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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
    Notes: The effects of the nature of the polyols used in polyurethane (PUR) synthesis on the structural transformations after ageing by UV irradiation has been studied. The investigations were performed on PUR prepared from polyester and polyether diol oligomers.The characterization of the samples before and after ageing in view of the structural changes, which influence the course of the photooxidative degradation and photocrosslinking as well as in view of changes of mechanical properties has been done. Comparative investigations were performed by spectroscopic and viscometric measurements.The results show pronounced heterogeneity of the degradative reactions, including the existence of crosslinking processes and producing thus very inhomogeneous polymeric material. The course and the intensity of photooxidative degradation of PUR differ together with changes of mechanical properties depending whether polyester or polyether polyol have been used. The processes of photooxidative degradation is less expressed in polyesterurethane then in polyurethane based on polyether, under the same conditions of experiments. Different structures of polyester diols caused the various ageing behaviour of PUR too.
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  • 2
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: QUALIFICATION OF HALS COMPOUNDSA complex method of examination has been developed suitable for the qualification of light stabilizers; by this method, according to experience, the efficacy of HALS compounds can be extensively and expediently characterized.Several light stabilizers of the HALS-type were examined and qualified, used alone or together with a UV-absorber.It has been found that, when selecting the appropriate structure for a given polymer, the weatherability of polyolefine foils is effectively increase to six-eightfold; the increase is even tenfold when the stabilizer is combined with a benzophenone-type compound.As a utilization of these experiences, a contract with the industry, led to the production of an LDPE based agricultural foil with a life-time of several years.
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  • 3
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Natural hail impact tests are scarcely available because hailstorms are limited to a small area and cannot be predicted regarding time, place and intensity. Therefore we relied on laboratory tests simulating natural hailstones by polyamide balls (5-50 mm dia.) whose final velocity could be varied according to meteorological data. So the influence of diameter (weight) and velocity of the artificial hailstones could be taken into consideration independently.The energy of damage or equivalent natural hailstone diameter were determined for 16 mm double skin sheet from PMMA as 0.2 J (14 mm dia.) for star shaped cracks and 2 J (26 mm dia.) for holes. These values do not significantly decrease after 10 years weathering. 10 mm double skin sheets from PC show an extremly high energy of damage of abt. 10 J (38 mm dia.) which decreases to a medium level of 2 J (26 mm dia.) after several years weathering. This decrease is remarkably reduced by weather resistant protective coating.As hailstorms consist to more than 80% of hailstones below 10 mm dia. (0.04 J) the mentioned sheet materials are quite hail resistant also after long weathering periods, but they cannot withstand an extreme hail catastrophe as in Munich July 12, 1984.
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  • 4
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of the specimen temperature on many ageing processes is well known. Two aspects is dealt with: -Measurements of the specimen temperature on several positions of a specimen in commercial weathering devices at different exposure conditions. Technical measures to achieve to uniform ageing at all positions of a planar and homogeneous specimen. Examples from practical use.-Changing specimen temperatures (+60°C to -20°C) during the course of accelerated weathering, i.e. a combination of conventional accelerated weathering with a temperature cycle test.
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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: An Folien (Dicke 100 pm) aus isotaktischem Polypropylen mit verschiedenen Antioxidansgehalten (0,0% bis 0,1%) wird die thermooxidative Alterunq mit der isothermen Langzeit-Differential-Thermo-Analyse (ILDTA) bis zu Temperaturen weit unter dem Kristallitschmelzbereich verfolqt und die Messwerte mit Ergebnissen aus dem Zeitstand-Zugversuch korreliert. Dabei zeigt sich, daß aus Messunqen mit der ILDTA bereits vor Einsetzen der autokatalytischen Zersetzunq sreaktion Ruckschlüsse auf die thermische Vorqeschichte der Proben und Aussagen auf das rnit einem Abfall der mechanischen Eigenschaften verbundene Ende der thermo-oxidativen Stabilität des Polymeren getroffen werden können.Weiters bietet die ILDTA die Moglichkeit, durch den direkten Zusamenhang zwischen Oxidationszeit und Antioxidansögehalt die örtliche Stabilisatorverteilung in Platten und in Folien zu bestimmen und damit Diffusionsvorqange zu verfolgen.
    Notes: Thermo-oxidative ageing processes were investigated in films (100 μm thick) made from isotactic polypropylene with different antioxidant concentrations between 0% and 0.1% using isothermal long-term differential thermal analysis (ILDTA). The end of the oven life of polypropylene coincided with the loss of mechanical properties which was confirmed by tensile tests at temperatures far below the crystallite melting range. Already prior to the beginning of autocatalytic decomposition, ILDTA experiments permits conclusions to be drawn on the thermal history of the specimens and statements made regarding the end of thermo-oxidative stability of the polymer, which is accompanied by a deterioration in the mechanical properties.In consequence of the correlation between oxidation time and antioxidant concentration the local antioxidant concentration in sheets or films can be measured by ILDTA. Thus, investigating the diffusion of an antioxidant in polypropylene using ILDTA is possible.
