in unter verschiedenen Bedingungen extrudiertem Polyethylen hoher Dichte wurde mit einem an ein computergesteuertes Dunkelfeldmikroskop gekoppeltes Mikrophotometer quantitativ bestimmt. Mit dieser Methode lassen sich durch geringe Änderungen der Verarbeitungsbedingungen hervorgerufene Unterschiede in der Dispergiergüte feststellen. Da die Meßapparatur vergleichsweise preiswert ist, ist dieses Verfahren besonders für Kleinmengenverarbeiter interessant.
    Notes: A microphotometer attached to a computer-controlled darkfield microscopy system has been used for the quantitative measurement of the degree of pigment dispersion in high-density polyethylene extruded at specified varying processing conditions. The method distinguishes levels of pigment dispersion in extrudates obtained from subtle changes in processing conditions. Since the set-up is comparatively inexpensive, the technique promises to be particularly useful to small-scale manufacturers.
    Additional Material: 8 Ill.
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  • 58
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    Angewandte Makromolekulare Chemie 201 (1992), S. 23-31 
    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 Mechanik des elastoplastischen Bruchs wurde auf eine Reihe von Probekörpern aus EPDM-modifiziertem Polyamid 6 mit unterschiedlichem EPDM-Gehalt angewandt, um ihr Bruchverhalten einwandfrei zu charakterisieren. Insbesondere wurde das Integral JR gemessen, um die Festigkeit JIC am Ursprung des Bruchs sowie den Ausbreitungsparameter dJ/da abzuleiten. Die erzielten Ergebnisse werden auf ihre Abhängigkeit von Gummigehalt, Temperatur und Verformungsgeschwindigkeit untersucht und diskutiert.
    Notes: Elasto-plastic fracture mechanics has been applied to a series of EPDM-modified polyamide-6 samples with varying rubber content, in order to characterize properly their fracture behaviour. J-testing has been carried out to determine the J-resistance (JR) curve and to evaluate therefrom the fracture initiation resistance, JIC, and the fracture propagation parameter dJ/da. The results obtained are analyzed and discussed as a function of rubber content, temperature, and strain rate.
    Additional Material: 6 Ill.
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  • 59
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    Angewandte Makromolekulare Chemie 200 (1992), 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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  • 60
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    Angewandte Makromolekulare Chemie 201 (1992), S. 11-21 
    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 kinetics of the polycondensation of Na2S · 3H2O and 1,4-dichlorobenzene to poly(phenylene sulfide) in 1-methyl-2-pyrrolidone as solvent was studied in a differential scanning calorimeter at temperatures from 220°C to 260°C. Stainless steel high-pressure capsules of 30 μl volume were used as micro reactors.The reaction is highly exothermic. At 220°C the enthalpy of reaction reaches a value of 180 kJ/mol. The polycondensation is characterized by an autocatalytic behaviour. The kinetics can be modelled by a second order equation with respect to the stoichiometrically charged monomers and a propagation rate constant being dependent on conversion. The activation energy of the polycondensation is 95 kJ/mol.
    Notes: Die Polykondensation von Na2S·3H2O und 1,4-Dichlorbenzol im Lösungsmittel 1 -Methyl-2-pyrrolidon wurde in kleinen Hochdruck-Kapseln aus Edelstahl mit einem Volumen von ca. 30 μl in einem Differentialkalorimeter im Temperaturbereich von 220°C bis 260°C kinetisch untersucht. Die Reaktion ist stark exotherm, bei 220°C beträgt die Reaktionsenthalpie ca. 180 kJ mol-1. Sie ist durch ein autokatalytisches Verhalten gekennzeichnet, welches mit einem Zeitgesetz 2. Ordnung in bezug auf die Konzentration der stöchiometrisch eingesetzten Monomeren und einer vom Umsatz abhängigen Reaktionsgeschwindigkeitskonstante des Kettenwachstums beschrieben werden kann. Die Aktivierungsenergie beträgt 95 kJ mol-1.
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  • 61
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    Angewandte Makromolekulare Chemie 201 (1992), S. 229-229 
    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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  • 62
    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 photoinduzierte radikalische Polymerisation von Acrylamid in Kombinationen von zwei Polymeren, die Carbonsäuregruppen enthalten, wurde untersucht. Die kinetischen Parameter dieser Polymerisation, gemessen mit Hilfe einer kalorimetrischen Methode, hängen vom Mischungsverhältnis der beiden Polymeren im System ab. In Gemischen mit der niedrigsten Glasübergangstemperatur ist die Polymerisationsgeschwindigkeit am hochsten. Diese Ubergangstemperaturen wurden mit Hilfe einer speziellen Fluoreszenztechnik unter Benutzung von Kristallviolett bestimmt. Die gemessenen Effekte werden wahrscheinlich durch die stark polaren Wechselwirkungen zwischen den Carboxygruppen der beiden Polymeren verursacht.
    Notes: The photo-induced radical polymerization of acrylamide has been investigated in combinations of two polymers containing carboxy groups. The kinetic parameters of this polymerization, measured with a calorimetric method, depend on the proportion of the two polymers in the system. In mixtures with the lowest glass transition temperature, the polymerization rates are the highest. These transition temperatures have been determined with a special fluorescene technique using crystal violet as probe. Presumably, the effects measured in the systems are based on the strong polar interactions between the carboxy groups of both polymers.
