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  • 1
    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 this part properties and efficiency of the developed model1,2 are discussed. A variation of the parameters shows that vigorous effects are caused by the effective aggregation. All calculations show that at low conversion there are little temporal steps between the sequential aggregation steps. In the range of 5% to 20% conversion the velocity of aggregation decreases and the aggregative stability agrees with experiences given in the literature. It is shown that the calculated results are in agreement with the experimental results and therefore the presented model is a suitable possibility to describe the formation of some PVC-morphology properties.
    Notes: In der vorliegenden Arbeit werden die Eigenschaften des früher1,2 entwickelten Modells untersucht und diskutiert. Die Variation der Modellparameter zeigt einen großen Einfluß der Aggregationsprozesse auf die Subkornmorphologie. Bei niedrigen Monomerumsätzen ist das Zeitintervall zwischen zwei aufeinanderfolgenden Aggregationsschritten sehr klein, so daß für das Teilchenwachstum die Geschwindigkeit der Aggregation der Unterstrukturen entscheidend ist. Im Bereich zwischen 5% und 20% Monomerumsatz sinkt die Aggregationsgeschwindigkeit sehr stark, so daß für das Teilchenwachstum zunehmend die Polymerisationsreaktion an Bedeutung gewinnt. Aggregative Stabilität wird nach dem Modell für einen Teilchengrößenbereich erhalten, der sich in Übereinstimmung mit experimentellen Daten aus der Fachliteratur befindet. Die berechneten Teilchengrößen entsprechen ebenfalls den in der Literatur publizierten experimentellen Werten, so daß das Modell eine gute Grundlage für die Beschreibung einiger morphologisch bestimmter Polymereigenschaften bildet.
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  • 2
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 21-34 
    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 unidirektionale Verbundwerkstoffe aus Novolakharz mit Kohlenstoff-Fasern gemäß der Prepreg-Methode verarbeitet. Das Novolakharz wurde durch Polymerisation von Phenol mit Formaldehyd (Mol-Verhältnis 1 : 0,82) und Oxalsäure als Katalysator (1,5 Gew.-% von Phenol) hergestellt. Die Härtung des Novolakharzes wurde mit Hexamethylentetramin (Hexa) durchgeführt, während das geeignete Verhältnis durch die IR-Spektroskopie bestimmt wurde.Es wurden Proben aus Novolak/Hexa (Gew.-Verhältnis 14: 1), verstärkt mit kommerziellen Kohlenstoff-Fasern, unter verschiedenen Bedingungen (z. B. verschiedene thermische Programme und verschiedene Verhältnisse von Novolakharz : Kohlenstoff-Fasern) hergestellt. Die mechanischen Eigenschaften der hergestellten Proben (wie Biegefestigkeit, Zugfestigkeit, usw.) wurden bestimmt, und ihre Struktur wurde mit Hilfe der Elektronenmikroskopie untersucht.Mit zunehmendem Volumenverhältnis der Kohlenstoff-Fasern werden nicht nur alle mechanischen Eigenschaften des verstärkten Materials verbessert, sondern auch sein Nutzungsgrad nimmt zu, und die Herstellungsbedingungen üben einen größeren Einfluß aus. Die mit dem gleichen Verhältnis von Kohlenstoff-Fasern (z. B. 15 Vol.-%) hergestellten Proben weisen mit zunehmendem Härtungsgrad des Novolaks verbesserte mechanische Eigenschaften auf. Der Häirtungsgrad des Novolaks während der Anfangsphase (Gel-Zeit) als auch während der Endphase (Nachhärtung) kann mit Hilfe der IR-Spektren des härtenden Novolaks verfolgt werden, während der Härtungsgrad der Zwischenphase nur indirekt aus den Werten der mechanischen Eigenschaften der entsprechenden Proben bestimmt werden kann.Aus der Korrelation zwischen den Herstellungsparametern und den mechanischen Eigenschaften der Proben ergeben sich optimale Bedingungen für die Verarbeitung in der Wärmepresse zur Herstellung von mit Kohlenstoff-Fasern verstärkten Novolakharzen (1. Phase: T1 = 125-145°C, t1 = 20 min - 1 h, ohne Druck; 2. Phase: T2 = 180-195°C, t2 = 40 min, P2 ≃ 1,5 kN /cm2).
    Notes: Unidirectional composite materials of novolac resin with carbon fibers were fabricated according to the prepreg method. Novolac resin was prepared by polymerization of phenol with formaldehyde (mole ratio 1 : 0.82) in the presence of oxalic acid as catalyst (1.5 wt.-% to phenol). The curing of novolac resin was performed with hexamethylenetetramine (hexa), while the appropriate proportion was determined by using the IR-spectroscopy.Specimens of novolac/hexa (weight ratio 14:1) reinforced with carbon fibers commercially available were fabricated under different conditions (e.g. different thermal programs and different proportions of novolac/carbon fibers). The mechanical properties of the fabricated specimens (like flexural strength, tensile strength, etc.) were determined and their structure was examined by scanning electron microscopy.By increasing the volume proportion of carbon fibers, not only all mechanical properties of the composite material were increased, but also their degree of utilization was increased and also the production conditions had greater influence. Concerning the specimens produced by the same proportion of carbon fibers (e.g. 15 vol.-%) their mechanical properties were improved by increasing the curing of novolac. The degree of curing of novolac during the initial phase (gel time) and during the ultimate phase (post-curing) can be followed with the aid of IR-spectra of the cured resin, while the degree of curing for the intermediate phase can be obtained only indirectly from the values of the mechanical properties of the corresponding specimens.From the correlation between the production parameters and the mechanical properties of the samples the optimal conditions for processing of the thermopress for the manufacture of carbon fiber reinforced novolac were concluded (1. phase: T1 = 125-145°C, t1 = 20 min - 1 h, without pressure; 2. phase: T2 = 180-195°C, t2 = 40 min, P2 ≃ 1,5 kN/cm2).
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  • 3
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 69-78 
    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 dieser Arbeit interessieren wir uns für den Einfluß von Konzentration und Temperatur auf den elektrischen Widerstand eines Butyl-Kautschuks (IIR), der mit zwei Typen von Ruß (Hoch-Abrasion-Schmelzofen-Ruß (HAF) und Schnell-Extrusion-Hochofen-Ruß (FEF)) versetzt ist. Ergebnis war, daß die Leitfähigkeit bei niedrigem Rußgehalt hauptsächlich durch thermische Aktivierung der Ladungsträger erreicht wird. Bei mittleren Konzentrationen überwiegt der Tunnel-Mechanismus bei niedriger Temperatur, gefolgt von der thermischen Aktivierung bei relativ hoher Temperatur. Dies gilt für beide Rußarten. Das metallartige Verhalten bei Gemischen mit hoher Rußkonzentration kann sowohl der thermischen Ausdehnung der Tunnelwege zwischen Kohlenstoff-Agglomeraten als auch dem Zusammenbruch der Kohlenstoff-Agglomerate bei steigender Temperatur zugeschrieben werden.
    Notes: In this study we are interested in the effect of concentration and temperature on the electrical resistivity of butyl rubber (IIR) loaded with two types of carbon black, (namely, high abrasion furnace black (HAF), and fast extrusion furnace black (FEF)). It was found that the conductivity at low carbon black concentrations is mainly achieved by thermal activation of carriers. Tunneling mechanism at low termperature followed by thermal activation at relatively high temperature is found to be predominant for moderate concentrations for both carbon blacks. The metal-like behaviour which was observed in highly loaded compounds was attributed to both, the thermal expansion of the tunneling paths between carbon-carbon agglomerates and the breakdown of carbon agglomerates with temperature.
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  • 4
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 79-87 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Arbeit beschreibt die Synthese von Halogenderivaten des Phenylglycidylethers und die Möglichkeiten der Verwendung von diesen Komponenten als Flammverzögerer und reaktive Verdünnungsmittel für Epoxidharze.Mit Hilfe der Nelder-Mead-Simplexmethode wurden die besten Reaktionsbedingungen gefunden. Die so hergestellten Produkte zeichnen sich durch eine hohe Qualität aus und wurden mit einem niedermolekularen Epoxidharz gemischt und mit Diaminodiphenylmethan gehärtet.Die Viskosität von Harzgemischen und die Brennbarkeit der gehärteten Systeme wurden untersucht. Mit dem erhöhten Gehalt an Halogen (Chlor oder Brom) steigt die Viskosität, und die Brennbarkeit der Epoxide wird reduziert.
    Notes: This study deals with the synthesis of halogenated derivatives of phenyl glycidyl ether and with possibilities of their use as flame retardants and reactive diluents of epoxy resin.The best reaction conditions optimized by Nelder-Mead simplex method were found. The products of very high quality were prepared. They were mixed with a lowmolecular epoxy resin and cured by diamino diphenyl methane.The viscosity of the resin mixtures and limiting oxygen index of cured systems were determined. It was found that a higher content of halogen, both chlorine and bromine, causes increasing viscosity and reduced flammability of the epoxides.
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  • 5
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Messungen von Tg, Tm und Tc (Trübungspunkt) wurden Phasendiagramme der vier verträglichen Polymermischungen von chlorierten isotaktischen Polypropylenen (Chlorgehalt 39,2 (CPP-40) und 49,8 Gew.-% (CPP-50)) mit Poly(ethylen-co-vinylacetat)en (Vinylacetatgehalt 40 (EVA-40) und 45 Gew.-% (EVA-45)) untersucht. Von den vier Mischungspaaren war die Mischung von CPP-50 mit EVA-40 am besten verträglich.
    Notes: By measuring Tg, Tm and Tc (cloud point) phase diagrams for the four miscible blends of chlorinated isotactic polypropylenes (chlorine content 39.2 (CPP-40) and 49.8 wt.-% (CP-50)) with Poly(ethylene-co-vinyl acetate)s (vinyl acetate contents 40 (EVA-40) and 45 wt.-% (EVA-45)) were investigated. The blend of CPP-50 with EVA-40 was the most compatible of the four blend pairs.
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  • 6
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Synthese und Charakterisierung von Kationenaustauschmembranen aus PE-PS-DVB-Interpolymeren für die Elektrolyse von Borax-Lösung zur Erzeugung von Borsäure und Natronlauge wurden durchgeführt und mit den Eigenschaften von im Handel erhältlichen Membranen („Nafion 324“ und „Permaplex C-20“) verglichen.
    Notes: The synthesis and the characterization of the PE-PS-DVB interpolymer cationexchange membranes in the electrolysis of borax solutions to produce boric acid and sodium hydroxide simultaneously was carried out. The characterization of the teflon based “Nafion 324” and polystyrene-DVB based “Permaplex C-20” membranes was also performed in the same system for comparison.The DVB contents were varied between 3 - 12% (by wt. in total monomers) and the increase of the cross-links resulted in the decrease of the water contents and ionexchange capacities of the membranes. The PE present in the membrane acted as a barrier for electroosmotic water transport. The membranes with high DVB contents showed better electrolysis performance due to their low water contents and low electroosmotic water transport properties. The use of the interpolymer membrane containing 11.6% DVB resulted in high current efficiency and high sodium cation dynamic transport number and worked satisfactorily at the process conditions of borax electrolysis.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 165 (1989), S. 125-131 
    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: Aus Rizinusöl und difunktionellen Säuren, wie Oxal-, Malon-, Bernstein-, Glutar-, Adipin-, Suberin- und Sebacinsäure, wurden Prepolyester hergestellt. Diese Prepolyester (PPE) wurden anschließend mit Methylmethacrylat und 1% Ethylenglykoldimethacrylat als Vernetzer interpenetriert. Die Polymerisation wurde radikalisch mit Benzoylperoxid gestartet. Die neuen PPE/Polymethylmethacrylat (PMMA)-interpenetrierenden Netzwerke wurden als Pulver erhalten. Sie wurden durch ihr Löseverhalten, IR-Spektroskopie und ihr thermisches Verhalten charakterisiert.
    Notes: Prepolyesters were obtained from castor oil and dibasic acids, viz oxalic, malonic, succinic, glutaric, adipic, suberic and sebacic acid. These prepolyesters (PPE) were subsequently interpenetrated with methyl methacrylate containing 1% ethylene glycol dimethacrylate as crosslinker by radical polymerization initiated with benzoyl peroxide. The novel PPE poly(methyl methacrylate) PPE/PMMA interpenetrating polymer networks (IPNs) were obtained as powder. They were characterized by solubility behaviour, IR spectral study and thermal behaviour.
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  • 8
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 2,4-Ionen, ein polymeres quartäres Ammoniumsalz, wurde auf einem makroporösen chlormethylierten Poly(Styrol-co-Divinylbenzol)-Harz (XAD-2) immobilisiert. Der Ionen-Gehalt des Harzes, der durch CHN-Elementaranalyse bestimmt wurde, betrug 50,2 g/kg Harz. Der wichtigste Nebeneffekt des modifizierten Harzes, das Ausbluten des Katalysators 2,4-Ionen, kann durch eine spektrophotometrische Methode, die extrem geringe Konzentraionen an freiem Ionen an der Oberfläche des Harzes messen kann, ermittelt werden.Die Aktivität der immobilisierten 2,4-Ionen/Kobalt(II)-phthalocyanin-tetranatriumsulfonat-Komplexe in bezug auf die oxidative Kupplung von Thiolen ist viel niedriger als im homogenen Fall, aber noch beträchtlich höher als im polymerfreien System. Die beobachtete Abnahme der Reaktionsgeschwindigkeit resultiert nicht aus Behinderungen des Massentransports, sondern vorzugsweise aus den Katalysatoreigenschaften wie z. B. einem sehr niedrigen N+/Co-VerhtUtnis. Die aktiven Zentren scheinen nur in der äußeren Hiille der Harzpartikel vorhanden zu sein.
    Notes: A poly(quaternary ammonium) salt, 2,4-ionene, has been immobilized on a macroporous chloromethylated poly(styrene-divinylbenzene) resin (XAD-2). The ionene content of the resin, determined by CHN elemental analysis, was 50.2 g/kg resin. The most important side effect of the modified resin, catalyst (2,4-ionene) bleeding, can be detected by a spectrophotometric method capable of determining extremely low concentrations of free ionene in the supernatant of the resin.The activity of these immobilized 2,4-ionene/cobalt(II)phthalocyanine-tetrasodiumsulfonate (CoTSPc) complexes towards the oxidative coupling of thiols is much lower than in the homogeneous case, but still considerably higher than for the polymer free system. The observed decrease in reaction rate does not originate from the considerable mass transfer resistances but predominantly from catalyst properties like a very low local N+/Co ratio. The active sites appear to be present in the outer shell of the resin particles only.
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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: Röntgendiffraktometrische Untersuchungen und DSC-Messungen an Blend-Filmen, die aus Lösungen von PEEK und PES hergestellt wurden, zeigen eine Phasenseparation bei den Filmen, die bei 340°C hergestellt wurden. Das Kristallisationsverhalten von Filmen, die bei 340°C hergestellt, anschließend abgeschreckt und bei 180°C getempert wurden, ist identisch mit dem von PEEK. Filme, die bei 300°C hergestellt wurden, kristallisierten erst durch Tempern bei 250°C. Blockcopolymere, die aus Oligomeren von PEEK und PES erhalten wurden, unterscheiden sich in dieser Hinsicht von Blends der gleichen Zusammensetzung. Die Glastemperatur von Copolymeren mit einem PEEK-Gehalt von mehr als 50% liegt höher als die von PEEK selbst, während der Schmelzpunkt dieser Copolymeren niedriger als der von PEEK ist.
    Notes: Polymer blends of PEEK with PES were prepared by the solution blending method. Copolymers composed of PEEK and PES components were synthesized from these oligomers. The formation conditions exerted an influence over the molecular aggregation and the crystallization behaviors of the blend films and block copolymers which were examined by X-ray diffractometry and DSC analysis. As a result, phase-separation in the blend films was found when the formation temperature was high. The blend films formed at 340°C, quenched and annealed at 180°C, exhibited the same crystallization behavior as those of PEEK. In the case of the blend films formed at 300°C, the annealing of the films at 250°C was required to crystallize the blend films. The Tg of a copolymer with a PEEK component content of more than 50% tends to shift toward a higher temperature than the Tg of PEEK itself, and the Tm of the copolymer toward a lower temperature than that of PEEK ist.