    Additional Material: 5 Ill.
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  • 63
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 201 (1992), 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: Die Bedingungen für die Synthese von 2-(2-Carboxybenzoyloxy)ethylmethacrylat (CEM) durch Alkoholyse von Phthalsäureanhydrid (PA) mit 2-Hydroxyethylmethacrylat (HEMA) wurden optimiert. Für die nicht katalysierte, die basen- und säurekatalysierte Reaktion von PA mit HEMA bei 50°C wurden als Geschwindigkeitskonstanten zweiter Ordnung die Werte 4,74 × 10-6, 14,5 × 10-5 bzw. 5,4 × 10-5 dm3 mol-1 s-1 ermittelt. Unter Säurekatalyse fand außerdem eine weitgehende Veresterung von CEM unter Bildung von Bis(2-methacryloyloxyethyl)phthalat statt. Für die Emulsionspolymerisation von CEM (Wasserlöslichkeit 13 mmol dm-3 bei 25°C) in Gegenwart von Natriumdodecylsulfat als Emulgator mit dem Initiatorsystem K2S2O8 - K2S2O5 wurde nach dem Emulsionspolymerisationsmodell von Smith-Ewart eine Wachstumsgeschwindigkeitskonstante von 610 dm3 mol-I s-l bestimmt. Die Copolymerisationsparameter und Q- und e-Werte von CEM für die radikalische Copolymerisation von CEM (M1) mit Butylmethacrylat (M2) betragen r2 = 0,85, r2 = 0,75, Q = 0,82 und e = 0,4.
    Notes: Conditions of the synthesis of 2-(2-carboxybenzoyloxy)ethyl methacrylate (CEM) by the alcoholysis of phthalic anhydride (PA) with 2-hydroxyethyl methacrylate (HEMA) were optimized. For the uncatalyzed, base-catalyzed and acid-catalyzed reaction of PA with HEMA at 50°C the respective second-order rate constants were 4.7 × 10-6, 14.5 × 10-5 and 5.4 × 10-5 dm3 mol-1 s-1. Also, a consecutive esterification of CEM with formation of bis(2-methacroyloxyethyl)phthalate took place under conditions of the acid catalyzed reaction. The emulsion polymerization of CEM (solubility in water 13 mmol dm-3 at 25°C) was carried out in the presence of sodium dodecyl sulfate as the emulsifier and of the redox initiation system based on K2S2O8-K2S2O5. Using the Smith-Ewart model of emulsion polymerization, the growth rate constant of CEM, kp = 610 dm3 mol-1 s-1 at 25°C was determined. The monomer reactivity ratios and Q and e values determined for the radical copolymerization of CEM (M1) with butyl methacrylate (M2) were r1 = 0.85, r2 = 0.75, Q = 0.82, and e = 0.4.
    Additional Material: 6 Ill.
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  • 64
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular theories of rubberlike elasticity are surveyed, starting with the earliest attempts carried out in the 1930's and ending with work still very much in progress. The models are variously based on phenomenological arguments, affinely-deforming networks, phantom networks, constrained junctions, constrained chains, slip-links, molecular tubes, van der Waals concepts, or rotational isomeric chains. Most of the theories are analytical, but some involve computer simulations based on Monte Carlo methods. The theories are generally for networks of Gaussian chains, but there have been significant advances for non-Gaussian networks as well, and these are particularly important with regard to a better understanding of ultimate properties. The major outstanding problem on the theory side, however, seems to be a quantitative treatment of chain entanglements.There have also been numerous advances on the experimental side. These include preparation of model networks of known structure, accumulation of elasticity data for deformations other than the much-studied simple elongation, development of new characterization techniques (such as fluorescence polarization, and X-ray and neutron scattering), investigation of the phenomenon of gel collapse, borrowing of ideas from the area of bioelastomers, and preparation of novel reinforcing fillers.
    Additional Material: 8 Ill.
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  • 65
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semi-IPN's of different composition, based on linear poly(methyl vinyl ether) (PVME) and crosslinked polystyrene are studied using stress and birefringence measurements in simple elongation. From quasistatic stress-strain experiments at constant T(experiment)-Tg, it can be deduced that the stress results only from the deformation of the polystyrene network, while the PVME chains do not contribute to the macroscopic stress. The concentration dependence of the network modulus is adequately described by the rubber elastic theories. In the concerntration range between 20 and 60 wt.-% of polystyrene the obtained optical anisotropy parameter is different to the value of pure polystyrene and the absolute value decreases with increasing PVME content. Based on the mechanical response and the stress-optical behaviour of a radically crosslinked pure PVME network possible explanations for the observed behaviour of semi-IPN's are discussed.
    Additional Material: 9 Ill.