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  • 10
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 129-134 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Reaktionsprodukt eines Cyclohexanon-Formaldehyd-Harzes mit dem Säurechlorid des Radikalinitiators 4,4′-Azo-bis(4-cyanopentansäure) wurde als Initiator für die Styrolpolymerisation eingesetzt, um ein Cyclohexanon-Formaldehyd-Harz/Polystyrol-Copolymeres zu bilden. Das Copolymere zeigte ähnliche Löslichkeit wie Polystyrol.
    Notes: The reaction product of cyclohexanone-formaldehyde resin with an acid chloride of a radical initiator, 4,4′-azo-bis(4-cyano pentanoic acid) was used as initiator for styrene polymerization to form a cyclohexanone-formaldehyde resin/polystyrene copolymer. The copolymer showed similar solubility as polystyrene.
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  • 11
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 145-155 
    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: Entgegengesetzte Ladungen wurden durch tertiäre Amin- und Carboxylgruppen in Polyurethan (PU) und Polystyrol (PS) eingeführt, um durch gemeinsame Massepolymerisation ein interpenetrierendes PU/PS Polymernetzwerk (IPN) zu erhalten. Vier IPNs wurden hergestellt: ein Voll-IPN, zwei Semi-IPNs und ein lineares Blend. Die Wirkung der geladenen Gruppen auf die mechanischen Eigenschaften und die Morphologie der vier Polymermischungen wurde untersucht.Es wurde gefunden, daß PU/PS IPNs mit geladenen Gruppen keine Phasenseparation und somit homogene Verteilung aufweisen, was durch elektronenmikroskopische (SEM) Aufnahmen nachgewiesen wurde. Dynamisch-mechanische Messungen zeigen, daß die Übergangspeaks des Verlust-Moduls E″ in die Mitte zwischen den beiden Übergangspeaks der beiden Komponenten ohne geladene Gruppen liegen. Dies ist von der Zunahme des Gehaltes an geladenen Gruppen abhängig. Gleichzeitig nimmt der Speichermodul E′ in einer Stufe ab, was im Gegensatz zu der zweistufigen Abnahme bei Proben ohne Ladungsträger steht.Die Zugfestigkeit nimmt in allen vier Polymermischungen mit der Zunahme an Acrylsäure (AA) in Poly(Styrol-Acrylsäue) PSAA zu, was in dem PU/PSAA Voll-IPN besonders deutlich wird.
    Notes: Opposite charges, namely tertiary amine and carboxyl groups, were introduced into polyurethane (PU) and polystyrene (PS), respectively, to prepare PU/PS interpenetrating polymer networks (IPNs) by means of simultaneous bulk polymerization. Four IPNs were synthesized: a full-IPN, two semi-IPNs and a linear blend. The effect of charge groups on the mechanical properties and morphology of the four polymer alloys was investigated.It is found that the PU/PS IPN which was incorporated with charge groups is free of any phase-separation, and sufficiently uniformly distributed, as can be seen from the corresponding scanning electron microscopy (SEM) photographs. Dynamic mechanical analysis indicates that the transition peak of the loss modulus E″ will move towards the centre between the two transition peaks of both components in the absence of charge groups, as a function of an increase in the contents of the opposite charge groups. Meanwhile the storage modulus E′ will decrease in a single-stage way from the previous two-stage mode.The tensile strength in all the four polymer alloys increased markedly along with an increase in the contents of acrylic acid (AA) in the poly(styrene-acrylic acid) (PSAA), which clearly can be seen for the PU/PSAA full-IPN.
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  • 12
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 157-168 
    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: Pyrolysis behaviour and coke characteristics of different precursors for carbon processing: thermosetting resins (resol, novolak), hydrolytic lignin, pitch, tar as well as their blends were studied using differential thermal analysis (DTA) and X-ray diffraction techniques. The blends novolak-pitch, resol-tar and resol-hydrolytic lignin show a higher coke yield after carbonisation up to 1000°C compared to the corresponding individual substances. A good correlation between the integral procedural decomposition temperature T*A of the investigated precursors and their coke yield is found.
    Notes: Mittels Thermo- und Röntgenstrukturanalyse wird eine vergleichende Untersuchung des Pyrolysevorganges und der Mikrostruktur des aus zwei Gruppen organischer Bindemittel und deren Mischungen gewonnenen Koksrückstandes durchgeführt. Gruppe I umfaßt reine und mit Hydrolyselignin gefüllte Resol- und Novolak-Phenol-Formaldehydharze und Gruppe II Steinkohlenpech und -teer. Es wird festgestellt, daß sich die Mischungen Novolakharz-Pech, Resolharz-Teer und Resolharz-Hydrolyselignin beim Erhitzen nicht wie mechanische Gemische verhalten und eine erhöhte Ausbeute an Koksrückstand liefern. Weiterhin wird gefunden, daß die integrale Endtemperatur der Pyrolyse (T*A) dieser Substanzen als quantitatives Maß für die Ausbeute an Koksrückstand im Anschluß an die Carbonisierung der Proben dienen kann.
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  • 13
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    Angewandte Makromolekulare Chemie 168 (1989), S. 217-223 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper describes the successful synthesis of silicon containing bismaleimide resin 4,4′-carbo(4,4′-bismaleimido phenoxy)diphenyl silane. The char yield of the bismaleimide resin in N2 atmosphere was found to be 55% at 800°C. Chain extension of bismaleimide with 4,4′-diamino diphenyl sulfone reduced the char yield and thermal stability.
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  • 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: As hard blocks in polyether block amides, polyamides are used whose length is intensively regulated by dicarboxylic acids. Since, with regard to melting and crystallization behaviour, this acid constitutes an interfering structural unit in the chain, and in the case of a completely converted product each chain contains one acid molecule, it is essential to know where in the chain incorporation will occur. As opposed to monofunctional chain regulators which always form a chain end, a bifunctional chain regulator can a priori also be randomly incorporated into the inner part of the chain. This leads to a far greater interference than occurs if the chain regulator molecule and the chain end, which acts as an interfering unit in any case, coincide with each other.By means of adipic acid-regulated oligoamides based on lauryl lactam, the incorporation of the chain regulator was examined by NMR spectroscopy and compared with model calculations. This resulted in a close match only if it was presupposed that the incorporation was carried out randomly with the same degree of probability at any point whatsoever between two lauryl lactam structural units or at the chain end.Further calculations illustrate the effects of the incorporation of the chain regulator on the size of the amorphous portion.
    Notes: Als Hartblöcke in Polyetherblockamiden werden durch Dicarbonsäuren stark geregelte Polyamide eingesetzt. Da die Säure in Hinblick auf das Schmelz- und Kristallisationsverhalten einen Störbaustein in der Kette darstellt und bei einem ausgeregelten Produkt jede Kette ein Säuremolekül enthält, ist es von Bedeutung zu wissen, wo in der Kette der Einbau erfolgt. Anders als bei monofunktionellen Reglern, wo der Regler stets ein Kettenende bildet, kann ein bifunktioneller Regler a priori auch statistisch im Inneren der Kette eingebaut werden. Dies führt zu einer viel stärkeren Störung, als wenn das Reglermolekül und das sowieso als Störstelle wirkende Kettenende zusammenfallen. Anhand adipinsäuregeregelter Oligoamide auf Basis von Laurinlactam wird kernresonanzspektroskopisch der Einbau des Reglers untersucht und mit Rechnungen verglichen. Es ergibt sich nur dann gute Übereinstimmung, wenn vorausgesetzt wird, daß der Einbau statistisch erfolgt und dabei mit gleicher Wahrscheinlichkeit für jede beliebige Stelle zwischen zwei Laurinlactambausteinen oder am Kettenende abläuft. Weitere Rechnungen verdeutlichen den Einfluß des Reglereinbaus auf die Größe des amorphen Anteils.
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  • 15
    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: Auf Grund von mikroskopischen Beobachtungen wurde festgestellt, daß unter dem Einfluß von UV-Strahlung die Oberfläche von PVC-Filmen einer Formveränderung unterliegt. Auf der Oberfläche erscheinen Bläschen und Löcher. Die sich absondernden Gasprodukte der Polymerfotodestruktion verursachen die Bildung dieser Bläschen und Löcher. Größere Oberflächenänderungen wurden in Filmen mit einem Zusatz von 1-5% eines MMA/MA-Copolymeren beobachtet. Das weist auf eine in diesem Modifikator stattfindende Photoabbaureaktion hin, deren Ergiebigkeit größer ist als in reinem PVC. Dieser Modifikator wird in PVC eingeführt, um die Filmoberfläche zu verbessern, beschleunigt allerdings ihre Zerstörung unter dem Einfluß von UV-Strahlung. Es wurde festgestellt, daß Cyclohexanonspuren in den Proben den Photoabbau von MMA/MA retardieren, diesen Prozeß in PVC aber beschleunigen.
    Notes: By means of microscopic observation, the deformation of the surface of PVC films caused by 253.7 nm UV radiation was investigated. Numerous blisters and holes were formed by the gaseous photodecomposition products of the polymer.More apparent deformation of the films containing MMA/MA suggests that the photodecomposition of this modifier occurs with higher efficiency than that of PVC.MMA/MA copolymer is introduced into PVC films to improve the smoothness of their surface, but this modifier accelerates the deformation of this surface under UV irradiation. It was also found that traces of cyclohexanone in samples retard the photodecomposition of MMA/MA and accelerate this process in PVC.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 170 (1989), S. 29-41 
    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 Anzahl von Harzen wurde durch gemeinsame Kondensation von p-Aminoacetophenon (p-AAph), substituierten Benzoesäuren wie m-Tolylsäure (m-TA), o-Tolylsäure (o-TA), Phthalsäure (PhA), p-Nitrobenzoesäure (p-NBA), p-Chlorbenzoesäure (p-CIBA) und Formaldehyd (F) in Gegenwart von verschiedenen Säuren und Basen als Katalysatoren hergestellt. Die Harze wurden IR-spektroskopisch charakterisiert. Die Löslichkeitsparameter wurden gemäß Small's Gruppenbeteiligung berechnet; sie stimmen gut mit den experimentellen Werten überein. Das thermische Verhalten und die bakteriologischen Eigenschaften der Harze wurden auch untersucht.
    Notes: A number of resins has been prepared by condensing p-amino-acetophenone (p-AAph) with substituted benzoic acid such as m-toluic acid (m-TA), o-toluic acid (o-TA), phthalic acid (PhA), p-nitrobenzoic acid (p-NBA), p-chlorobenzoic acid (p-CIBA) and formaldehyde (F) in presence of some acids and bases as catalysts. The resins were characterized by infrared spectra of the characteristic groups. The solubility parameters were calculated from Small's group contribution which agreed well with the experimental values. The thermal behaviour and the bacteriological properties of the resins have also been investigated.
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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
    Notes: Notwithstanding their more common beginnings, liquid crystals and molecular biology developed mainly parallel and independently during the last one hundred years.Molecule-phase relationships on the one and complex static-dynamic treatments on the other hand seem to forward mutually integrative views in our days.Biomesogen approaches will deepen our insights into the spatio-temporal coherences of biological systems. They might contribute significantly to the understanding of life processes.
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  • 18
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recent studies on ionic distribution in solutions and in suspensions were reviewed. Suspensions of latex particles, which were large enough to be seen under an ultramicroscope, were investigated by the 2-D Fourier transformation. The micrograph showing ordered structures gave discrete scattering spots, whereas those of disordered arrangements displayed no spots or halos. The two-state structure gave a limited number of halo, confirming our previous conclusion that the very frequently observed single, broad scattering peak was reminiscent of some kind of ordering of solute species. By using an image data analyser, the crystallization process was shown to follow the Ostwald ripening mechanism. The concurrent study by the quasi elastic light scattering method and by the Fourier analysis gave consistent scattering profiles, which indicated that the ordering phenomena took place in the entire volume of suspensions. The scattering intensity (correctly the lattice factor) was calculated for cubic systems with paracrystalline distortion. The peak intensity was lowered by enhanced distortion, while the peak position itself was not affected. This justifies our previous treatment of the single, broad peak in terms of the Bragg equation. The experimentally found scattering curve was compared with this theoretical calculation; the degree of distortion was evaluated.
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  • 19
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Lyotropic liquid crystalline phases of cellulose derivatives were explored as an analytical tool. Molar mass dependent measurements of the helicoidal cholesteric pitch of a cellulose tricarbanilate/solvent system may be used to determine the molar mass of this derivative by optical means. The compatibility of a ternary liquid crystalline system can be adequately investigated by a study of the supermolecular structure with spectroscopic measurements.
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  • 20
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The application of carotenoids as natural additives in various water-based or water-compatible formulations for the pigmentation of foods and feeds is seriously hampered by their insolubility in aqueous systems.Therefore, in order to develop the full potential of colour strength and to achieve a high degree of bioavailability during gastro intestinal passage, the coarse crystalline material has to be transformed into a microdisperse state.Exemplified with β-carotene, a novel non-mechanical process is described that transforms the carotenoids into a colloidal hydrosol characterized by an average particle size of about 0.1 μm.The process is based on the preparation of a transient high temperature solute state of the carotenoid in a water-miscible solvent, coupled with succeeding rapid aqueous precipitation in the presence of a stabilizing polymer colloid. The obtained hydrosols are characterized by photon-correlation-spectroscopy(size), and microelectrophoresis(colloidal stabilization).The bioavailability was tested by monitoring plasma levels of β-carotene in veal calves.
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  • 21
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer science is mature enough to allow one to think about tailor-making macromolecular compounds aimed at interacting purposely with living systems. Reasons for developing bioresorbable polymers for temporary therapeutic applications are discussed with respect to property adjustments and economical factors. The field of the applications is first described and guidelines for tailor-making multimeric macromolecules with desired properties are presented. The approach led to focuss investigations on poly(α-hydroxy acids) and functional poly(β-hydroxy acids) derived from natural hydroxy acids, namely lactic, glycolic and malic acids. Physical, mechanical and biological properties of some corresponding polymers and copolymers are presented. Last but not least, examples of applications currently investigated are recalled.
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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
    Notes: When blood comes into contact with an artificial surface, a number of events occur which include protein adsorption, platelet activation and the activation of the intrinsic pathway of blood coagulation. With the increased application of blood containing artificial devices, there is a great demand to develop new biomaterials which retard thrombus formation. Our new approach to solving this problem is to mimic the non-thrombogenic surface of natural biological membranes at least in a simple form. We have developed a polymerisable phospholipid and polyesters based on the major phospholipid polar head group present on the erythrocyte outer membrane surface. The coagulation of blood exposed to these polymers was examined by the technique of Material Thrombelastography, a relatively simple test for the in vitro screening of polymer thrombogenicity. We present results which indicate that the polymerised phospholipid and polyesters show reduced thrombogenicity, and may therefore have potential for future biomaterials.
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  • 23
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After implantation a stable bond between the implant and the surrounding tissue is required. Therefore a high cell adhesion of the polymer surface of the implant must be achieved. Depending on the treatment time of a polydimethylsiloxane foil with oxygen plasma, the cell adhesion can be improved. FT-IR spectroscopy and ESCA analysis were used to characterize the surface modification. The cell spreading and cell adhesion increase with increasing hydrophilic character of the polymer surface after plasma treatment. A pronounced correlation was found between the efficiency of DNA and protein content, characterizing cell growth, and the spreading of the cells.Polydimethylsiloxane, Glow-Discharge, Surface Modification, Cell Adhesion, Cell Proliferation.
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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
    Notes: We have used synthetic polymers as tools to probe endocytosis and lysosome function. Their particular value lies in their well-defined chemical constitution and in the possibility to custom-synthesize molecules with desired characteristics. Polyvinylpyrrolidone, Percoll and polystyrene beads have been 125I-labelled and used to explore the borderland of pinocytosis and phagocytosis. Derivatized poly(aspartamide), poly(hydroxypropylmethacrylamide) and a polylysine-poly(ethylene oxide) block copolymer have been used to investigate the effects of hydrophobic moieties and sugar residues on substrate-selection in pinocytosis. The effect of cationic moieties has been studied using vinylpyrrolidone-vinylamine copolymers.Poly(hydroxypropylmethacrylamide) with certain oligopeptide side---chains have been shown to be susceptible to lysosomal peptidases. Ethylene glycol oligomers are being used to study the basal permeability of the lysosome membrane.Soluble macromolecules have considerable potential in targeted drug-delivery. Drugs attached to appropriate polymers by covalent links that are susceptible to lysosomal enzymes can deliver drug to target cells and avoid unwanted sideeffects. Synthetic macromolecules have several advantages over their natural counterparts: they are chemically more robust, less immunogenic, and easier and cheaper to prepare in bulk.