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  • 66
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sulfur crosslinking systems are well established for curing of rubbers containing olefinic bonds and are well optimized for various processing and end product requirements. This is achieved by the clever selection of accelerator or their combinations or varying sulfur to accelerator ratio. This ratio defines primarily the structure and density of the sulfur crosslinks. Semi efficient crosslinking systems allow in NR as in SBR best compromise of properties with respect to processing, static and dynamic behaviour and ageing. In NR the structure of the crosslinks contrary to SBR has a larger influence on dynamic crack propagation. Polysulfidic crosslinks are preferred for higher tensile strength, tear and fatigue resistance.Great challenges for accelerated sulfur crosslinking exist to meet new ecological and toxicological requirements such as avoidance of nitrosamines in rubber industry. The present work shows that there is a potential for new developments in the classical sulfur vulcanization to satisfy the present needs and meet the future challenges.
    Additional Material: 13 Ill.
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  • 67
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tensio-active properties of different types of diesters can be used to synthesize two-dimensional model networks at the interface between oil and water. We have systematically studied rubber-elastic, glass-like and transient membrances which are stabilized and crosslinked by physical or chemical contacts.The adsorption process of the monomeric diesters was investigated by measuring the interfacial tension at the boundary between oil and water. The experimental results can be interpreted on the basis of the “Szyskowski”- equation which holds for monomolecular films under ideal conditions. From the measured values of the interfacial tension it is possible to determine the surface concentration. The polymerization process occurs through radical-reactions which can be initiated by UV-irradiation.We have systematically studied the kinetics of surface gelation by measuring the two-dimensional shear modulus as a function of the reaction time. The experimental results can be interpreted in the framework of simple reaction mechanisms. The quantitative analysis of the experimental data allows to evaluate many details of the photo-reaction as the free radical concentration. the number of linear chains and the rate constant of the cross-linking process.The two-dimensional sol-gel transition can easily be described in the framework of percolation theories which were proposed by Stauffer and de Gennes. According to these models, one expects to find a steep increase in the elastic modulus after passing the gel point. The two-dimensional percolation exponent, determined in our experiments, agrees very well with the calculated result of 4/3. This holds for rubber-elastic and glass-like membranes.Rubber-elastic, cross-linked films exhibit interesting features, which can be explained by simple models. The shear modulus depends upon the surface concentration of elastically effective chains. The interfacial polymerization is not restricted to flat surfaces, and the corresponding films can be used for the stabilization of different types of emulsions. Oil droplets which are surrounded by cross-linked membranes, from simple systems which exhibit interesting properties of biological cells. The microcapsules can, for instance, be used in order to simulate blood flow in living vessels. We have measured the deformation process and the aggregation behavior of these microcapsules in Couette flow under a microscope, and we have investigated the influence of the membrane elasticity on the flow behavior of these emulsions. The data, thus obtained, can be compared with the particle behavior of rigid spheres and deformable liquid drops. The rheological properties of these artificial cells are useful to get a clearer picture of the complicated flow processes which occur in biological systems.
    Additional Material: 8 Ill.
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  • 68
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Todays tires are formed from a multitude of very different components of which polymers constitute ca. 60%. The report centers on some developments in elastomers, viz. natural rubber (NR) polybutadiene (BR) and polyisoprene (IR), the various styrene-butadiene rubbers (SBR) and their blends and some other copolymers. On the part of polymeric organic fibers, only a brief glance is thrown on newer polyamides.
    Additional Material: 15 Ill.
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  • 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: The conditions of an emulsion polymerization (polymerization rate, emulsifier system) influence the concentration of the regulator within the latex particles. All this effects the molecular weights, molecular weight distributions, chain branchings, and gel contents of polymers. The frequency dependence of the storage modulus and loss modulus of polymers and their rubber networks were measured and discussed in connection with their structure parameters.
    Notes: Die Veränderung der Polymerisationsbedingungen (Polymerisationsgschwindigkeit, Emulgatorsystem) beeinflußt die Konzentration der Regler im Latexteilchen und damit die Molmassen, die Molmassenverteilung, Kettenverzweigungen und Gelgehalte der Polymeren. Die Speicher- und Verlustmodul-Frequenzabhängigkeiten für die Kautschuke und ihre Netzwerke wurden aufgenommen und im Zusammenhang mit den Strukturparametern diskutiert.
    Additional Material: 9 Ill.
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  • 70
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to ascertain structure-property-relationships of poly(butadiene-g-styrene) copolymers the preparation of these model copolymers has been carried out by the anionic copolymerization of butadiene and styryl-terminated polystyrene macromonomers in solution. With this method it is possible to determine exactly the graft length and to vary the graft density or the polystyrene content. Besides, the products are almost free of homopolystyrene and are not cross-linked. The almost statistically regular distribution of the polystyrene grafts along the backbone chain has been achieved by the application of the initiator system: sodium tert-butoxide/n-butyl lithium.The materials have been tested by the determination of selected mechanical characteristic values. They yielded the following relationships: maxima of properties (stress strain, hardness, elasticity) already appear in the range of molar mass of the PS-grafts from 5 000 to 8 000 g/molethe position and the width of the maxima depend on the PB/PS-phase ratiowith increasing PS-content, the tensile strength increases up to about 20 MPa at nearly 40 %the hardness of the products is strongly and linearly influenced by the PS-contentthe elasticity shows a maximum in the range of 20 to 25 % PS-content.All in all, the materials exhibit good thermoelastoplastic behaviour in comparison with the SBS-three or -star block copolymers.Electron microscopic examination of the products result in phase separation phenomena.
    Additional Material: 11 Ill.
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  • 71
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The properties of filled elastomers are obviously dependent on the nature of the iller/matrix interface. However, one can expect the physical or chemical interactions which are able to take place between the surface of the solid and the polymeric matrix to be controlled by the surface activity of the filler. In this respect some of the methods, which have been devised for the characterization (identification and titration of surface functional groups, measurement of the surface free energy, determination of the distribution functions of energies,…) and the monitoring (activation, deactivation,…) of he surface reactivity of reinforcing fillers, are used in view of the establishment of relationships with the reinforcing ability of the corresponding fillers.
    Additional Material: 3 Ill.
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  • 72
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: HNBR rubbers, which are made by selective hydrogenation of the olefinic bonds of NBR rubbers, have been developed, because they show improved resistance towards heat and chemicals. In this study, two other properties are discussed that arise from the fact that HNBR rubbers are fairly alternating copolymers of unpolar butylene and polar acrylonitrile units: At intermediate compostions, HNBR rubbers form homogeneous blends with PVC, and near the symmetric composition they exhibit strain-induced crystallisation. The thermal transitions of the HNBR rubbers and their miscibility with PVC were analyzed, as well as the crystallisation and the stress-strain behaviour of a HNBR of symmetric composition.
    Additional Material: 12 Ill.
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  • 73
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The utilization of rubber mixtures is to achieve a desired combination of properties and performance spectrum of elastomers is nowadays of a considerable technological and economical importance. The successful implementation of this concept requires the knowledge of the factors governing both the phase behaviour of rubber blends and the morphology of phase separated blends. Thermodynamic theories referring to miscibility and phase separation of polymers are briefly reviewed, with a specific focus on nonpolar polymers with high chain flexibility. It can be shown on the simple lattice that this theory works qualitatively for these systems. Reliable predictions are questionable due to the lack of equation of state parameters for the polymers of interest and temperature and concentration dependence of the interaction parameter χ.Concerning the morphology of phase separated rubber blends the main influences governing the structure of the entire system (i) the interfacial tension, (ii) the viscosity of the matrix (iii) and the shear stress are discussed in more detail. It has been pointed out that for technological usability a better knowledge about the interdiffusion of polymers and the properties of the interphase, built in this would be not only of scientific interest but also beneficial for high performance elastomer blends. It would also be useful to know more about the dispersion of polymers at short mixing times and elevated temperatures. Because it has been considered until recently that polymer miscibility occurs only if strong specific segmental interaction are involved, emphasis was dedicated to oligomer/rubber- and rubber/rubber-systems which exhibit miscibility and phase transitions through a convex coexistence curve into a homogeneous region. Consequences of phase transitions at high mixing temperatures for specific tire applications are suggested.
    Additional Material: 20 Ill.
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  • 74
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermotropic poly(diethylsiloxane) is a new type of the mesophase elastomers. Mechanical Measurements in extension and contraction and stretching calorimetric measurements of heat and energy effects resulting from extension and contraction were combained with thermo-mechanical measurements under constant loads and opto-mechanical measurements to obtain molecular understanding of the deformational behaviour of these mesophase rubber-like materials in a wide temperature range with particular emphasis on the temperature range of the mesophase stability as a function of extension. The stress-strain curves of semi-mesomorphic films resemble the strain-strain behaviour of crystalline polymers with a very low degree of crystallinity. During stretching of amophous films the strain-induced mesophase occurs. The influence of stress on the temperature range of the stability of the strain-induced mesophase is very strong due to a very small heat of isotropization. The cyclic deformations of the mesophase elastomers are accompanied by the necking-renecking phenomena resulting from the train-induced mesophase formation on stretching followed by the immediate isotropization during contraction. Some potential practical applications of the mesophase elastomers are considered.
    Additional Material: 9 Ill.
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  • 75
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 1-1 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution structure of the photodimer cis, syn-dUp [ ]dT is derived with the aid of the genetic algorithm. The conformational space available for the molecule is sampled efficiently using the computer program DENISE and tested against a set of constraints available from nmr experiments. The dominant conformation in solution found with this approach can be described by the following combinations of sugar-phosphate backbone torsion angles: ε (t), ζ(t), α(+), β(-ac), and γ(t). The conformation of the sugars and glycosidic torsion angles are S type and syn, respectively. The cyclobutane ring and pyrimidines are puckered. In addition, other conformations that exist in equilibrium with the first are found. It is concluded that the cyclobutane-pyrimidine system is rigid, whereas the sugar-phosphate backbone is flexible. The solution structures are compared with the crystal structure of the strongly related cyano-ethyl ester of cis, syn-dTp [ ]dT.
    Additional Material: 6 Ill.