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  • 25
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diagnostics are e. g. reagents or combinations of reagents or measure bloodcomponents down to concentrations of 10-15 mol/1 in reproducable form. To achieve this target diagnostics have to fullfill special requirements in purity, uniformity, producibility and reproducibility. These requirements are also valid for integrated polymers and plastics. Examples of the application of polymers and plastics in diagnostics are e. g. materials for the blood-plasma-separation, the stabilization of proteins, solid phases in immunoassays as reagent tubes, microtiterplates and latexparticles.Reciprocal actions between polymers, plastics, polymer additives, blood and bloodsubstances like proteins in diagnostic tests can be seen as indications to similar effects by the intracorporeal applications of plastics in surgery and in general for contacts of natural materials with plastics, as usual in the foodpacking.
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  • 26
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using Eupergit, a synthetic resin, as an example, the necessary characteristics of a support for high performance affinity chromatography (HPAC) are demonstrated. To such a support different ligands can be immobilized and used for the separation of biopolymers.From the range of possible applications a few examples are chosen. Immunoglobulins are isolated in one step by protein A-HPAC, the purified antibodies are immobilized and applied to immunoaffinity-HPLC for the isolation of corresponding antigens. Concanavalin A-HPAC of membrane proteins was chosen to represent chromatography with immobilized lectins. Antithrombin could be isolated from human plasma by the use of immobilized heparin. HPAC has the advantage of affinity chromatography, which is above all highly specific. As the support is resistant to high pressure and has well defined microparticles with a particular pore size, it provides a much higher yield at considerable flow rates. The handling of materials like this is simpler, the separation of the sample is quicker and can be reproduced more easily.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 166 (1989), S. 257-272 
    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: Controlled polyelectrolyte adsorption can be used to render phospholipid bilayer membranes sensitive to physical and chemical signals. We describe in this paper the design and construction of macromolecular switches for bilayer membranes, which can be used to create lipid vesicles that release their contents rapidly and quantitatively in response to changes in pH, temperature, light intensity or glucose concentration. The kinetics and mechanisms of the molecular switching processes observed in such systems are also discussed.
    Notes: Kontrollierte Adsorption von Polyelektrolyten kann ein wirksames Werkzeug im Design von dünnen molekularen Filmen sein. Man kann erwarten, daß die Adsorption von Polyelektrolytketten das empfindliche Kräftegleichgewicht erheblich beeinflußt, das die strukturellen und funktionellen Eigenschaften von geordneten Strukturen wie Einzel-, Doppel- und Mehrfachschichten bestimmt. Andererseits ist die Adsorption von Polyelektrolyten außerordentlich sensitiv auf Umgebungsparameter, z.B. pH, Temperatur oder lonenstärke. Kontrollierte Adsorption kann daher zu Sensitivität auf bestimmte chemische oder physikalische Stimuli führen, sodaß auf diese Weise ein molekularer Schaltmechanismus entworfen werden kann. Durch Umsetzen dieser ldee in reale Systeme gelang es uns, molekulares Schalten in Mischungen von Poly(2-ethylacrylsäre) mit natürlichen oder synthetischen Phosphatidylcholinen zu bewirken. Insbesondere haben wir Phosphatidylcholinvesikel hergestellt, die ihren lnhalt nach einer Änderung von pH, Temperatur, Glukosekonzentration oder nach Bestrahlung mit Licht schnell und quantitativ freisetzen. Die Entwicklung und die Herstellung von Doppelschichtmembranen, die auf solche Änderungen reagieren, sowie die Kinetik und der Mechanismus des damit verbundenen molekularen Schaltprozesses werden im vorliegenden Artikel diskutiert.
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  • 28
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Enzymes can be immobilized by gel entrapment, by microencapsulation, by physical or ionic adsorption, by covalent binding to inorganic or organic carriers, or by whole cell immobilization. Of particular interest is the large number of chemical reactions developed for the covalent binding of enzymes via their nonessential functional groups to inorganic carriers such as glass, ceramics and iron, to natural polymers such as cellulose and Sepharose, and to synthetic polymers such as nylon, polyacrylamide, and other vinyl polymers and copolymers possessing reactive chemical groups. The stability of certain enzymes is markedly increased on their immobilization. It was thus possible to transform the biologically active polymer derivatives into active enzyme beads, enzyme capsules, enzyme columns and enzyme membranes and these enabled the construction of enzyme reactors such as the batch-stirred tank reactors, the continuous packed bed reactors, and fluidized bed reactors. So far mainly immobilized hydralases and isomerases are being used in industry on a large scale. It seems likely, however, that once adequate techniques become available for cofactor recycling, the use of immobilized enzymes will be extended to other organic reactions, particularly those involving stereospecific synthesis of simple or complex organic molecules. Among the industrial processes in which immobilized enzymes are being used, it is worth mentioning the industrial-scale continuous production of fructose enriched syrup from glucose by immobilized glucose-isomerase, the batch process for the production of 6-aminopenicillanic acid (6-APA) from penicillin G with the aid of immobilized penicillin amidase; the production of aspartame from aspartic acid and phenylalanine by immobilized thermoase; the large scale production of optically active amino acids with immobilized amino acid acylase; and the large scale production and application of immobilized lactase for the hydrolysis of lactose. The recently developed process for acrylamide production using immobilized nitrilase containing microbial cells should also be referred to. The successful use of an NAD-polyethylene glycol conjugate (NAD-PEG) as a nondialyzable water-soluble coenzyme derivative in the enzymic synthesis of leucine from α-ketoisocaproic acid and ammonia, in a membrane-enclosed reactor containing L-leucine dehydrogenase, NAD-PEG, formate and formate dehydrogenase, illustrates the new possibilities opened up by making use of cofactor-polymer conjugates. The use of enzyme-polymer conjugates in analytical and clinical is also illustrated.
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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
    Notes: The genetic make-up of living systems especially of isolated cells can be altered by a variety of methods including chemical or light-induced mutation. More modern procedures are the in vitro recombination of nucleic acids and the cell-cell fusion.The new methods are especially useful to reprogram microorganisms to produce valuable proteins or other natural products in excess quantties. In the following we will elucidate the importance of the new techniques by describing the bacterial production of glucose dehydrogenase, of the proteinase inhibitor stefin A and by outlining the methods and promisses of substractive cloning. Although the economic value of genetic engineering techniques still awaits justification, the importance of the methodology for basic biological research is well documented.
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  • 30
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immobilization of whole cells has become an efficient tool for biosynthesis, biotransformation and analysis. High cell density, high operational stability, easy handling, propably in continuous systems, and multiple reuse are important advantages of immobilized cells. In comparison to other methods like adsorption, crosslinking and encapsulation, the entrapment within a polymeric network is the most widely applied technique in heterogeneous biocatalysis. For immobilizing mammalian cells nearly exclusively the adsorption onto micorcarriers is used. Requirements for the polymers to be used in such immobilized cell systems are discussed in detail.
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  • 31
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 168 (1989), S. 1-8 
    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: Vier Pyridazinderivate wurden synthetisiert und als Beschleuniger für Naturkautschukmischungen entwickelt. Die rheologischen Eigenschaften wurden mit Hilfe eines Monsanto Rheometers 100 bestimmt. Die rheometrischen Daten wurden für die Berechnung der kinetischen Konstanten der Vulkanisationsreaktion in Anwesenheit der synthetisierten Verbindungen benutzt. Verglichen mit Mercaptobenzthiazol (MBT), einem Beschleuniger der häufig in der Kautschukindustrie eingesetzt wird, zeigten diese Verbindungen eine gute Beschleunigerwirksamkeit.
    Notes: Four pyridazine derivatives were synthesized and evaluated as accelerators in natural rubber (NR) mixes. The rheological characteristics were determined by a Monsanto Rheometer 100. The kinetic constants for the vulcanization reaction in the presence of the synthetic compounds were calculated using the rheometric data. The compounds showed a good accelerating efficiency compared with mercaptobenzothiazole (MBT), which is widely used in rubber industry.
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  • 32
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 170 (1989), S. 173-182 
    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 Ansammlung von als inaktiv angenommenen „Dimeren“ und „Trimeren“ sowie der Verbrauch von aktiven Spezies mit der Reaktionszeit im säurekatalysierten Furfurylalkohol (FA)/Formaldehyd (F) System wurde durch GPC-Technik unter Anwendung eines Doppeldetektors bewiesen.Ein Reaktionsmechanismus wurde für den Kondensationsprozeß vorgeschlagen, der einige Widersprüche der bisherigen Untersuchungen erklären kann.
    Notes: Accumulation of “dimers” and “trimers” considered to be inactive and consumption of active ones with reaction time in furfuryl-alcohol (FA)/formaldehyde (F) acid catalyzed condensation system was proved by GPC technique using double detector.A reaction mechanism was proposed for the condensation process explaining some contradictions of investigations collected so far.
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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: Dieser Artikel befaßt sich mit silylierten bzw. maleinisierten Polybutadienölen und ihren Effekten in Kieselsäure und Silicate bzw. Kreide enthaltenden Kautschukmischungen. Sie erweisen sich als wirksame Hilfsstoffe für die Substitution von Ruß durch mineralische Füllstoffe.
    Notes: This paper deals with silylated and maleated polybutadiene oils and their effects in rubber compounds containing silica(tes) resp. chalk as fillers. They are shown to be efficient aids in the substitution of oil-dependent carbon black by mineral fillers.
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  • 34
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 171 (1989), S. 79-89 
    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: Die isotherme und nichtisotherme Kristallisation von isotaktischem Polypropylen, das mit ausgewählten organischen Pigmenten gefärbt war, wurde mittels DSC untersucht. Es wurde gefunden, daß die Nukleierungsfähigkeit der Pigmente mit deren chemischem Aufbau und mit der Erniedrigung der freien Energie für den Keimbildungsprozeß verbunden ist. Die experimentellen Daten wurden mit Hilfe der bekannten Avrami-Gleichung analysiert.Blau-Pigment und Rot-Lack beschleunigen die Kristallisation von isotaktischem Polypropylen, während Orange-Pigment die Kristallisationsgeschwindigkeit etwas herabsetzt.
    Notes: The isothermal and non-isothermal crystallization of isotactic polypropylene coloured with selected organic pigments was examined by differential scanning calorimetry. It was found that the nucleating ability of pigments is connected with their chemical nature and with the reduction of the free energy for critical nucleus formation. The experimental data were analysed in terms of the well known Avrami equation.Blue pigment and Red lake are substances which accelerate the crystallization of isotactic polypropylene, while Orange pigment decreases the crystallization rate slightly.
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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: Um bei Kationen-Austauschmembranen eine dauerhafte Selektivität für die Durchlässigkeit von einwertigen Kationen zu erzielen, wurde eine Polyethylenimin-Schicht auf der Membranoberfläche durch Säureamidbindung zwischen Polyethylenimin und den —SO2Cl-Gruppen einer Styrol-co-Divinylbenzol-Membran erzeugt. Nach der Reaktion wurden die im Inneren der Membran verbleibenden —SO2Cl-Gruppen durch Tauchen in wäßrige Natronlauge hydrolysiert.Die so gewonnenen Kationen-Austauschmembranen wurden mittels Elektrodialyse von Seewasser hinsichtlich ihrer Selektivität für die Durchlässigkeit von einwertigen Kationen, ihres elektrischen Widerstandes, ihrer Stromleistung und ihrer überfüh-rungszahlen für Natrium-Ionen untersucht. ATR-IR-Messungen auf der Membran-oberfläche belegen, daß die Shäureamidbindung gegenüber starker Hydrolyseeinwirkung stabil war.
    Notes: In order to give the monovalent cation permselectivity to the cation exchange membrane permanently, polyethyleneimine layer was formed on the membrane surface by acid-amide bond between polyethyleneimine and the —SO2Cl groups of a styrene-divinylbenzene copolymer membrane. After the reaction, the —SO2Cl groups remaining in the inner part of the membrane were hydrolyzed by immersing the membrane into an aqueous sodium hydroxide solution.The resultant cation exchange membranes were evaluated by electrodialysis of sea water from the point of view of the monovalent cation permselectivity, electric resistance of the membrane, current efficiency, and transport number of sodium ions calculated by membrane potential in connection with reduced viscosity of the various commercial polyethyleneimines, ATR-IR measurements on the membrane surface suggested that the acid-amide bond was stable for severe hydrolysis reaction.
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  • 36
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    Angewandte Makromolekulare Chemie 171 (1989), S. 141-152 
    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 Epoxidgruppen eines Copolymeren, das man durch Pfropfung von 2,3-Epoxypropylmethacrylat auf isotaktisches Polypropylen erhält, wurden mit niedermolekularen Carbonsäuren umgesetzt. Die Reaktion verläuft in Gegenwart von organischen Lösungsmitteln heterogen und kann durch tertiäre Amine beschleunigt werden. Die Geschwindigkeitskonstanten der Reaktion werden mit der Dissoziationskonstanten der gebundenen Säure und mit der Art des verwendeten Beschleunigers korreliert. Die Reaktivität der polymergebundenen Epoxidgruppen ändert sich im Vergleich mit Reaktionen unter homogenen Bedingungen nicht.
    Notes: Epoxy groups on isotactic polypropylene, to which 2,3-epoxypropylmethacrylate was grafted, were reacted with low molecular carboxylic acids. The reaction proceeds under heterogeneous conditions in the presence of organic solvents and it may be catalysed by tertiary amines. The rate constants of this reaction are correlated with the dissociation constant of the bonded acid and with the character of the used catalyst. The reactivity of polymer-bonded epoxy groups is not changed when comparing with reactions performed under homogeneous conditions.
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  • 37
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird eine neue Methode zur Einführung von hydrophilen Polyetherseitenketten in segmentierte Polyurethane unter Verwendung eines Polypropylenoxid-Macromeren mit 1,3-Diol-Gruppen an einem Kettenende, die als Kettenverlängerer fungieren, beschrieben. In diesem Prozeß wird eine Seitenkette quantitativ und direkt in medizinische Polyurethanelastomere eingebaut. Diese Entwicklung ist auch für Biowerkstoffe in künstlichen Organen von Interesse.
    Notes: A new method of introducing a hydrophilic polyether side chain into segmented polyurethane using a polypropylene oxide macromer with 1,3-diol at one chain-end, which behaves as chain extender, is described. In this procedure, a molecular-designed side-chain is incorporated quantitatively and directly into polyurethane biomedical elastomer. The design is also of interest to biomaterials in artificial organs.
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  • 38
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    Angewandte Makromolekulare Chemie 172 (1989), S. 233-233 
    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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  • 39
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    Angewandte Makromolekulare Chemie 173 (1989), S. 85-100 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Orientierungsmechanismus von kaltverstrecktem, teilkristallinem Polyoxymethylen wurde durch Messung der Intensität der Weitwinkel-Röntgenstreuung (WAXS) untersucht. Die Anisotropie der Proben wurde im einachsigen Zugversuch bei etwa 130°C im Temperaturbereich zwischen Glasübergangstemperatur und Schmelzpunkt erzeugt. Der Prozess der plastischen Deformation wurde für verschiedene Stadien der Verstreckung diskutiert. Die Orientierungsverteilung der Kristalllamellen wurde qualitativ charakterisiert durch die Berechnung von Polfiguren aus den WAXS Streuintensitätsdaten. Der Grad der Orientierung wurde durch die Berechnung des Orientierungsfaktors für den [100] Flächennormalenvektor der Einheitszelle beschrieben. Die Textur der eingeschnürten Proben mit hoher Orientierung wurde als Mischung von axialer und uniplanar-axialer Textur erkannt. Als mögliche Erklärung für diesen Orientierungstyp wird ein Einfluß der Probengeometrie angenommen.