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  • 77
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The analysis of the factors that control the helical folding of Aib-rich peptides is extended to include sensitivity to sequence patterns, and in particular the presence of contiguous non-Aib α-mono-alkylated residues. The distinct hydrogen-bonding network of the 310-helix, as contrasted with that of the competing α-helical structure, is explicitly incorporated into a theoretical model for the 310-helix/α-helix equilibrium constant for a given peptide. Finite length effects and the “extra” intrahelical hydrogen bond of the 310 form are expressed naturally as a result of this loop analysis. This semiempirical model captures all the established features of existing empirical rules for helical conformational transitions in Aib-rich sequences, as well as the recently detected helical transition induced solely by sequence permutation.
    Additional Material: 5 Ill.
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  • 78
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 79
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 3-10 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general formula is derived for the relation between the pair correlation function and the histogram of interparticle distances in small nonuniform systems. The formula is applied to random packings of spheres in a spherical container, which are generated by a Monte Carlo method. When measured properly, the resultant correlation functions are very similar to ones in bulk systems with the same volume fraction of particles. In contrast, the density is very nonuniform as a function of distance from the center of the container. The variation is an order of magnitude for the number density of particle centers, or several fold for the occupied volume fraction. It is described how these results can be used to analyze the forces that determine protein structure.
    Additional Material: 5 Ill.
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  • 80
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extended simulated annealing process (ESAP) has been developed in order to obtain an ensemble of conformations of a peptide segment from a protein fluctuating at a given temperature. The annealing process was performed with a fast Monte Carlo method using the scaled collective variables developed by Noguti and Gō. The system was divided into two parts: one consists of one or more peptide segments and is flexible around the main-chain and side-chain torsional angles; the other represents the rest of the molecule and was maintained fixed at the atomic positions determined by x-ray experiments. The target function included the nonbonding atomic interactions and a distance function to anchor the N and C terminal ends of each segment to the fixed part. Three systems of complementary determining regions (CDR) of antibodies were tested and compared to x-ray data: L2 loop (7 residues) of the light chain of α-type Bence-Jones protein, H1 and the H2 loops (14 residues) of McPC603, and H1 and H2 loops (12 residues) of HyHEL-5. Each state of CDR conformations was characterized at room temperature by the average of their coordinates (average conformation) and the internal energy. With a limited number of annealing processes (10), starting from the extended conformation, we have obtained states with conformations close to the observed x-ray structures, from 1.1 to 1.7 Å root mean square deviation (rmsd) of main-chain atoms depending on the system. These states were identical or within 0.25 Å rmsd of those of lowest internal energy. For unknown CDR structures the criteria of lowest internal energies from ESAP can be used to predict hypervariable loop structures in antibodies with an accuracy comparable to other methods.
    Additional Material: 4 Ill.
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  • 81
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 97-106 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structures of 7-oxo-1-azabicyclo[3.2.0] heptane and its 4-oxa, 3-ethylene-4-oxa, and 3-ethylene-6-methyl-4-oxa derivatives, and of 8-oxo-1-azabicyclo[4.2.0] octane and its 5-oxa derivative, were studied by ab initio methods. Conformations were refined without constraints using the 4-21G and the 4-21G* basis sets, and energies and charge distributions were improved by single-point 6-31G*/4-21G* calculations. The results are interpreted in terms of structural trends related to β-lactamase inhibitor capability.
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  • 82
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 85-96 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interactions between the positively charged neuropeptides substance P (SP), bradykinin (BK), and zwitterionic Met-enkephalin (ME) neuropeptides, and negatively charged SDS and zwitterionic lysophosphatidylcholine (LPC) membrane model systems, have been investigated using one- and two-dimensional nmr experiments. Proton longitudinal relaxation studies were used to characterize these interactions as intrinsic or extrinsic. An extrinsic interaction are similar to those observed for extrinsic membrane proteins. An intrinsic interaction are similar to those observed for intrinsic membrane proteins, and would require that the hydrophobic residues penetrate or insert into the hydrophobic core of the membrane. The interactions between both SP and BK and SDS, based on nmr results, may be characterized as intrinsic, and the interaction between ME and SDS may be characterized as extrinsic. Two-dimensional nuclear Overhauser enhancement spectroscopy experiments proved the insertion of the phenylalanine residues on both SP and BK into the hydrophobic core of SDS micelles. The interaction between SP and BK with LPC based on nmr results are characterized as extrinsic, with the interaction between ME and SDS characterized as weakly intrinsic.
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  • 83
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational behavior of the synthetic peptide, Boc-Gly-Val-Gly-Gly-Leu-OMe, containing the X-Gly-Gly and Gly-Gly-X (X = Val or Leu) repeating sequences and constituting a fragment of elastin was investigated by molecular mechanics and molecular dynamics (MD) simulation. The results suggest that, irrespective of the approximations used, the molecule shows a manifold of low energy conformations characterized by γ-turns and type II β-turns. Furthermore, MD simulations point out a conformational floppiness due to very low barriers between different conformations. Experimental CD measurements in a virtually apolar medium (dioxane - ε = 2.209), which better mimics the vacuum conditions of the simulation, support the theoretical results. The general emerging picture, indicating the molecule as characterized by a combination of flexibility with conformational preferences, is in agreement with previous experimental findings and enriches of new aspects the description of the microscopic behavior of this molecule suggesting more detailed interpretation of previous data.