    Notes: The orientation mechanism of cold-drawn, partially crystalline polyoxymethylene (ULTRAFORM) samples was studied by performing wide angle X-ray scattering (WAXS) measurements. The anisotropic samples were prepared in uniaxial tensile tests around 130°C, in a temperature range between the glass transition and the melting point. The process of the plastic deformation is discussed for different degrees of anisotropy. The orientation distribution of the crystalline lamellae was qualitatively characterized by performing pole figure intensity calculations from the measured WAXS intensities. The degree of orientation was quantitatively described by calculating the orientation factors for the [100] normal vector of the unit cell. The texture of the necked samples with high orientation degrees was a mixture of axial and uniplanar-axial textures. An explanation for the formation of this kind of orientation is proposed assuming an influence of the sample geometry on the orientation process.
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  • 40
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    Angewandte Makromolekulare Chemie 173 (1989), S. 205-212 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Herkömmliches Vernetzen von Polyethylen niedriger Dichte (LDPE) wurde mit Dicumylperoxid (DCP) als Vernetzer durchgeführt. DCP wurde in verschiedenen Konzentrationen mit LDPE-Schnitzeln in einem Extruder bei 135 - 145°C gemischt. Monofilamentfäden wurden bei 110°C auf einer Laborziehmaschine gezogen. Die Zugdehnungseigenschaften, der prozentuale Schrumpf und die Dichte wurden mit Zunahme der DCP-Konzentration und der Heizdauer verbessert, während jedoch die prozentuale Quellung abnahm.
    Notes: Conventional crosslinking of low density polyethylene (LDPE) was carried out using dicumyl peroxide (DCP) as crosslinking agent. DCP in various concentrations was mixed with LDPE chips in an extruder at 135 - 145°C. Monofilaments were drawn on a laboratory drawing machine at 110°C. It was found that tensile properties, percent shrinkage and density were improved with the increase in the concentration of DCP and in the heating period, whereas, however, the percent swelling decreased.
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  • 41
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Resultate von Untersuchungen über die chemische Wechselwirkung zwischen einigen monofunktionellen Modellverbindungen, die die Struktur und Reaktivität von wärmehärtbaren Phenol- und Harnstoff-Formaldehyd-Harzen simulieren, mit Holzkomponenten (Hemicellulosen, Cellulose und Lignin) werden dargelegt. Während Hemicellulosen deutlich dazu neigen, Kondensationsprodukte mit diesen Modellverbindungen zu ergeben, reagieren Lignine in manchen Fällen weniger leicht und abhängig davon, durch welchen Prozeß sie gewonnen worden sind, und abhängig von der Art der Modellverbindung. Cellulose reagierte wegen ihrer Kristallinität nicht unter den gegebenen Bedingungen.
    Notes: Results are presented on the chemical interactions occurring when some monofunctional model compounds simulating the structure and reactivity of thermosetting phenol- and urea-formaldehyde resins are mixed with wood components (hemicelluloses, cellulose, and lignins). Whereas hemicelluloses clearly show a propensity to give condensation products with these model compounds, lignins can react less readily in some instances depending on the delignification procedure used to isolate them and on the type of model compound. Cellulose did not react under the conditions chosen, mostly because of its crystalline character.
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  • 42
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    Angewandte Makromolekulare Chemie 173 (1989), S. 183-193 
    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: XPS-, SSIMS- und Wasserkontaktwinkelmessungen wurden verwendet, um den chemischen Einfluß von CF4/O2-Entladungen auf Polycarbonat (PC) aus Bisphenol A zu charakterisieren. Die durch Plasmabehandlung erzeugte Oberflächenmodifizierung kann auf der Basis der im Plasma vorhandenen aktiven Spezies, deren Konzentration durch Actinometrie bestimmt worden ist, erklärt werden.Bei kleinen Gehalten an O2 im Gas (1%) tritt eine umfassende Fluorierung der Oberfläche bedingt durch die Pfropfung von Fluorkohlenstoff-Radikalen ein. Es werden perfluorierte Inseln gebildet, wie der hohe Wert des zunehmenden Kontaktwinkels zeigt. Bei 20-80% O2 reagieren Fluoratome mit der Oberfläche und ätzen sie teilweise. Kleine Gehalte an Fluor, aber keine perfluorierten Inseln werden beobachtet. Sauerstoff trägt zum Ätzen bei und oxidiert die PC-Oberfläche. Die Sauerstoffkonzentration auf der Oberfläche nimmt mit Zunahme des O2-Gehalts im Gas zu, ebenso die Bildung von stark oxidierten Inselchen auf der Probenoberfläche, wie die dramatische Abnahme der Kontaktwinkel zeigt. Eine Verminderung der Aromatizität der Oberfläche, die mit Hilfe von XPS und SSIMS beobachtet wird, ist die Folge dieser Reaktionen.
    Notes: XPS, SSIMS and water contact angle measurements have been used to characterize the chemical effect of CF4/O2 discharges on polycarbonate (PC) made from bisphenol A. We found that the surface modification induced by plasma treatment can be clearly explained on the basis of the acitve species present in the plasma, whose concentration has been studied by actinometry.With very low amounts of O2 in the gas feed (1%) extensive fluorination of the surface occurs, due to grafting of the fluorocarbon radicals. Perfluorinated islands are formed, as shown by the high value of advancing contact angles. In the 20-80% O2 range, fluorine atoms react with the surface, partially inducing etching. Low amounts of fluorine are observed on the sample and no perfluorinated islands. Oxygen participates in etching and oxidizes the PC surface. We observed an increase of the surface concentration of oxygen with increasing the O2 amount in the gas feed and also the formation of strongly oxidized islets on the sample surface, as shown by the dramatic reduction of receding contact angles. A reduction of surface aromaticity, observed by XPS and SSIMS, is the consequence of these reactions.
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  • 43
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    Angewandte Makromolekulare Chemie 173 (1989), S. 213-218 
    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: An attempt was made to obtain cationic cellulose derivatives of highest possible degrees of substitution by treating dissolving grade pulps under homogeneous conditions with glycidyltrimethylammonium chloride in the solvent system dimethylacetamide/lithiumchloride. The influence of temperature, reaction time and molar ratio of the reagents was examined. A reaction time of 8 h and a temperature of 70°C have been found to be optimal. The cellulose content in solution and the molar ratio of the reagents have to be adapted to the used pulp.
    Notes: Es wurde der Versuch unternommen, durch Umsetzung von Zellstoffen mit Glycidyltrimethylammoniumchlorid im Lösungsmittelsystem Dimethylacetamid/Lithiumchlorid kationische Cellulosederivate mit möglichst hohen Substitutionsgraden zu erhalten. Hierzu wurden Temperaturabhängigkeit, Reaktionsdauer und Molverhältnis der Reaktanden untersucht. Als optimal erwies sich eine Reaktionsdauer von 8 h bei einer Reaktionstemperatur von 70°C. Der Cellulosegehalt in Lösung und das Molverhältnis der Reaktanden müssen dem verwendeten Zellstoff angepaßt werden.
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  • 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: Polyethylene terephthalate (PETP)-multifilament yarns with different thermal history were used as testing materials. Stress-strain-curves from 0.1 up to 100000%/s were determinated. These data were used to compute relaxation- and retardationcurves over 7 decades of time. By superponing relaxation-functions for various elongations respectively retardation-functions for various stresses, mastercurves over 21 respectively 13 decades of time were obtained which can be subdivided into 4 regions, associating the following changes of structure: Region 1: suddenly recovering quasielastic deformation with relaxation times between minor 1 and 10 sRegion 2: irreversible deformation, consolidation, with relaxation times between 10 and 105 s,Region 3: elastic behaviour of the physical network with relaxation times between 105 and 107 s andRegion 4: transformation and destruction of the network with relaxation times between 107 and 1016 s.
    Notes: Von Polyethylenterephthalat (PETP)-Multifilamentgarnen mit unterschiedlicher thermischer Vorgeschichte wurden Kraft-Dehnungs-Kurven mit den Dehngeschwindigkeiten 0,1 bis 100 000%/s ermittelt. Diese lassen sich zu Relaxations- und Retardationskurven über sieben Zeitdekaden umrechnen. Durch Superponieren von Relaxationsfunktionen für unterschiedliche Dehnungen bzw. Retardationsfunktionen für unterschiedliche Fadenzugspannungen werden Relaxations- und Retardationsfunktionen bis 21 bzw. 13 Zeitdekaden bestimmt, die sich in vier Bereiche unterteilen lassen, denen folgende Strukturveränderungen zugeordnet werden können: Bereich 1: sofort erholbare, quasielastische Deformation mit Relaxationszeiten kleiner 1 bis 10 s,Bereich 2: irreversible Deformation, Verfestigung, mit Relaxationszeiten zwischen 10 und 105 s,Bereich 3: elastisches Verhalten des physikalischen Netzwerkes mit Relaxationszeiten zwischen 105 und 107 s undBereich 4: Umbau und Zerstörung des Netzwerkes mit Relaxationszeiten zwischen 107 und 1016 s.
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  • 45
    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: Interferometric measurements of a PETP-monofilament yarn show that the orientation of the high pre-orientated material decreases after stretching and relaxing. The effect of desorientation is more distinctive by a slower deformation then by a high-speed deformation. The lower decrease is caused by a slower deformation. Material strained with a rate of 104%/s shows “crazes” visible by interferometry. These “crazes” are not cracks but sites with lowered orientation. For slower deformation it is visible interferometrically that the orientation of the macromolecules in the fiber is asymmetric. DTA-curves from PETP-fibres show an exothermic peak between 30 and 80°C which can be related to specific structures of the non cristalline regions. By low-speed straining this peak shifts to lower temperatures. Stress-free storing of the material causes the peak to move back to the original temperature. For material deformated at high-speeds this peak does not change its position.
    Notes: Interferenzmikroskopische Messungen eines PETP-Monofilamentgarns zeigen, daß die Orientierung des schon hoch vororientierten Materials durch Dehnen und wieder Entspannen abnimmt, langsame Verformung wirkt dabei stärker desorientierend auf das Material als eine schnelle Verformung. Die Packungsdichte nimmt durch Dehnen ab. Die größte Dehngeschwindigkeit bewirkt die größte Abnahme.Ein mit der Dehngeschwindigkeit ∊ = 104%/s gedehntes Monofilament zeigt interferenzmikroskopisch sichtbare „Crazes“. Diese „Crazes“ sind keine Risse, sondern nur rißförmige Orte verminderter Orientierung. Für kleinere Dehngeschwindigkeiten ist interferenzmikroskopisch Unsymmetrie der Orientierung sichtbar. DTA-Kurven von PETP-Fasern zeigen zwischen 30 und 80°C einen exothermen Peak, der spezifischen Strukturen der fehlgeordneten Bereiche zugeordnet werden kann. Bei niedrigen Dehngeschwindigkeiten verlagert sich dieser Peak zu niedrigeren Temperaturen. Durch Lagern des Materials kehrt er zur ursprünglichen Temperaturlage zurück. Für schnell deformiertes Material ändert dieser Peak seine Temperaturlage nicht.
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  • 46
    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: p-Acryloyloxy-tri-n-butylzinnbenzoat (ABTB) wurde durch Reaktion von p-Hydroxy-tri-n-butylzinnbenzoat und Acrylsäure in Gegenwart von Dicyclohexylcarbodiimid hergestellt. Die Monomerreaktivitätsverhältnisse für die Copolymerisationen von ABTB (M1) mit Methylacrylat (M2), Ethylacrylat (M2), n-Butylacrylat (M2), Methylmethacrylat (M2), Styrol (M2) und Acrylnitril (M2) wurden entsprechend zu r1 = 0,080, r2 = 1,046; r1 = 0,039, r2 = 1,585; r1 = 0,019, r2 = 2,076; r1 = 0,150, r2 = 1,710; r1 = 0,113, r2 = 1,339 und r1 = 0,007, r2 = 2,853 bestimmt. Die Q- und e-Werte für das zinnorganische Monomere wurden berechnet. Die Copolymerisationen wurden in Lösung bei 70°C mit 1 mol-% Azobisisobutyronitril als Initiator durchgeführt. Die Struktur von ABTB und der hergestellten Copolymeren wurde durch IR-und 1H-NMR-Spektroskopie untersucht.
    Notes: p-Acryloyloxy-tri-n-butyltin benzoate (ABTB) was prepared by the reaction of p-hydroxy-tri-n-butyltin benzoate and acrylic acid in the presence of dicyclohexylcarbodiimide. The monomer reactivity ratios for the copolymerizations of ABTB (M1) with methyl acrylate (M2), ethyl acrylate (M2), n-butyl acrylate (M2), methyl methacrylate (M2), styrene (M2) and acrylonitrile (M2) have been found to be r1 = 0.080, r2 = 1.046; r1 = 0.039, r2 = 1.585; r1 = 0.019, r2 = 2.076; r1 = 0.150, r2 = 1.710; r1 = 0.113, r2 = 1.339 and r1 = 0.007, r2 = 2.853, respectively. The Q and e values for the prepared organotin monomer were calculated. Copolymerization reactions were carried out in solution at 70°C using 1 mol-% azobisisobutyronitrile. The structure of the ABTB monomer and the prepared copolymers was investigated by IR and 1H-NMR spectroscopy.
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  • 47
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    Angewandte Makromolekulare Chemie 169 (1989), S. 49-58 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde die Herstellung von ungesättigten Polyestern untersucht, die aus Mischungen von Fumarsäure und Adipinsäure in verschiedenen Verhältnissen ohne zusätzlichen Katalysator entstehen. Der Verlauf der Polyveresterung wurde durch die Bestimmung der während der Reaktion produzierten Wassermenge verfolgt. Die kinetischen Parameter der Polyveresterung (Reaktionsordnung n, Aktivierungsenergie E, Frequenzfaktor k0) wurden bestimmt, und es wurde n = 3 in allen Fällen festgestellt, während die Werte von E und k0 mit zunehmendem Fumarsäureanteil in der Anfangsmischung zunehmen. Ein mathematisches Modell für die Polyveresterung wurde bestimmt, was auf den Herstellungs-Parametern (z. B. Aufheizprogramm) und den kinetischen Parametern basiert, und es wurde festgestellt, daß die Korrelation zwischen den Kurven der experimentell entstandenen Wassermenge und der theoretischen (berechneten) Wassermenge sehr gut ist. Die Eigenschaften der Endprodukte, wie Viskosität und die schwach gelbe Farbe, nehmen mit zunehmendem Fumarsäureanteil in der Anfangsmischung zu. Es wurden auch generelle Perspektiven für die praktische Anwendung dieser Methode diskutiert.
    Notes: The production of unsaturated polyesters based on mixtures of fumaric acid and adipic acid for different proportions without added catalyst was studied. The progress of the polyesterification was followed by determining the amount of water produced during the reaction. The kinetic parameters (reaction order n, activation energy E, frequency factor k0) of the polyesterification were determined and it was found out that n = 3 in all cases, while E and k0 increased by increasing amount of fumaric acid in the initial mixture of the reaction. A mathematical model for the polyesterification based on the production parameters (e.g. the heating program) and on the kinetic parameters was used and very good correlation was found between the corresponding pair of curves of water produced during the polyesterification, which were determined experimentally and theoretically (by calculating). With regard to the properties of the final product it was found out that its viscosity and its slight yellow colour increased by increasing the amount of fumaric acid in the initial mixture of raw materials. General prospects for practical application of this method were also discussed.
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  • 48
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    Angewandte Makromolekulare Chemie 170 (1989), S. 137-143 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die vorliegende Arbeit untersucht das linear-elastische Bruchverhalten von (PMMA) mit Poly(ethylen-co-vinylacetat) (EVA) oder EVA  -  g-Bernsteinsäureanhydrid (EVA-g-SA) mittels Kerbschlagzähigkeitsmessungen nach Charpy. Rasterelektronenmikroskopaufnahmen zeigen, daß in Blends, die durch „in situ“-Polymerisation des acrylischen Monomeren in Gegenwart des Elastomeren hergestellt wurden, eine IPN-Morphologie vorliegt, während ein Blend, das durch Mischung der Polymerkomponenten im Schmelzezustand gebildet wurde, die typische zweiphasige Struktur von dispergierten Elastomerdomänen in einer glasartigen Matrix zeigt.Die Ergebnisse der mechanischen Messungen stimmen gut mit den beobachteten Morphologien überein.