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  • 84
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 209-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several harmonic models of protein fluctuations are used to calculate the heat capacity. They get the spectral density of conformational modes from inelastic neutron scattering, normal mode calculations, or macroscopic elasticity (Debye model). It is assumed that the low-frequency spectral density depends only weakly on temperature and protein species. The Debye model predicts temperatures below which modes are primarily in their ground states: 10 and 80 K for the lattice and conformational modes, respectively. The models differ most below 100 K. The mode calculations yield the most accurate predictions, though all three models are within twofold of the data. The heat capacity has the power law form aTb for T 〈 30 K. The experimental b's of proteins are 1.6-1.8, and the theoretical, 1.1-1.3. One possible explanation for the discrepancy is the occurrence of transitions between discrete conformations. All of the models approach the measured data in the range 100-200 K. They are very similar above 200 K, where the heat capacity includes significant contributions from bond stretching and bending. This masks the possible anharmonic behavior of the conformational modes. Hydration substantially increases the heat capacity above 200 K. This effect seems to be a consequence of conformational transitions that have higher energy than the ones seen with low hydration. The analysis also predicts that denaturation with constant hydration produces a negligible increase of heat capacity. The larger increment in solution arises from the different hydration of the folded and unfolded states, and is responsible for the existence of cold denaturation. This phenomenon is thus predicted not to occur when the hydration is constant.
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  • 86
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preferred conformations of ribo and deoxyribo α-nucleosides and β-nucleotides, the stereoisomers of the naturally occurring β-isomers, are worked out by minimizing the conformational energy as a function of all the major parameters including the sugar ring conformations along the pseudorotation path. The results of the studies bring out certain distinct conformational features that are at variance with their β counterparts. The range of glycosyl conformations are found to be not only quite restricted here but favor predominantly the anti conformation. The syn glycosyl conformation for the entire region of α values are found to be energetically less favorable, with the barrier to anti ⇆ syn interconversion being higher especially in α-ribonucleosides. The energetically preferred range of pseudorotation phase angles (P) is also considerably restricted and P values corresponding to the C1′-exo range of sugars are highly unfavorable for α-nucleosides, in sharp contrast to the broad range of sugar ring conformations favored by β-isomers. While both trans ≃ 180° and skew ≃ 270° conformations around the C3′-O3′ (φ′) bond are favored for β-3′-nucleotides with deoxyribose sugars, ribose sugars seem to favor only the skew values of φ′. Most interestingly and in sharp contrast to β-stereoisomers, an energy barrier is encountered at P values corresponding to O4′-endo sugars. This suggests that the possible sugar pucker interconversion between C2′-endo/C3′-exo and C3′-endo/C2′-exo in a-anomers could take place only through the O4′-exo region. Likewise the possible path of anti ⇆ syn interconversion in α-nucleosides is not via high anti, in sharp contrast to α-nucleosides. These observations should be borne in mind while assigning the sugar ring conformers in α-nucleosides and those containing them from nmr investigations. Comparison of the results with α-anomers seem to suggest on the whole a lack of conformational variability or the restricted nature of α-stereoisomers. This could be one of the reasons for its nonselection in the naturally occurring nucleic acids.
    Additional Material: 12 Ill.
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  • 87
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    Biopolymers 32 (1992), S. 271-276 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In previous work, it was shown that poly [d(AC) · d(GT)] could be forced into the Z form by strong dehydrating conditions, provided EDTA was not present. Presumably multivalent impurities were also necessary for the transition. In order to gain control over the B to Z transition for this DNA, we carefully removed all divalent contaminants from the sample and asked the obvious question: What ions are necessary for the transition under dehydrating conditions? We systematically investigated the effect of various multivalent ions. The common contaminants Ca2+, Mg2+, and Fe3+ will not cause the transition, but Co2+ and Ni2+ facilitate the transition, undoubtedly because of their well-known propensity to bind to purine N7. Since the transition also depends on the synergistic dehydrating action of sodium perchlorate and ethanol, we include CD spectra for the independent variations of these two factors. In addition, vacuum-uv CD spectra for the A form and various B forms of poly [d (AC) · d (GT)] are presented for the first time.
    Additional Material: 7 Ill.
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  • 88
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    New York : Wiley-Blackwell
    Biopolymers 32 (1992) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 89
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    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 293-301 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have examined intramolecular hydrogen bonding in four homologous compounds, N-acetyl-, N-propionyl-, N-i-butyryl-, and N-pivaloyl-proline-methylamide, in methylene chloride, by means of 1H-nmr and ir measurements. At room temperature, the major trans conformer of MeCO-Pro-NHMe appears to be approximately 68% intramolecularly hydrogen bonded, the trans conformers of EtCO-Pro-NHMe and i-PrCO-Pro-NHMe are approximately 75% intramolecularly hydrogen bonded, and t-BuCO-Pro-NHMe is approximately 50% intramolecularly hydrogen bonded. Thus, the internally hydrogen-bonded state (C7 or γ-turn) is significantly less populated for the N-pivaloyl compound than for the other three molecules in this series. Variable temperature measurements indicate that for each proline derivative there is very little enthalpic difference between the intramolecularly hydrogen-bonded and nonhydrogen bonded states of the trans rotamer. Changing the N-terminal acyl group also affects intramolecular hydrogen bonding (including β-turn formation) in end-blocked Pro-Gly dipeptides.
    Additional Material: 4 Ill.
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  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Normal mode calculations have been done on 92 disulfide bridges in 25 known protein structures in order to correlate the SS stretch frequency with the CCSS dihedral angle. It is possible to classify the frequencies into four major categories, which provide a more detailed classification scheme than previously proposed from dialkyl disulfide correlations.
    Additional Material: 3 Tab.
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  • 91
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    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 347-351 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Prediction of the structures of long polypeptides and small proteins has been carried out using conformational energy calculations. These calculations can be applied to large proteins if structured regions of their sequences can be identified. Three different approaches to identifying such sequences are presented. First, sequences of five or more contiguous hydrophobic residues tend to nucleate α-helices. Second, peptide sequences from parent proteins that have the same biological activities as the parent proteins are highly structured. Third, structured synthetic peptide segments from proteins inhibit the folding of the parent proteins by competing with the corresponding segment of the protein chain for associating with complementary regions. Examples of each of these approaches are presented.
    Additional Material: 2 Ill.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Energy refinement of the structure of a linear peptide, hirudin56-65, bound to thrombin was carried out using a conformational search method in combination with restrained minimization. Five conformations originated from nmr data and distance geometry calculations having a similar global folding pattern but quite different backbone conformations were used as the starting structures. As a result of this approach, a series of low-energy conformations compatible with a set of upper and lower bounds of interproton distances determined from transferred nuclear Overhauser effects were found. A comparison among the lowest energy conformations of each run showed that the combination of energy refinement plus distance constraints led to a very well-defined structure for both the backbone and the side chains of the last 7 residues of the polypeptide. Furthermore, the low-energy conformations generated with this technique contain a segment of 310-helix involving the last 5 residues at the COOH terminal end.
    Additional Material: 3 Ill.
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  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural studies of globular proteins by nmr can be enhanced by the use of isotope enrichment. We have been working with proteins enriched with 15N, and with both 15N and 13C. Due to the isotope enrichment we could assign several large proteins with up to 186 residues and could address structural questions. Furthermore, we can accurately measure heteronuclear and homonuclear vicinal coupling constants. This involves in part multidimensional multiple resonance experiments. This is important for characterization of minor conformational changes caused by mutations. We have also made use of isotope enrichment to study the internal mobility of proteins. We also have developed novel methods for measuring accurately 15N relaxation parameters, in particular transverse relaxation rates. This has led us toward a method for directly mapping spectral density functions of the rotational motions of N-H bond vectors in proteins. The protein systems that are discussed include the unlabeled proteins kistrin and cytochrome c551, and the labeled proteins eglin c, a flavodoxin, and human dihydrofolate reductase.
    Additional Material: 7 Ill.
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  • 94
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fusion of enveloped viruses to target membranes is promoted by certain viral fusion proteins. However, many other proteins and peptides stabilize bilayer membranes and inhibit membrane fusion. We have evaluated some characteristics of the interaction of peptides that are models of segments of measles and influenza fusion proteins with membranes. Our results indicate that these models of the fusogenic domains of viral fusion proteins promote conversion of model membrane bilayers to nonbilayer phases. This is opposite to the effects of peptides and proteins that inhibit viral fusion. A peptide model for the fusion segment of the HA protein of influenza increased membrane leakage as well as promoted the formation of nonbilayer phases upon acidification from pH 7-5. We analyze the gross conformational features of the peptides, and speculate on how these conformational features relate to the structures of the intact proteins and to their role in promoting membrane fusion.
    Additional Material: 3 Ill.
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  • 95
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    Biopolymers 32 (1992), S. 341-346 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of three fragments of uteroglobin in aqueous solution and in the presence of SDS micelles is described. Two of these fragments correspond to helix II and helix III of uteroglobin, the crystal structure of which is made of four helices. The third peptide comprises helices II and III, with the connecting β-turn. While helix II does not interact strongly with the micelles, helix III adopts a rather clear α-helix in this system. The elongation of helix III with the addition of helix II at the N-terminus somewhat stabilizes the ordered structure. It is possible that the β-turn found in the crystal is also present in solution.
    Additional Material: 5 Ill.
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  • 96
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    Biopolymers 32 (1992), S. 327-334 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general approach is described for measuring homo- and heteronuclear spin coupling constants in polypeptides and small proteins. This method uses selective magnetization transfer to generate cross peaks similar to exclusive correlated spectroscopy (E.COSY) and a large direct spin coupling (1J) in one dimension to “pull apart” cross-peak components by frequencies much larger than the resonance line width. A general description of this method is presented, along with a brief discussion of spin topology and relaxation effects that must be considered in designing multidimensional nmr pulse sequences for measuring vicinal coupling constants. The principles are demonstrated in designs of several two-dimensional nmr experiments for determining coupling constants in polypeptides and proteins. These include experiments for measuring 3J(HN-Hα), 3J(Hi-1α-15Ni), 3J(15N-Hβ), and 3J(Hα-Hβ) coupling constants, which depend on the polypeptide dihedral angles φ, ψ and χ1. Multidimensional nmr experiments developed with this approach will allow measurements of many vicinal coupling constants in peptides, proteins, and other molecules. Coupling constants measured in these spectra can be used to determine backbone and side-chain conformations, to obtain stereospecific resonance assignments of prochiral atoms, and to characterize conformational distributions of dihedral angles. Combined with information obtained from nuclear Overhauser effect measurements, these data will provide more precise determinations of protein solution structures by nmr spectroscopy.