    Notes: In the present work blends between poly(methylmethacrylate) (PMMA) and poly(ethylene-co-vinylacetate) (EVA) or its derivative EVA-g-succinic anhydride (EVA-g-SA) have been investigated by linear elastic fracture mechanics (LEFM) with Charpy impact tests and by scanning electron microscopy (SEM). Blends prepared by “insitu” radical polymerization of the acrylic monomer in the presence of the rubbers have an IPN morphology, while a blend prepared by melt-mixing the polymer components shows the typical biphasic structure of rubbery domains dispersed in a glassy matrix.Furthermore, a different behaviour is found when using EVA-g-SA instead of EVA. A fair agreement is found between the response of the LEFM analysis applied to the results of Charpy impact tests and the observed morphologies.
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  • 49
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    Angewandte Makromolekulare Chemie 170 (1989), S. 159-172 
    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: Some routes to synthetize covalently bound chelating groups as 8-hydroxyquinoline or 8-hydroxyquinoline-5-sulfonic acid to cellulose are given. The products show a capacity of 500-800 μmol/g, fast kinetics of exchange and good stability against the eluent. The apparent stability constant of the complexes with Zn2+ are around 2 · 105 mol-1 dm3.
    Notes: Es werden mehrere Synthesemöglichkeiten für die Herstellung von an Cellulose immobilisierten 8-Hydroxychinolin- und 8-Hydroxychinolin-5-sulfonsäure-Derivaten beschrieben, die zu einem Produkt mit einer Kapazität von 500-800 μmol/g, hoher Austauschgeschwindigkeit und guter Stabilität gegenüber dem Eluenten führen. Die scheinbare Komplexbildungskonstante der Oxincellulosen mit Zn2+ ist etwa 2 · 105 mol-1 dm3.
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  • 50
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    Angewandte Makromolekulare Chemie 170 (1989), S. 203-210 
    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: This paper reports the results of UV-laser-irradiations of elastomer fibres under application of varying external tensions on the fibres and under varying laser conditions. It is known that tension as well as temperature fields can lead to these synergetic effects that are supposed to cause the surface structuring by UV-laser-irradiation. Therefore the purpose of the reported experiments was to evaluate whether tension or temperature as the source of the system instabilities eventually lead to surface structuring.
    Notes: Dieser Beitrag berichtet über die UV-Laserbestrahlung von Elastomerfasern unter dem Einfluß verschieden großer äußerer Spannungsfelder und unterschiedlicher Laserbedingungen. Aus der Literatur ist bekannt, daß synergetische Effekte, die als Ursache der Oberflächenstrukturierung angesehen werden, sowohl durch Temperaturwie auch Spannungsfelder getrieben sein können. Daher sollen die beschriebenen Experimente untersuchen, welche der genannten Bedingungen in der Hauptsache zur Instabilität des Systems und damit zur Oberflächenstrukturierung führen.
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  • 51
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    Angewandte Makromolekulare Chemie 173 (1989), S. 47-53 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde die Vernetzung von Polyethylen mit Benzo- und Naphtochinonen als Photoinitiatoren untersucht. Die Quantenausbeuten (ϕ) der Initiatorreaktionen in Polyethylen unter UV-Bestrahlung wurden gemessen. Die ϕ-Werte für Benzochinon, Tetrachlorbenzochinon, Tetrabrombenzochinon, Tetrafluorbenzochinon, Naphthochinon und 2,3-Dichlornaphtochinon waren 0,23, 0,18, 0,14, 0,26, 0,09 bzw. 0,11. Naphthochinone waren als Initiatoren zur Photovernetzung von Polyethylen effektiver.
    Notes: Crosslinking of polyethylene (PE) photoinitiated by some benzoquinones and naphthoquinones has been studied. The quantum yields (ϕ) of the initiator reactions in PE under UV irradiation were measured. The ϕ-values for benzoquinone, tetrachlorobenzoquinone, tetrabromobenzoquinone, tetrafluorobenzoquinone, naphthoquinone, and 2,3-dichloronaphthoquinone were equal to 0.23, 0.18, 0.14, 0.26, 0.09, and 0.11, respectively. Naphthoquinones were more effective as initiators in photocrosslinking of polyethylene.
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  • 52
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    Angewandte Makromolekulare Chemie 173 (1989), S. 101-110 
    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: Polystyrol (PS) wurde mit gepfropftem thermomechanischem Zitterpappel- und Birkenzellstoff verstärkt bzw. gefüllt. Die Abhängigkeit der Zugfestigkeitseigenschaften der Verbundstoffe von verschiedenen Gehalten an Füllstoff, vom Polymergehalt der gepfropften Faser, von der Anwesenheit von Homopolymerem in der gepfropften Faser und von der Imprägnierung der Fasern mit PS wurde untersucht. PS, das mit gepfropftem Zitterpappel- und Birkenzellstoff gefüllt war, zeigte eine deutliche Verbesserung der Zugfestigkeit und des Spannungswertes. Die Bruchenergie und die Dehnung der Verbundstoffe nahm mit Zunahme der Konzentration an Füllstoff ab.
    Notes: Polystyrene (PS) was reinforced/filled with grafted thermomechanical pulp (TMP) of aspen and birch. The dependence of tensile properties of composites on different loadings of filler, on polymer loading in grafted fiber, on the presence of homopolymer in grafted fiber, and on impregnation of fibers with PS were studied. PS filled with grafted aspen and birch (lower polymer loading) showed a significant increase in tensile strength and modulus. Fracture energy and elongation of the composites decreased with an increase in the concentration of filler.
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  • 53
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    Angewandte Makromolekulare Chemie 165 (1989), S. 153-164 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde der Einfluß der durch Terpolymere modifizierten Polystyrolfilme auf ihre Widerstandsfähigkeit gegenüber UV-Strahlung untersucht.ESR, IR, UV, Massenspektroskopie sowie Viskositäts- und Löslichkeitsmessungen ergeben, daß 3% ABS oder MBS in den Polystyrolfilmen einen bedeutenden Einfluß auf die photochemischen Prozesse hat. Proben mit Terpolymeren, die mit UV-Licht bestrahlt waren, weisen auf eine größere Konzentration von Radikalen mit kürzerer Halbwertszeit hin. Beide Terpolymere bewirken eine höhere Ausbeute der Photooxidation und Vernetzung des Polystyrols und setzen seine Photodehydrierung herab.
    Notes: The influence of acrylonitrile-butadiene-styrene-terpolymer (ABS) and methyl methacrylate-butadiene-styrene-terpolymer (MBS) modifying the polystyrene (PS) films on its resistance to UV radiation were investigated.On the basis of the results of ESR, IR, UV, mass spectroscopy, viscosimetric and solubility measurements it was found that 3% of ABS or MBS in polystyrene films have a clear influence on the course of photochemical processes. After UV-irradiation of the samples, at the presence of this terpolymers, a greater concentration of free radicals with shorter half-life times was observed.Both terpolymers increase the productivity of photooxydation of polystyrene as well as its crosslinking and decrease its dehydrogenation.
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  • 54
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    Angewandte Makromolekulare Chemie 173 (1989), S. 219-243 
    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: Epoxy resins of Bisphenol A, cyanuric acid, and their mixtures were synthetized with epichlorohydrin. The obtained products were characterized by gel permeation chromatography, FT-IR-spectroscopy, 1H-NMR-, 13C-NMR-spectroscopy and DSC-analysis. During the syntheses besides the glycidyl-derivatives of Bisphenol A and cyanuric acid also biuret-derivatives were formed as a result of cracking the isocyanurate-ring. The formed resins of Bisphenol A-cyanuric acid mixtures can be crosslinked by heat without additional curing agents.
    Notes: Aus Bisphenol A, Cyanursäure und deren Mischungen wurden mit Epichlorhydrin Epoxidharze hergestellt. Die entstandenen Produkte wurden durch Gelpermeationschromatographie, FT-IR-, 1H-NMR-, 13C-NMR-Spektroskopie und DSC-Analyse charakterisiert. Bei den Synthesen entstehen außer den Glycidylderivaten von Bisphenol A und Cyanursäure Spaltprodukte des Isocyanuratringes bzw. deren Glycidylderivate. Die erzeugten Mischharze lassen sich ohne Härtungsmittel in der Wärme vernetzen.
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  • 55
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 56
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    Angewandte Makromolekulare Chemie 166 (1989), S. 71-80 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The lipid bilayers of cell membranes are usually connected to two types of biopolymers: the cytoskeleton and the glycocalix. These structures are not only responsible for the stabilization of the lipid bilayer, they also alter the surface properties of the cells. Among the various attempts to mimick membrane properties using polymeric systems(1), one method is the fixation of amphiphilic polymers via hydrophobic anchor groups to lipid bilayers. In the experiments reported here the influence of amphiphilic polymers on the morphology of giant unilamellar liposomes has been investigated. Therefore a series of amphiphilic polyvinylpyrrolidone and dextran derivatives has been synthesized. The fixation of these polymers to the liposomal membranes could be shown with a fluorescence-labelled derivative by using epifluorescence microscopy. The polymer-membrane interaction caused by the insertion of the anchor groups leads to drastic morphological changes in this model membrane system. The exclusive interaction with the outer membrane of multilamellar liposomes could be demonstrated by freeze fracture electron microscopy. In addition, the anchoring of a natural capsular polysaccharide in liposomes has been proven by immunofluorescence. In these experiments, also a clustering (patching) of the antigen caused by the binding of the antibody could be observed.
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  • 57
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    Angewandte Makromolekulare Chemie 168 (1989), S. 91-108 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Copolymerisation von Acrylnitril (AN) und Glycidylmethacrylat (GMA) in Tetrahydrofuran wurde untersucht. Die Reaktivitältsverhältnisse wurden bestimmt und das thermische Verhalten der Homo- und der Copolymeren wurde mit Hilfe der Differentialthermoanalyse (DTA) und der Thermogravimetrie (TG) untersucht. Es wurde gefunden, daß GMA beim Aufheizen die Nitriloligomerisationsreaktion initiiert. Die Anfärbbarkeit und die Bleichung in UV-Licht wurden ebenfalls untersucht. Verglichen mit Homopolyacrylnitril zeigen die Copolymeren bessere Affinität gegen basische Farbstoffe. Diese Affinität steigt mit zunehmendem GMA-Anteil im Copolymeren an.
    Notes: The copolymerization of acrylonitrile (AN) with glycidyl methacrylate (GMA) has been investigated in tetrahydrofuran (THF). The reactivity ratios were estimated and the thermal behaviour of the homo- as well as the copolymers, both in air, and under nitrogen atmosphere was investigated using differential thermal analysis (DTA) and thermogravimetry (TG) techniques. GMA was found to initiate the nitrile oligomerization reaction in the copolymers upon heating. The dyeing ability, as well as the colour fastness towards UV light have also been investigated. It was found that the copolymers showed better affinity towards basic dyes compared to homopolyacrylonitrile. This affinity increases with increasing the GMA content in the copolymer.
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  • 58
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    Angewandte Makromolekulare Chemie 168 (1989), S. 109-117 
    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: Unverstreckte und verstreckte Polyethylene mit unterschiedlichen Molekulargewichten wurden mit Salpetersäure oxidiert. Der Einfluß der Oxidation auf die Schmelz- und Kristallisationstemperatur der Polymeren wurde mittels Differentialkalorimetrie untersucht.
    Notes: Melting, recrystallisation and remelting of undrawn and drawn linear polyethylene with different molecular weight were studied by differential scanning calorimetry before and after oxidation with nitric acid.
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  • 59
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    Angewandte Makromolekulare Chemie 168 (1989), S. 119-127 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die thermischen Eigenschaften von nur durch C—C-Bindungen vernetzten Polyurethanen aus 4,4′-Diphenylmethandiisocyanat und Poly(ethylenadipat) wurden mit Hilfe der isothermen und nicht-isothermen Thermoanalyse in Stickstoffatmosphäre untersucht. Die thermische Stabilität von diesen Polyurethanen wurde mit der Stabilität von früher untersuchten, mit Allophanat-Bindungen vernetzten Polyurethanen verglichen.Es wurde festgestellt, daß die chemische Struktur der Vernetzungsbindungen das Anfangsstadium des Abbauprozesses bestimmt.
    Notes: Thermal properties of polyurethanes based on 4,4′-diphenylmethane diisocyanate and poly(ethylene adipate) crosslinked only by C—C linkages were studied by isothermal and non-isothermal thermogravimetry carried out in nitrogen atmosphere. Previously studied polyurethanes crosslinked only with allophanate groups were used for comparison.It was found that the structure of crosslinks determines the initial stage of degradation process.
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  • 60
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    Angewandte Makromolekulare Chemie 168 (1989), S. 205-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde die Dehydrofluorierung von Polyvinylidenfluorid (PVDF)-Pulvern und -Filmen durch verschiedene basische Lösungen untersucht. Speziell die Reaktivität von 1,8-Diazabicyclo[5.4.0]-7-undecen (DBU) in Ethanol, KOH in 2-Propanol und wäßriger NaOH-Lösung mit Tetrabutylammoniumbromid wurde mit Hilfe von Veränderungen der Absorptionsbanden von PVDF-Filmen im Infrarot-(IR) und Ultraviolett-sichtbaren Bereich (UV-VI) untersucht. Neben den durch DBU oder KOH bewirkten Eliminierungsreaktionen treten sicherlich auch Substitutionsreaktionen auf. Die elektrische Leitfähigkeit von dehydrofluorierten PVDF-Filmen nimmt durch Dotierung mit Iod merklich zu, und die Aktivierungsenergien der Leitung liegen zwischen 0,4 und 0,5 eV. Verstrecken eines dehydrofluorierten und mit Iod dotierten PVDF-Films führt zu einer Anisotropie der Leitfähigkeit.
    Notes: The dehydrofluorination of poly(vinylidene fluoride) (PVDF) powder and films was studied using several kinds of base solution. Especially the reactivity of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) in ethanol, KOH in 2-propanol and aqueous NaOH solution with tetrabutylammonium bromide was investigated by the change in infrared (IR) and ultraviolet-visible (UV-VI) absorptions of PVDF films. The elimination reactions by DBU or KOH were considered to be accompanied by substitution reaction. The electrical conductivity of dehydrofluorinated PVDF films increased markedly by doping with iodine, and the activation energies of conduction were found to be between 0.4 and 0.5 eV. When a drawn PVDF film was dehydrofluorinated and doped with iodine, anisotropy in conductivity was observed.
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  • 61
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    Angewandte Makromolekulare Chemie 169 (1989), S. 29-36 
    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: Schmelzrheologische Untersuchungen an Nylon 6/Polyethylenterephthalat (PETP) Blends (PETP-Gehalt zwischen 10 und 50%) wurden mit Hilfe eines Kapillar-Rheometers mit Schergeschwindigkeiten im Bereich von 58 s-1 bis 1,15 · 103 s-1 durchgeführt. Mit steigendem PETP-Gehalt im Blend wurde eine Abnahme der Schmelzviskosität und des nicht-Newtonschen Verhaltens beobachtet. Die Modellgleichung, von Uemura und Takayanagi für viskoelastisch schmelzende Blends entwickelt, wurde zum besseren Verständnis der Dispersion und Morphologie der Nylon 6/PETP-Blends benutzt. Ferner wurde eine umgekehrt proportionale Beziehung zwischen der Schmelzviskosität (η) und dem Elastizitätsmodul (E') von Fasern beobachtet.
    Notes: Melt rheological studies of nylon 6/polyethylene terephthalate (PETP) blends (PETP content varying from 10 to 50%) were carried out using capillary rheometer in the shear rate range of 58 s-1 to 1.15 · 103 s-1. With increasing PETP content in the blend a decrease of the melt viscosity as well as non-Newtonian behaviour was observed. The model equation developed by Uemura and Takayanagi for viscoelastic melt blends has been used to understand the state of dispersion and morphology of a nylon 6/PETP blend system. Further, an inverse relationship between polymer melt viscosity (η) and elastic modulus (E') of fibres was observed.
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  • 62
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Wirkungsmechanismus des Antioxidans N,N′-Diphenyl-1,4-phenylendiamin (I, DPPD) wurde bei Modellbedingungen untersucht. Die Verbindung I reagiert nach der Oxidation zum Semichinonradikal VIII oder Wursters Kation IX mit 1-Cyano-1-methylethyl (Modellradikal) auf zwei verschiedenen Wegen, und die Reaktion wird durch schwache Säuren beschleunigt. Eine Reaktionsweise führt zur Bindung von Alkyl an Stickstoff unter Bildung von Verbindung III. Diese Verbindung ist unbeständig und, besonders in Gegenwart von Säuren, spaltet leicht Olefin unter Regeneration von DPPD ab. Dieses Verhalten ist ein Modell des Regenerationsmechanismus beim Stabilisierungseffekt von DPPD. Bei diesem Mechanismus werden Alkylperoxy- und Alkylradikale, wührend der Alterung der Kohlenwasserstoffsubstrate unter der Bedingung von relativem Sauerstoffmangel durch DPPD und seinem Oxidationsprodukt (VIII oder IX) desaktiviert. Der zweite Weg führt zur Bindung von Alkyl an den Benzolring unter Bildung von den Verbindungen IV und V. Er stellt so ein Modell für die Bindung von DPPD in die Polymerkette oder auch bei der Vernetzung der Polymerkette während der Alterung des mit DPPD stabilisierten Polymeren dar. Die Verbindung IV unterliegt wegen der Anwesenheit einer Nitrilgruppe noch anderen Veränderungen, bei denen die Verbindungen VI und VII entstehen.
    Notes: The mechanism of action of an antioxidant, N,N′-diphenyl-1,4-phenylene diamine (I, DPPD)Decoding of abbreviations see p. 48., was investigated under model conditions. After oxidation to a semiquinone radical, phenyl (4-phenylamino phenyl)aminyl (VIII), or to Wurster's cation phenyl (4-phenylamino phenyl)ammoniumyl (IX), I reacts with 1-cyano-1-methylethyl (model alkyl) by two routes, both of which are accelerated by weak acids. One of these routes results in alkyl being bound to nitrogen with formation of N,N′-diphenyl N-(1-cyano-1-methylethyl)1,4-phenylene diamine (III). The latter compound is labile, and particularly in the presence of acids readily splits off olefin with regeneration of DPPD. This behaviour is a model of the regeneration mechanism of the stabilizing effect of DPPD, which alternately with its oxidation product (VIII or IX) deactivates the alkylperoxyl and alkyl radicals during the ageing of hydrocarbon substrates under conditions of the relative deficiency of oxygen. The other route leads to binding of the alkyl in the benzene ring with formation of N,N′-diphenyl 2-(1-cyano-1-methylethyl) 1,4-phenylene diamine (IV) and N,N′-diphenyl 2-(1-cyano-1-methylethyl) 1,4-benzoquinone diimine (V), thus modelling the binding of DPPD in the polymer chain, and even the crosslinking of the chain during the ageing of a polymer inhibited with DPPD. Due to the presence of the nitrile group, IV undergoes some further changes, which give rise to the formation of 3,3-dimethyl 2-imino-1-phenyl 5-phenylamino indoline (VI) and 2-acetylimino 3,3-dimethyl-1-phenyl 5-phenylamino indoline (VII).
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  • 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: Insoluble spherical xerogel particles of aluminium carboxymethyl cellulose are prepared by partial drying of ionotropic gels formed by dropping aqueous solutions of sodium carboxymethyl cellulose into crosslinking solutions of aluminium salts. The swelling ability of the porous and mechanically stable carriers, which are surrounded by a dense surface, rises by partial transformation of carboxy groups into the sodium salts and diminishes with growing content of free acid groups and increasing temperature of drying.
    Notes: Unlösliche sphärische Aluminiumcarboxymethylcellulose-Xerogelpartikel werden durch partielle Trocknung ionotroper Gele hergestellt, die durch Eintropfen wäßriger Lösungen von Natriumcarboxymethylcellulose in vernetzende Aluminiumsalzlösungen entstehen. Das Quellvermögen der porösen und mechanisch stabilen Trägermaterialien, die von einer dichten Außenschicht umgeben sind, erhöht sich durch partielle Umwandlung von Carboxygruppen in die Natriumsalze; es verringert sich mit zunehmendem Gehalt an freien Säuregruppen und steigender Trocknungstemperatur.
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  • 64
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    Angewandte Makromolekulare Chemie 169 (1989), S. 93-100 
    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 Modifizierung von Polybutadien durch katalytische und photolytische Spaltung von Dimethyldiazomalonat (dmdm) wird beschrieben. Durch diese Methode werden hochreaktive Carbene erzeugt, die die Bildung von Additions- und Insertionsprodukten bewirken. Die chemischen Strukturen der modifizierten Polymeren wurden durch NMR-Spektroskopie bestätigt. Auch Carbendimere wurden in nicht unbedeutendem Maße gebildet, was vom Molekulargewicht und der Mikrostruktur des Ausgangspolymeren abhängt.
    Notes: Modifications of polybutadienes via catalytic and photolytic decomposition of dimethyldiazomalonate (dmdm) are described. This method pertains to the generation of highly reactive carbenes which give rise to the formation of addition and insertion products. Chemical structures of the modified polymers were confirmed by NMR spectroscopy. It was found that carbene dimers were also formed in a significant extent depending on the molecular weight and microstructure of the initial polymers.
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  • 65
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    Angewandte Makromolekulare Chemie 169 (1989), S. 101-117 
    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 pfropfcopolymerisation von N-Methylolacrylamid auf Flachs/Polyester-Mischgewebe mit Hilfe eines Eisen/Cellulosethiocarbonat/H2O2-Redoxsystems wurde unter verschiedenen Bedingungen, wie Wasserstoffperoxid-Konzentration (1-60 mmol/l), Eisen-Ammoniumsulfat-Konzentration (1-50 mmol/l), N-Methylolacrylamid-Konzentration (5-200%, bezogen auf das Probengewicht), Polymerisationszeit (10-90 min), Temperatur (20-50°C) und pH-Wert des Mediums (1,1-11) untersucht. Zur Berechnung der Pfropfausbeute wurde der Stickstoff-und/oder der Methylolgehalt benutzt. Die erhaltenen Ergebnisse zeigen, daß die Pfropfausbeute, die durch Stickstoffanalyse bestimmt wurde, umso h6her ist, je mehr die H2O2-Konzentration steigt; ab 40 mmol/l bleibt die Ausbeute konstant. Auf der anderen Seite hat die Pfropfausbeute, die aus dem Methylolgehalt bestimmt wurde, einen Maximalwert bei 10 mmol/l H2O2. Die Ergebnisse zeigen, daß die Pfropfung sehr begünstigt abliruft, wenn die Reaktion mit 1 mmol/l Eisen-Ammoniumsulfat bei einem pH von 4,4, einer Temperatur von 30°C und 60 min lang durchgefuhrt wird. Die Aktivierungsenergie der Copolymerisationsreaktion betrirgt 9,74 kJ/mol, und die Pfropfausbeute steigt mit steigender N-Methylolacrylamid-Konzentration. Weiterhin wurde ein Vergleich der Polymerisatonswirksamkeit in Bezug auf die Pfropfung von N-Methylolacrylamid auf Flachs/Polyester-Mischgewebe zwischen einem Eisen-/Cellulosethiocarbonat/H2O2- und einem Eisen/H2O2-Redoxsystem durchgefuhrt. Diese beiden Systeme wurden bezuglich der Pfropfausbeute, des Homopolymeranteils, des Gesamtumsatzes, des Pfropfungsgrades und des Polymerisationsgrades des Homopolymeren untersucht.
    Notes: Graft copolymerization of N-methylolacrylamide onto flax/polyester blend fabric using ferrous cellulose thiocarbonate/H2O2 redox system was investigated under different conditions including hydrogen peroxide concentration (1-60 mmol/l), ferrous ammonium sulphate concentration (1-50 mmol/l), N-methylolacrylamide concentration (5-200%, based on weight of sample), polymerization time (10-90 min), temperature (20-50°C), and pH of the medium (1.1-11). The nitrogen content and/or the methylol content were used for calculation of graft yields. Results obtained indicated that graft yields, derived from nitrogen analysis, are higher the greater the H2O2 concentration increases till 40 mmol/l, then level off. On the other hand, graft yields derived from methylol content exhibit maximum value at 10 mmol/l H2O2. The results indicate also that grafting was highly favoured when it was carried out using 1 mmol/l ferrous ammonium sulphate and pH 4.4 at 30°C for 60 min. The apparent activation energy of the copolymerization reaction amounts to 9.74 kJ/mol. Furthermore, the graft yield increases by increasing N-methylolacrylamide concentration within the range studied. The work was further extended to include a comparison between the polymerization efficiencies of the ferrous cellulose thiocarbonate/H2O2 redox system and the ferrous/H2O2 redox system in inducing grafting of N-methylolacrylamide onto flax/polyester blend fabric. For this reason, the two systems were studied with respect to graft yield, homopolymer proportion, total conversion, graft efficiency, and homopolymer efficiency.
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  • 66
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    Angewandte Makromolekulare Chemie 169 (1989), S. 137-142 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Flammschutz von Polymeren durch Entstehung von intumeszierender Kohle wird allgemein auf die physikalischen isolierenden Eigenschaften der bei der Verkohlung entstehenden Oberfläche zurückgeführt. Diese Eigenschaften wiederum hängen von der physikalisch-chemischen Struktur der Kohle ab, über die nur wenig bekannt ist. Es wird gezeigt, daß die Elektronenrastermikroskopie und Mikroanalyse durch ein energiedispersives System Aufschluß geben über die Morphologie und Zusammensetzung solcher intumeszierender Systeme. Die erhaltenen Daten tragen zum Verständnis der Schwerentflammbarkeit bei.
    Notes: The protection provided by intumescent chars against the action of the flame is generally attributed to their physical insulating properties. These in turn depend on the physical chemical structure of swollen char, which however has been scarcely studied. It is shown that scanning electron microscopy and microanalysis by energy dispersive system supply detailed information on the morphology and the chemical composition of intumescent systems. The data obtained contribute to the understanding of the fire retardance mechanism.
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    Angewandte Makromolekulare Chemie 169 (1989), S. 143-151 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: CO2- und Eximer-Laser-(193, 248, 350 nm) Behandlungen wurden an Polyetheretherketon (PEEK) vorgenommen. Hochintensive Eximer-Laser-Strahlung verursacht wirksame Ätzung, hauptsächlich durch thermische Effekte. Die Bestrahlung mit CO2-Lasern und hochintensiven Eximer-Lasern führt zu Änderungen in der Oberflächenchemie und -morphologie.Intensitätsschwache Eximer-Laser-Bestrahlung bei 193 und 248 nm begünstigt das Auftreten photochemischer Phänomene. Die chemische Modifizierung der Oberfläche führt zur Sauerstoffabnahme, und eine bevorzugte Eliminierung der Ketonbrücke wurde festgestellt. Gleichzeitig wurden morphologische Veränderungen der Oberfläche gefunden; Beugungseffekte führen zu konischen Strukturen, und die Abscheidung größerer Oligomerer bewirkt die Bildung von Ablagerungen auf der Oberfläche.
    Notes: CO2 and excimer laser (193, 248, 350 nm) treatments were performed on poly(etheretherketone) (PEEK). High fluence excimer laser irradiation induced efficient etching, mainly due to thermal effects. The irradiation with CO2 lasers and high fluence excimer lasers introduced limited changes in surface chemistry and morphology.Low fluence excimer laser irradiation, particularly at 193 nm and 248 nm, favored the occurence of photochemical phenomena. Surface chemical modifications leading to oxygen depletion and preferential elimination of the ketonic bridge were assessed. At the same time surface morphological alterations were found, diffraction effects led to cone-like structures while the redeposition of heavy oligomers caused the formation of debris on the surface.
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  • 68
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    Angewandte Makromolekulare Chemie 168 (1989), S. 9-21 
    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: Die Ergebnisse von Untersuchungen über die molekulare Überstruktur von Mischungen aus teilkristallinem Polyamid-6 (PA-6) und amorpher Poly(methacrylsäure) (PMA) werden vorgestellt.Die Bestimmung der molekularen Überstruktur gelang durch Berechnung von Korrelationsfunktionen und Grenzflächenverteilungsfunktionen aus SAXS-Aufnahmen.Der Einbau von Poly(methacrylsäure) bewirkt eine Transformation der Kristallstruktur des PA-6 vom γ-Typ zum α-Typ. Bei einem PMA-Gehalt von weniger als 46% hat die Mischung eine lamellare Struktur; ein zunehmender PMA-Anteil vergrößert die Langperiode. PMA bildet mit dem amorphen Anteil von PA-6 eine homogene Phase; Mikrodomänen werden nicht beobachtet.Mit zunehmendem PMA-Gehalt sinkt der Kristallinitätsindex. Gleichzeitig nimmt die Dicke der Übergangsschicht zwischen den kristallinen Regionen und der aus PMA und amorphem PA-6 bestehenden Phase zu. Bei hohem PMA-Gehalt verschwindet die lamellare Struktur.
    Notes: The results of investigations of the supermolecular structure of the mixture of a semicrystalline polymer polyamide-6 (PA-6) and of an amorphous one, poly(methacrylic acid) (PMA), are presented. The determination of the supermolecular structure was realized using the correlation functions and the interface distribution functions calculated from SAXS patterns. It was stated that the introduction of poly(methacrylic acid) results in a transformation of the γ-type crystalline structure into the α-type structure. Until the PMA content is less than 46%, the blend has a lamellar structure, and an increase in the PMA content causes an increase in the long period. PMA and the amorphous phase of PA-6 form a homogeneous phase, there are no microdomains of PMA.An increase in the PMA content results in a decrease of the crystallinity index. Simultaneously, the thickness of the transition layers between the crystalline regions and the phase composed of PMA and of the amorphous phase of PA-6 increases. When the content of PMA is large, the lamellar structure disappears.
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  • 69
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    Angewandte Makromolekulare Chemie 168 (1989), S. 23-35 
    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: N-substituierte Maleinimide sind thermische Stabilisatoren für Hart-Polyvinylchlorid (PVC). Dies wurde durch Messung der Dehydrochlorierungsrate und des Ausmaßes der Verfärbung des Polymeren bei 180°C in Luft untersucht. Die Ergebnisse zeigen die höhere Stabilisierungswirkung dieser Produkte im Vergleich zu Stabilisatoren wie basisches Bleicarbonat, Dibutylzinnmaleat und Cadmium-Bariumstearat, die üblicherweise in der Industrie benutzt werden. Die Induktionszeit (Ts) steigt in dem Maße, in dem der positive Resonanzeffekt (+R) der Substituenten zunimmt. Ferner bewirken die untersuchten Stabilisatoren gegenüber Stearatstabilisatoren bessere Farbbeständigkeit der abgebauten Proben. Diese Stabilisatoreffektivität ist darauf zurückzuführen, daß der Stabilisator Radikale einfangen kann, die bei dem radikalischen Abbau von PVC entstehen. Die gute Farbstabilität resultiert aus der Fähigkeit des Stabilisators, mit den konjugierten Doppelbindungen, die durch den Abbau des PVC in der Polymerkette entstehen, in Wechselwirkung zu treten. Ein Mechanismus für die Wirkungsweise des Stabilisators wird vorgeschlagen.
    Notes: N-substituted maleimides have been investigated as thermal stabilizers for rigid polyvinylchloride (PVC) at 180°C in air by measuring the rate of dehydrochlorination and the extent of discoloration of the polymer. The results reveal the higher stabilizing efficiency of these products relative to basic lead carbonate, dibutyl tin maleate, and cadmium-barium stearate stabilizers commonly used in industry. The induction period (Ts) increases as a function of the positive resonance effect of the substituents (+R). Moreover, the investigated stabilizers impart better color stability for the degraded samples as compared with the stearate stabilizer. The stabilizer efficiencies are attributed to their radical trapping potency which intervenes with the radical degradation process of PVC, while the good color stability is due to the ability of the stabilizer to interact with the conjugated double bonds formed on the PVC chains as a result of degradation. A mechanism illustrating the stabilizer's action is proposed.