    Additional Material: 8 Ill.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Many neuropeptides exert their action between the presynaptic vesicles and postsynaptic transmembrane receptors, crossing different layers of specialized cytoplasm. Biomimetic media usually employed to study bioactive peptides do not reproduce the physico chemical environment of cytoplasm - in particular, the high viscosity of this biological fluid. Here we describe a Conformational study of a δ-selective opioid peptide, deltorphin I, at variable temperatures in several biocompatible media characterized by varying values of viscosity and dielectric constant. It was found that only viscosity, among these parameters, induces ordered conformations; that is, it acts as a Conformational sieve. This finding suggests that the high viscosity of the intersynaptic fluid contributes, in addition to the membrane catalysis proposed by Schwyzer, in overcoming the so-called entropic barrier to the transition state of peptide-receptor interaction by selecting ordered conformations prior to receptor interaction.The folded conformer found in the 80 : 20 (v : v) DMSOd6/H2O cryoprotective mixture at 265 K has a shape consistent with those of rigid nonpeptidic opiates.
    Additional Material: 3 Ill.
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  • 98
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    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 391-397 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this work we describe calcium binding to two synthetic 34-residue peptides, determined by 1H-nmr spectroscopy. The peptides investigated, SCIII and SCIV, encompass the calcium-binding sites III and IV, respectively, of troponin-C. In the absence of calcium it has previously been shown that each of these peptides possesses little regular secondary structure. Further, the 1H-nmr spectra of an equimolar mixture of both of these apo-peptides (apo-SCIII/SCIV) shows that little interaction occurs between peptides. Upon calcium binding the spectral changes that occur to SCIII/SCIV are consistent with global conformational changes in both peptides. We have shown previously that these conformational changes are a product of calcium binding to SCIII and SCIV to form a two-site heterodimer Ca2-SCIII/SCIV. It is proposed that this calcium-induced folding proceeds via calcium binding to SCIII to form Ca-SCIII, peptide association with apo-SCIV to form the heterodimer Ca-SCIII/SCIV, and calcium binding to form Ca2-SCIII/SCIV. The dissociation constants involved in this pathway, K1, Kd, and K2, respectively, have been determined by stoichiometric calcium titration of SCIII/SCIV, monitored by 1H-nmr spectroscopy. Using this procedure it has been determined that K1 = 3 μM, Kd = 10 μM, and K2 = 2 μM.
    Additional Material: 3 Ill.
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  • 99
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    New York : Wiley-Blackwell
    Biopolymers 32 (1992), S. 411-417 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Starting from L-tyrosine (Tyr) and its metabolites desaminotyrosine (Dat) and tyramine (Tym), four structurally related model dipeptides were prepared: Dat-Tym (neither N- or C-terminus present), Z-Tyr-Tym (N-terminus protected by benzyloxycarbonyl), Dat-Tyr-Hex (C-terminus protected by a hexyl ester group), and Z-Tyr-Tyr-Hex (both N- and C-termini present, protected by benzyloxycarbonyl and hexyl ester, respectively). The model dipeptides were used as monomers in the synthesis of polycarbonates. The polymerization reaction in the presence of either phosgene or triphosgene proceeded via the phenolic hydroxyl groups. Polymers with molecular weights of 105,000-400,000 da (by gel permeation chromatography, relative to polystyrene standards) were obtained. The physicomechanical properties (solubility, mechanical strength, glass transition and decomposition temperature, processibility) of the polymers were determined, and an attempt was made to correlate the polymer properties with the nature of the N- and C-terminus protecting groups. The presence of the urethane bond at the N-terminus protecting group was found to reduce solubility, ductility, and processibility, probably due to interchain hydrogen bonding. The presence of a C-terminus alkyl ester group increased solubility and processibility. Thus, the most promising candidate polymer for biomedical applications was obtained from Dat-Tyr-Hex, the monomer carrying a C-terminus protecting group only. Since very similar results had recently been obtained for a series of structurally related polyiminocarbonates, the structure property correlations seem to be generally valid.
    Additional Material: 2 Ill.
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  • 100
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    Biopolymers 32 (1992), S. 427-433 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The constitution and configuration of Ro 09-0198 (cinnamycin) have been determined in DMSO. Further investigations in aqueous solution, in SDS micelles and in a lipid bilayer have been done to study the influence of different environments on the conformation of the peptide. It turned out that in spite of the polycyclic structure of the molecule, the conformation is drastically changed going from water to SDS micelles. Ro 09-0198 orients itself in lipid bilayers as expected from its amphiphilic structure. According to a nuclear Overhauser effect spectroscopy experiment under magic angle spinning (MAS) conditions, the molecule is incorporated into the membrane with its hydrophobic part inside the bilayer.
    Additional Material: 2 Ill.
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