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  • 70
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    Angewandte Makromolekulare Chemie 168 (1989), S. 37-52 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The stress-strain behaviour of filament yarns has been determined by variation of strain rates from 10-1 up to 105%/s. Strain rates up to 10%/s are obtained with a tensile testing machine. The higher strain rates up to 105%/s are obtained with an apparatus using a falling weight by variation of the height of fall and the length of the yarn.Because of the high-speed impact and time of strain/influence down to 10-4 s together with the variation of the height of fall between 0,6 and 166 cm a profound discussion of errors is necessary.
    Notes: Kraft-Dehnungs-Graphen von Filamentgarnen für die Dehngeschwindigkeiten zwischen 10-1 und 105%/s werden ermittelt. Für die niedrigen Dehngeschwindigkeiten bis 10%/s wird eine übliche Zugprüfmaschine benutzt, die höheren Dehngeschwindigkeiten werden mit einer Fallschlagapparatur durch Variation der Fallhöhe und der Fadenlänge erreicht.Aufgrund der hohen Dehngeschwindigkeit und der Meßzeiten bis minimal 10-4 s sowie der Variation der Fallhöhe zwischen 0,6 und 166 cm treten Fehler auf, die eingehend diskutiert werden.
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  • 71
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    Angewandte Makromolekulare Chemie 168 (1989), S. 81-89 
    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: Neue Esterimid- und Ketoimidpolymere, die Biphenylgruppen enthalten, wurden synthetisiert und die Strukturen durch thermogravimetrische (TGA) Messungen untersucht. Es zeigte sich eine unterschiedliche Beständigkeit in bezug auf die Struktur des Imides. Die entsprechenden Amid-Imid-Verbindungen wurden als Monomere geprüft, aber die Polymerisation verlief nicht wie erwartet, und es konnten Nebenreaktionen durch 13C-NMR Spektroskopie beobachtet werden.
    Notes: New esterimide and ketoimide polymers containing a biphenyl group have been synthesized and characterized by spectral techniques. Their thermal properties have been studied by thermogravimetric (TGA) measurements, showing a different stability with regard to the imide structure. The analogous amide imide compounds have been tested as monomers, but their polymerization has not taken place as we expected and side reactions have been detected by 13C-NMR spectroscopy.
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  • 72
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyethylene terephthalate (PETP) multifilament yarns with different thermal history were used as testing materials.The stress-strain curves for strain rates from 0.1 up to 100 000%/s show that the maximum tensile force increases and the elongation decreases with increasing strain rate. However, there are differences for yarns with different thermal history. So a free of stress treated yarn shows less change of the maximum tensile force with increasing strain rate than a yarn treated at the same temperature but under stress. The elongation by the maximum tensile force shows the opposite behaviour. With increasing influence of the elongation rate to the force of rupture the ratio of the maximum tensile force and the relevant elongation increases faster.The initial slope (modulus) of the stress-strain curves of the multifilament yarn increases for all futed stresses and temperatures with the strain rate. The local minimum of the modulus curves shifts to higher modulus with increasing strain rate while the position of the minimum as a function of the elongation remains constant.
    Notes: Untersucht werden Polyethylenterephthalat (PETP)-Multifilamentgarne mit unterschiedlicher thermischer Vorgeschichte.Die Kraft-Dehnungs-Kurven für die Dehngeschwindigkeit von 0,1 bis 100 000%/s zeigen, daß die Höchstzugkraft mit der Dehngeschwindigkeit zunimmt und die Höchstzugkraftdehnung abnimmt. Für die Garne mit unterschiedlicher thermischer Vorgeschichte bestehen jedoch Unterschiede, was die Änderung der Höchstzugkraftund Höchstzugkraftdehnungswerte mit der Dehngeschwindigkeit betrifft. So weist ein spannungslos thermisch behandeltes Material eine geringere Änderung der Höchstzugkraft mit steigender Dehngeschwindigkeit auf als ein bei gleicher Temperatur, aber unter Spannung thermofixiertes Material. Die Höchstzugkraftdehnungswerte zeigen dagegen ein umgekehrtes Verhalten. Mit wachsendem Einfluß der Dehngeschwindigkeit auf die Bruchkraft nimmt das Verhältnis von Höchstzugkraft zu Höchstzugkraftdehnung stärker zu.Die Anfangssteigung, d. h. der Anfangsmodul der K-D-Kurven des Fadenmaterials, nimmt für alle Fixierspannungen und -temperaturen mit der Dehngeschwindigkeit zu. Das lokale Minimum der ersten Ableitung der K-D-Kurven (lokales Modulminimum) verlagert sich mit zunehmender Dehngeschwindigkeit zu höheren Modulwerten, die Lage des Minimums als Funktion der Dehnung bleibt jedoch konstant.
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  • 73
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    Angewandte Makromolekulare Chemie 170 (1989), S. 43-57 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird über eine systematische Studie über die Herstellung von Dimethylacrylamid-Harzen, die Amino- oder Carboxylgruppen tragen, berichtet. Details werden über die Synthesen von Dimethylacrylamid (1) und einer Zahl vernetzender (2) und funktionelle Gruppen tragender (3-5) Monomerer auf Acrylamid-Basis mitgeteilt. Es wird die Terpolymerisation von 1 und 2 mit 3 (oder mit 4 oder 5) in Wasser/Öl-Suspension beschrieben, die zu Harzen mit weitem Bereich von Funktionalität und Quellverhalten führt. Die Quellfähigkeit verschiedener Harzproben in Dichlormethan, Dimethylformamid, Dimethylsulfsoxid, Methanol, Essigsäure und Wasser wurde festgestellt. Ferner werden typische chemische Umsetzungen von Dimethylacrylamid-Harzen beschrieben.
    Notes: A systematic study of the preparation of dimethylacrylamide resins carrying amino, carboxyl or activated carboxyl functionality is reported. Details of the syntheses of dimethylacrylamide (1) and a number of acrylamide-based crosslinking (2) and functional (3-5) monomers are given. The terpolymerization of 1 and 2 with 3 (or with 4 or 5) by a water in oil (w/o or reverse) suspension polymerization procedure is described for the preparation of dimethylacrylamide resins having a wide range of functionality and swelling behaviour. The swellability of several of the resin samples in dichloromethane, dimethylformamide, dimethylsulfoxide, methanol, acetic acid, and water is given. Typical chemical transformations of dimethylacrylamide resins are also described.
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  • 74
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    Angewandte Makromolekulare Chemie 170 (1989), S. 115-125 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Substitution von Chlor in PVC durch 3,6-Diamino-N-methyl-carbazol entsteht ein Kondensat, das in allen Lösungsmitteln für PVC unlöslich ist. Dieses Kondensat ist thermisch stabiler als PVC. Auch die dielektrischen Eigenschaften unterscheiden sich deutlich von denen von PVC. Die Sulfonierung des PVC-Carbazol-Kondensats liefert ein Kationenaustauscherharz mit SO3H- und COOH-Gruppen.
    Notes: The chlorine displacement reaction between PVC and N-methylcarbazole-3,6-diamine affords a condensate which is insoluble in all possible solvents of PVC. The overall thermal stability of this condensate is appreciably higher than that of PVC. The dielectric behavior is also significantly different from that of unmodified PVC. Sulfonation of the PVC-carbazole condensate affords a cation-exchange resin with —SO3H and —COOH functional moieties.
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Synthesis and Oxygen index (OI) of linear epoxide-amine addition polymers and prepolymers containing (dimethylphosphinyl)methanamine (DMAPO) as flame retardant unit were studied.The structural feature of these polymers and prepolymers was determined by elemental analysis, IR-, 1H-NMR-, 13C-NMR- and 31P-NMR spectroscopy.The OI of the addition polymer of bisphenol-A diglycidylether and DMAPO was found to be 29.5.
    Notes: Es wird über die Herstellung von linearen, hochmolekularen Epoxid-Amin-Additionspolymeren und telechelen Prepolymeren berichtet, die mit Dimethyl(aminomethyl)phosphinoxid (DMAPO) ein flammwidriges Kettenglied in der Polymerkette enthalten. Die Struktur dieser Polymeren und Prepolymeren wird mittels Elementaranalyse, Mn-Werten, IR-, 1H-NMR-, 13C-NMR- und 31P-NMR-Spektroskopie untersucht. Der Sauerstoffindex OI von DGEBA/DMAPO-Polymeren erreicht etwa 30.Auch der polare Charakter von Epoxid/Amin-Additionspolymeren, der für die Haftung an metallischen und oxidischen Werkstoffen bedeutsam ist, wird durch den Einbau von PO(CH3)2-Gruppen verstärkt. Ebenso wird hierdurch die photooxidative Stabilität verbessert.
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    Angewandte Makromolekulare Chemie 170 (1989), S. 183-190 
    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: Kationische Polyurethane mit Piperazinringen in der Polymerkette wurden durch eine Menschutkin-Reaktion dargestellt. Ein Prepolymer mit tertiären Dimethylaminoendgruppen und ein Dihalogenid wurden für die erste Stufe verwendet, N,N′-Dimethylpiperazin für die zweite Stufe. Das viskosimetrische Verhalten der verdünnten Lösungen in Lösungsmitteln mit hohen Dielektrizitätskonstanten wurde untersucht.
    Notes: Cationic polyurethanes containing piperazine rings on the macromolecular chain were synthesized by a Menschutkin reaction. A prepolymer with tertiary dimethylamino end groups and a dihalide were used in the first step, and N,N′-dimethylpiperazine in the second step. The viscometric behaviour of dilute solutions in solvents with high dielectrical constants was studied.
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  • 77
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    Angewandte Makromolekulare Chemie 170 (1989), S. 211-225 
    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 Synthesemethode für modifizierte Aminhärter mit β-Hydroxyurethanbindungen wird vorgestellt. Die physikalischen und chemischen Eigenschaften der modifizierten Polyamine, wie Viskosität und Reaktivität gegenüber einem Epoxidharz, wurden untersucht. Im Vergleich zu einem unmodifizierten Amin wurde eine Verkürzung der Gel- und Härtungszeit in Verbindung mit einer Verringerung des exothermen Effekts während der Härtung eines Epoxidharzes gefunden. Mechanische und thermomechanische Untersuchungen zeigten einen Anstieg der Erweichungstemperaturen, der Härte und der Festigkeitseigenschaften, wie Zugfestigkeit, Scher- und Schälfestigkeit, bei den mit modifizierten Aminen gehärteten Epoxidharzen im Vergleich zu einem Harz, das mit einem unmodifizierten Amin vernetzt wurde.
    Notes: A method of obtaining modified amine curing agents containing β-hydroxyurethane linkages is presented. The basic physical and chemical properties of the modified polyamines, such as viscosity and reactivity towards epoxy resins, have been studied.A shortening of the gel and curing times in addition to a decrease of the exothermic effect accompanying the curing of an epoxy resin was found in comparison with the system containing an unmodified amine. Mechanical and thermomechanical studies showed a rise of the deflection temperature, hardness and strength features such as tensile strength, shear and peel strength for epoxy resins crosslinked with modified curing agents in comparison with those parameters obtained for resins crosslinked with the initial amines.
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Untersucht wurde die Verträglichkeit von polymeren Chlorkohlenwasserstoffen mit verschiedener Comonomersequenzordnung. Eine erste Copolymerenserie (“PVCx”) wurde durch Reduktion von Polyvinylchorid hergestellt, eine zweite Serie (“PECx”) durch Chlorieren von Polyethylen. Die Polymer-Legierungen PECx/PECy, PVCx/PVCy und PVCx/PECy wurden bei 30°C und 110°C mit einer Lösungsfilmmethode analysiert. Im System PECx/PECy nimmt die Mischbarkeit mit steigendem Chlorgehalt der Copolymeren stetig zu. Bei den Systemen PVCx/PVCy und PVCx/PECy zeigt sich im Bereich um x = 1 eine erhöhte Tendenz zur Phasenseparation, die auf die bessere Comonomersequenzordnung der Copolymeren PVCx zurückzuführen ist. Im letzteren System ist diese Tendenz so stark, daß Polyvinylchlorid (PVCx=1) sogar mit dem chlorierten Polyethylen PECx=1, das die gleiche Bruttozusammensetzung hat, nicht mischbar ist.
    Notes: The compatibility of chlorinated hydrocarbon polymers of two different comonomer sequence orders was investigated. One series of copolymers (“PVCx”) was prepared via reduction of polyvinylchloride, the other (“PECx”) via chlorination of polyethylene in solution. The blends PECx/PECy, PVCx/PVCy and PVCx/PECy were analyzed with a film casting method at 30°C and 110°C. Miscibility increases in the system PECx/PECy steadily in the direction of increasing chlorine content. Due to the comonomer sequence order in the copolymers PVCx the systems PVCx/PVCy and PVCx/PECy show in the range around x = 1 an extra effect favouring phase separation. In the latter system this effect is so strong that polyvinylchloride (PVCx = 1) is even incompatible with the chlorinated polyethylene PECx=1 although both have the same overall composition.
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  • 79
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    Angewandte Makromolekulare Chemie 171 (1989), S. 119-130 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die aus Lösung hergestellten Polymermischungen zeigen den Typus der vollmischbaren Polymerlegierungen. Proben, die durch Formpressen der Polymermischungen unterhalb des Schmelzpunkts von Polyetheretherketon (PEEK) erhallten wurden, zeigen ein für mischbare Polymerlegierungen typisches viskoelastisches Verhalten. Hingegen zeigt sich bei Mischungen, die oberhalb des Schmelzpunktes von PEEK verpreßt wurden, im dynamisch-viskoelastischen Verhalten eine Phasentrennung.
    Notes: The polymer blends obtained by the solution blending method show a type of compatible polymer blends. The samples obtained by compression molding the polymer blends below the melting point of the polyetheretherketon (PEEK) exhibit dynamic viscoelastic behavior characteristic of compatible polymer blends, but those by compression molding above the melting point of the PEEK show a phase separation in dynamic viscoelastic behavior.
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  • 80
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    Angewandte Makromolekulare Chemie 171 (1989), S. 91-100 
    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 Cellulosenitratproben (CN-85) untersucht. Die Leitfähigkeit stieg für ungetemperte Proben mit der Temperatur an und nahm mit zunehmender Temperzeit ab. Die Aktivierungsenergie ist bei allen Proben gleich, sie beträgt 2.1 eV in einem Temperaturbereich von 322 bis 385 K. Das Verhalten ist metallisch (dσ/dT) 〈 0 für Temperzeiten, die mehr als 24 h betragen. Bei den gemessenen thermisch stimulierten Strömen (TSC) verschob sich die Lage des Maximums mit zunehmender Aufheizgeschwindigkeit leicht gegen höhere Temperaturen. Die Aktivierungsenergie im Fall des TSC Stromes betrug 0.21 eV, unabhängig von der Aufheizgeschwindigkeit. Die dipolare Relaxationszeit und scheinbare Dielektrizitätskonstante wurden theoretisch berechnet und als Funktion der Temperatur untersucht.
    Notes: The investigated samples were cellulose nitrate CN-85. The conductivity increases with temperature for unannealed samples and decreases with increasing time of annealing for annealed samples.The activation energy is equal for all samples and amounts to 2.1 eV in a temperature range from 322 to 385 K. The behaviour is metallic (dσ/dT) 〈 0 for times of annealing larger than 24 h. The TSC current was measured. The position of the maximum slightly shifted towards higher temperatures with increasing rate of heating. The activation energy in the case of the TSC current was 0.21 eV and independent of the rate of heating. The dipolar relaxation time and imaginary dielectric constant were calculated theoretically and studied as a function of temperature.
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  • 81
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    Angewandte Makromolekulare Chemie 171 (1989), S. 175-190 
    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: Es wurde ein Acrylester-Acrylimid-Copolymeres entwickelt, welches als Additiv in Mischungen mit PVC dessen Gebrauchstemperatur erhöht, ohne andere Eigenschaften des PVC, insbesondere die Transparenz, negativ zu beeinflussen.
    Notes: A major disadvantage of PVC is its low glass transition temperature which limits the service temperature of finished articles to about 70°C. An additive has been developed that can be formulated with PVC to form blends with increased service temperature. With proper formulating, higher heat distortion temperatures can be achieved without sacrificing other properties including clarity. This is especially important in clear PVC applications where no increase in haze is noted with the addition of the acrylic/imide copolymer.
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    Angewandte Makromolekulare Chemie 171 (1989), S. 153-164 
    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 Epoxidgruppen eines Copolymeren, das man durch Pfropfung von 2,3-Epoxypropylmethacrylat auf isotaktisches Polypropylen erhält, wurden mit niedermolekularen sekundären Aminen umgesetzt. Hohe Reaktionsgeschwindigkeiten zeigen heterocyclische Amine. Die Reaktion weniger stark basischer Amine wird in Gegenwart von sauren Katalysatoren beschleunigt. Der Mechanismus des Einflusses des Amin-Säure-Paares auf die Epoxidgruppen auf der Oberfläche eines festen Polymeren unter heterogenen Bedingungen wird diskutiert.
    Notes: Epoxy groups attached to isotactic polypropylene in form of 2,3-epoxypropylmethacrylate grafts were reacted with low molecular secondary amines. Secondary heterocyclic amines exhibit high reaction rates in this process. The bonding of less basic amines is accelerated in the presence of acid catalysts. The mechanism is discussed of amine-acid couple influence upon the epoxy group present in heterogeneous system on the surface of solid polymer.
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    Angewandte Makromolekulare Chemie 173 (1989), S. 69-84 
    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: With the help of a novel test method, diffusion-coefficients of ammonia were determined in 22 transparent, filmforming polymers at room temperature. This method is based upon the UV-VIS-spectroscopically followable reversible reaction of ammonia with 4-nitro phenol to a Meisenheimer-complex.The dye-building reaction was studied and analyzed by a simple approximation of the diffusion equation. Diffusion coefficients obtained are in good agreement with the few available data in the literature.The dependence of the NH3-diffusion coefficients upon the polymer structure corresponds with the obtained diffusion coefficients, which are known for permanent gases.The described method allows the measurement of diffusion coefficients, which are distinguished up to three orders of magnitude, without any problem (ethylcellulose: 1,07 · 10-7 cm2 · s-1; poly(vinylalcohol): 0.9 · 10-10 cm2 · s-1).
    Notes: Mit Hilfe einer neuartigen Untersuchungsmethode wurden die Diffusionskoeffizienten von Ammoniak (NH3) in 22 transparenten filmbildenden Polymeren bei Raumtemperatur bestimmt. Die Methode beruht auf der UV-VIS-spektroskopisch verfolgbaren reversiblen Reaktion von Ammoniak mit 4-Nitrophenol zu einem 4-Nitrophenolat-Ammoniak-Meisenheimer-Komplex.Die Farbbildungsreaktion im Polymerfilm wurde untersucht und anhand einer einfachen Näherung der Diffusionsgleichung ausgewertet. Die erhaltenen Diffusionskoeffizienten stimmen sehr gut mit den wenigen verfügbaren Literaturwerten überein.Die Abhängigkeit der NH3-Diffusionskoeffizienten von der Polymerstruktur ist weitgehend der für permanente Gase bekannten analog.Die beschriebene Methode erlaubt problemlos, Diffusionskoeffizienten zu messen, die sich bis zu drei Größenordnungen unterscheiden (Ethylcellulose: 1,07 · 10-7 cm2 · s-1; Polyvinylalkohol: 0,9 · 10-10 cm2 · s-1).
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  • 84
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    Die Makromolekulare Chemie 190 (1989), S. 69-82 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To verify the possibility of developing a ligand delivery system which is controlled by light pulses, we synthesized copolymers of N-(2-hydroxypropyl)methacrylamide (1) containing sidechains terminated in ligands (Boc-Gly, fluorescein, tetramethylrhodamine) bound via photocleavable 2-nitrobenzyl groups. Copolymers in solution were exposed to light of wavelength ≍ 360 nm which resulted in release of the bound ligands. Depending on the experimental conditions (type of solvent, presence of oxygen) changes in the structure of released fluorochromes were observed (photofading effect). These effects were quantified by determining the binding constants of released modified fluorochromes with monoclonal antifluorescyl anti-bodies.
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  • 85
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    Die Makromolekulare Chemie 190 (1989), S. 83-92 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intramolecularly crosslinked macromolecules (ICM) from unsaturated polyesters (UP) and styrene, respectively from technical divinylbenzene (t-DVB), were prepared by emulsion copolymerization (ECP). Saturated polyesters of different compositions and molar masses between 1200 and 2400 were used as emulsifiers (ESP). The influence of molar mass and structure at various concentrations of the ESP on yield, number and diameter of the ICM and their composition was studied. For comparison, also sodium dodecyl sulfate (SDS) was used as emulsifier.
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  • 86
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reactions of a set of organoalkaline compounds with trans-β-carotene (Car) were studied in solution (using UV/Vis, ESR, and mass spectroscopy) and compared with the reactions of the same set with insoluble polyacetylene. It was shown that the naphthalene radical ion and the dicarbanionic dimer of 1,1-diphenylethylene, 1,1,4,4-tetraphenyl-1,4-butanediide, react with Car by a simple electron transfer leading to Car radical ion and dianion. This dianion is protonated by methanol mainly at carbon 7 or 7′. On the contrary of diphenylalkyllithium compounds add to Car double bonds. This addition of 1 mol of diphenylalkyllithium per Car takes place mainly at the central double bond. sec-Butyllithium (sec-BuLi) reacts also by addition to Car. The addition products are in some cases instable and decompose to radical ions through a non-elucidated mechanism. These transfer or addition reactions with Car, as well as the exclusive electron transfer observed with polyacetylene, are rationalized on the basis of the relative redox potentials of reactants.
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  • 87
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    Die Makromolekulare Chemie 190 (1989), S. 107-115 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The paper deals with modelling the transport of magnesium and calcium ions in the cell wall of Gram-positive bacteria. The model compound, i. e. 2-ethylhexylpoly(trimethylene phosphate)Structure-based IUPAC nomenclature: α-2-Ethylhexyl-ω-hydroxypoly[oxy(hydroxyphosphonol)oxytrimethylene]. (EPTP), was synthesized in order to mimic the transport mediated by lipoteichoic acids. It was found that EPTP can transport preferentially magnesium ions in an ion exchange-diffusion process with the counter-transport of hydrogen ions.
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  • 88
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    Die Makromolekulare Chemie 190 (1989), S. 117-128 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper concentrates on the effect of introducing hydrogen bonding into otherwise immiscible blends on their miscibility and morphology. 1,1,1,3,3,3-Hexafluoro-2-hydroxypropyl-containing units are incorporated in polystyrene which is then mixed with carbonyl-containing polymers such as poly(methyl methacrylate) and poly(butyl acrylate). The infrared study confirms the formation of hydrogen bonding and shows that the frequency shifts of hydroxyl stretching caused by the H-bonds are independent on whether the hydroxyl-containing units are in the monomer or connected to polystyrene or polyisoprene chains and whether they are randomly distributed along the chains or only located at the ends of the polymers. Hydrogen bonding in the blends dramatically enhances miscibility judged by differential scanning calorimetry and transmission electron miscroscopy (TEM). TEM observations reveal apparent and regular variations of the morphology in the blends with the content of the hydroxyl-containing groups, which implies that the morphological features of the blends, such as size of the dispersed phase, or extent of interpenetrating between the components are controllable simply by changing the structure and/or amount of the introduced groups forming the specific interaction in the blends.
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  • 89
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The isothermal crystallization kinetics, the morphology and melting behaviour of blends of poly(tetramethylene terephthalate) {poly(butylene terephthalate), (PBT)} with a thermotropic liquid-crystalline polyester, poly(decamethylene 4,4′-terephthaloyldioxydibenzoate) (HTH10), were studied in the composition range 0 - 50 wt.-% of HTH10 by optical microscopy and differential scanning calorimetry. The spherulite growth rate and the overall crystallization rate of PBT from melt blends are markedly depressed by the presence of the mesomorphic component. Changes of superstructure and of primary nucleation density of PBT spherulites in the blends were observed. The analysis of the melting behaviour of these samples indicates that the stability of PBT crystals and their reorganization processes on heating are dependent on the blend composition. A decrease of the equilibrium melting temperature of PBT is found with increasing the amount of HTH10. According to previously reported investigations on the same system, the results are discussed in respect of the onset of interactions between the two polymers in the liquid state.
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  • 90
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrosilylation reactions of 1-allyloxy-3-phenoxy-2-propanol (3) as model compound were carried out with α-dimethylsilyl-ω-hydrooligosiloxane (7; M̄n = 1200) in the presence of hexachloroplatinic acid. It was found that under stoichiometric conditions only 75--80% of the allyl groups were hydrosilylated, due to some isomerization of the allyl groups into vinyl groups, which do not undergo hydrosilylation. This isomerization could be shown to be sensitive to the type of the allyloxy structure. Thus, for example, allyloxybenzene does not undergo isomerization.
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  • 91
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: GC-MS analysis of oligomers obtained by using a high concentration of chain transfer agents permits the identification and determination of the concentrations of all the compounds formed in the early propagation steps. From these data the exact structure of the starting chain end and the evaluation of a series of kinetic and probabilistic parameters can be obtained, thus allowing a more detailed description of the polymerization mechanism. Applying this method to the copolymerization of styrene (1) and methyl methacrylate (2), a value of 6 was obtained for the ratio of the reinitiation rate constants kr1/kr2 in the presence of 1-butanethiol at 60°C.
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  • 92
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The substitution reaction of PVC with sodium dimethyldithiocarbamate (NaDC) and sodium azide (NaN3) was performed in cyclohexanone and dimethylformamide at various temperatures. The degree of compositional heterogeneity was estimated and found to be important up to conversions of about 0,5%, but to vanish afterwards. The evolution of unreacted iso, hetero and syndiotactic triads was measured by 13C NMR spectroscopy. For conversions of at least up to 12%, the content of both the isotactic and heterotactic triads was found to decrease, relative to the syndiotactic ones, but at different relative rates depending on the nucleophile. From these results, together with the kinetic ones, it is concluded that the reaction proceeds by a stereoselective mechanism. The results are discussed on the basis of a hypothesis concerning the role of the local triad conformations in PVC that contain the TT isotactic diad conformation. The results enable the selective substitution of PVC with NaDC and NaN3, which may be used as a useful tool to prepare specific graft copolymers based on PVC.
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  • 93
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,8-Bis(dimethylamino)-4-(4-vinylphenyl)naphthalene (33), 1,8-bis(dimethylamino)-4-(4-vinylbenzyl)napthalene (35), 4,5-bis(dimethylamino)-9-(4-vinylbenzyl)fluorene (37) and 4,5-bis(dimethylamino)-9,9-bis(4-vinylbenzyl)-fluorene (38) were synthesized as potential vinyl monomers.
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  • 94
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly{1-[4-(2-chloroethyl)phenyl]ethylene} (3) was synthesized by bulk polymerization of 4-(2-chloroethyl)styrene (6) in two steps from commercial products. The polymer was characterized by means of GPC (weight-average molecular weight M̄w = 85 000 and number-average molecular weight M̄n = 63 500), 1H NMR and 13C NMR spectroscopy. The first stage of thermal degradation begins at 290°C and ends at about 410°C. The overall activation energy was calculated to be 43 kcal · mol-1 (180 kJ · mol-1). The solid residue was crosslinked and insoluble. The volatile products, identified by gas chromatography-mass spectroscopy (GC-MS), were chiefly hydrogen chloride, dichloromethane and monomer. In a strongly basic medium, nucleophilic substitution of chlorine was achieved without elimination.
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  • 95
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    Die Makromolekulare Chemie 190 (1989), S. 191-202 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction of catenapoly(diphenoxy-λ5-phosphazene) (1) with SO3 in 1,2-dichloroethane at 15°C, applying a mole ratio m = [SO3]/[--P(OC6H5)2N - ] ≤ 1,0 and subsequent quenching with water, leads to catenapoly(diphenoxy-λ5-phosphazene-co-diphenoxy-λ5-phosphazenium hydrogen sulfate) (2) containing up to 57% protonated nitrogen. At m 〉 1,0 C-sulfonation occurs, resulting in the formation of water-soluble catenapoly[diphenoxy-λ5-phosphazene-co-diphenoxy-λ5-phosphazenium hydrogen sulfate-co-bis(sulfophenoxy)-λ5-phosphazenium hydrogen sulfate] (3). The latter can be converted into catenapoly[diphenoxy-λ5-phosphazene-co-bis(sulfophenoxy)-λ5-phosphazene] (4b) by treatment with alkali and subsequent percolating through a cation exchange resin. Analytical results show that C-sulfonation is preceded by the formation of a polymer-SO3 donor-acceptor complex.
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  • 96
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    Die Makromolekulare Chemie 190 (1989), S. 255-265 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Principles and new approaches to the synthesis of functional poly(ethylene oxide)s (PEO) are considered. It could be shown that quantitative functionalization during initiation or deactivation of living polymers cannot be reached independently of the demands to achieve a desired molecular weight of the polymer. This is illustrated by the data of the synthesis of dinitrophenyl derivatives of PEO (molecular weights from 3 · 103 to about 105) which are synthetic immunogenes. Vinyl ether macromonomers of PEO with molecular weights in the range of 750-3000 were also synthesized by anionic polymerization of ethylene oxide with trimethylamine as initiator. These macromonomers were used for effective grafting of PEO onto a solid surface, grafted PEO being able to selectively binding alkali salts from the solution. Values of binding constants were evaluated.
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  • 97
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have found, that heteropolyacids (HPA) are efficient initiators of cationic polymerizations, including polymerizations of cyclic ethers and acetals, providing high-molecular-weight polymers. In several systems (e. g. THF, 1,3-dioxolane) the degree of polymerization is given by the ratio of concentrations of monomer and initiator, as for the living system. In the polymerization of cyclic formaldehyde trimer: 1,3,5-trioxane, the comparable polymerization rates may be obtained with ≈ 25 times less an initiator consumption on weight basis (≈ 103 times less on molar basis) than for typical initiators like BF3 · OR2.
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  • 98
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    Die Makromolekulare Chemie 190 (1989), S. 951-960 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of several variables on the gelation behaviour of the chitosan/glutaraldehyde system have been studied. The rate of gelation is increased by increase in concentration of either chitosan or glutaraldehyde, or by an increase in temperature, and reduced by an increase in the concentration of acetic acid. Addition of a number of neutral electrolytes also causes an increase in the rate of gelation, the increase being larger the greater the activity coefficient of the electrolyte. UV/visible and NMR spectra of glutaraldehyde, acetaldehyde and crotonaldehyde, together with those of their 2,4-dinitrophenylhydrazine derivatives, indicate that only a very small proportion (〈0,15%) of the aldehyde groups have undergone an aldol condensation reaction leading to α,β-unsaturated aldehyde groups. This, together with other evidence, suggests that the cross-linking mechanism involves formation of Schiff's base structures rather than Michael-type adducts as previously postulated.
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  • 99
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Low-molecular-weight phthalocyaninatocobalt compounds 2a-d and polymeric phthalocyaninatocobalt derivatives 4, 6a, b were prepared on the surface of the inorganic carriers SiO2 or γ-Al2O3 and of active charcoal, the range of loading being 11,9 - 0,2 wt.-%. The oxidation of 2-mercaptoethanol in an aqueous solution at pH 9 was used as a model reaction for demercaptizations of petroleum fractions with phthalocyanines on carriers as heterogeneous catalysts. The catalytic activity, related to the phthalocyanine content, was found to increase with increasing dispersion of the complex on the carrier. The influence of the type of support on the activity is given by the following order: SiO2 〈 γ-Al2O3 〈 Norit charcoal. Polymeric phthalocyanines exhibit a higher catalytic activity as compared with low-molecular-weight phthalocyanines. The mechanism of the oxidation of the thiol is discussed.
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  • 100
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    Die Makromolekulare Chemie 190 (1989), S. 975-983 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For producing hydrogen peroxide the suitability of stable polymeric nitroxyls as reaction carriers was investigated. These can be hydrogenated to the corresponding hydroxylamines, which are oxidized by oxygen exclusively to hydrogen peroxide and nitroxyls. The yield of hydrogen peroxide was determined in different solvents, at different reaction times and temperatures. Possible side reactions for the decomposition of hydrogen peroxide were investigated. The activation energy for the oxidation of polymeric hydroxylamine with oxygen in DMSO was calculated to be 67 kJ/mol.
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