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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 Größenverteilungsfunktion von Dispersionen mit extrem breiter Verteilung (Durchmesserbereich 20 〈 D 〈 2000 nm) kann in der analytischen Ultrazentrifuge (AUC) nicht durch eine Standardmethode, z. B. durch Messung der Trübung τ bei einer einzigen Konzentration, bestimmt werden, weil sich die spezifische Trübung τ/c von sehr kleinen und sehr großen Teilchen zu stark unterscheidet. Um dieses Problem zu lösen, haben wir eine neue AUC-Technik, die sogenannte Coupling-PSD-Technik entwickelt. Dabei werden zwei unterschiedliche Konzentrationen derselben Dispersion gleichzeitig in einem einzigen AUC-Lauf vermessen und zwei korrespondierende Lichtintensitiit-Zeit-Kurven aufgezeichnet. Bei einer niedrigen Standardkonzentration cs werden hauptsachlich die größeren Teilchen erfaßt während bei einer 5 bis 30 mal heheren Konzentration ch vor allem die kleineren Teilchen registriert werden. Die beiden I(t)-Kurven werden mathematisch verkniipft und unter Verwendung des Stokeschen Gesetzes und der Streutheorie von Mie für homogene isotrope Kugeln in die gesuchte breite Verteilungsfunktion umgerechnet. Wir benutzen eine mit einem 8-Zellen-Rotor und einem Multiplexer ausgestattete AUC. Da sehr groBe und sehr kleine Teilchen gleichzeitig in einem einzigen Zentrifugenlauf bestimmt werden, kennen wir nicht mehr wie zuvor eine konstante Rotorgeschwindigkeit N anwenden, sondern miissen diese mit Hilfe eines Geschwindigkeitsprogramms N(t) innerhalb einer Stunde von 0 auf 40000 U/min erhehen.
    Notes: The particle size distribution (PSD) of extremely broad distributed dispersions (diameter range 20 〈 D 〈 2000 nm) is not possible to be measured by analytical ultracentrifuge (AUC) using the standard technique, i.e. measuring turbidity τ at a single concentration c, because the specific turbidity τ/c varies too much between very small and very large particles. To solve this problem we have developed a new AUC technique, the so-called Coupling-PSD-Technique. Here two different concentrations of the same dispersion are measured simultaneously by one single AUC run with two corresponding curves of light intensity I vs. time t being registered. At a low standard concentration cs, mainly the larger particles are detected, while at a concentration ch 5 to 30 times higher mainly the smaller particles are registered. Both I(t)-curves are coupled mathematically and transformed into the requested broad distribution curve employing Stokes' law and Mie's light scattering theory for homogeneous isotropic spheres.We use an AUC together with an 8-cells-rotor and a multiplexer. Because very large and very small particles are to be measured simultaneously in one single run, we can no more apply a constant rotor speed N as before, but by means of a time program N(t) we always have to increase the rotor speed from 0 to 40000 rpm within one hour.
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  • 7
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 135-148 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die chemische Modifizierung von Polyvinylchlorid (PVC) durch ein Amin verleiht dem Polymeren höhere Reaktivität gegenüber der Pfropfcopolymerisation mit einem Vinylmonomeren. Die Pfropfcopolymerisation von Methylmethacrylat auf mit n-Butylamin modifiziertes PVC wurde thermisch mit Benzoylperoxid (Bz2O2) als Initiator oder photoaktiviert mit Benzophenon (BP) als Photosensibilisator gestartet. Das aus bestimmten Experimenten erhaltene rohe Polymerprodukt wurde durch fraktionierte Fällung in die verschiedenen Bestandteile wie Polymethylmethacrylat (PMMA, Homopolymeres), PVC-g-PMMA (Pfropfcopolymeres) und unverändertes (aminiertes) PVC aufgespalten. Die getrennten Fraktionen wurden mit Hilfe der IR-Spektroskopie und der Thermogravimetrie charakterisiert. Der Mechanismus der Pfropfcopolymerisation von den beiden verschiedenen Systemen wurde erörtert. In beiden Fällen wurden Pfropfausbeuten um 30 - 70%* und Pfropfcopolymerzusammensetzungen, PMMA/PVC (w/w) zwischen 2 und 3 erhalten.
    Notes: Chemical modification of poly(vinyl chloride), PVC, by an amine renders the polymer more reactive towards graft copolymerization with a vinyl monomer. The graft copolymerization of methyl methacrylate (MMA) on PVC modified by treatment with n-butylamine (n-BA) was started thermally at 30° using benzoyl peroxide (Bz2O2) as initiator and under photoactivation at 40° using benzophenone (BP) as photo sensitizer. The gross polymer products from selected experiments were fractionally separated into the constituent polymeric entities viz., poly(methyl methacrylate), PMMA (homopolymer), PVC-g-PMMA (graft copolymer), and unreacted (aminated) PVC following a method of fractional precipitation. The separated fractions were characterized by IR spectroscopy and thermogravimetry. The mechanisms of graft copolymerization for the two different systems have been discussed. In each case, grafting efficiencies of the order of 30-70% and graft copolymers having compositions given as PMMA/PVC (w/w) equal to 2-3 were readily obtained.
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  • 8
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 193-201 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe oberflächensulfonierter, makroporöser Styrol-Divinylbenzol-Copolymerer mit unterschiedlichen Gehalten an SO3H-Gruppen wurden hergestellt. Sowohl von diesen Copolymeren als auch vom nichtsulfonierten Copolymeren wurden Porenstruktur, Oberflächenhydrophilie und -polarität sowie das Sorptionsverhalten gegenüber einigen in Blut vorkommenden Substanzen bestimmt. Der Sorptionsgrad wird umso kleiner, je größer die Oberflächenpolarität ist. Die teilsulfonierten Polymeren könnten eine Anwendung in der Hämoperfusion finden.
    Notes: A series of surface sulphonated macroporous styrene-divinylbenzene (S-DVB) copolymers containing various amounts of  - SO3H groups was obtained. Porous structure, surface hydrophilicity and polarity, and sorption properties of these copolymers as well as those of starting S-DVB resin towards some substances which are present in blood were determined. The sorption degree becomes the smaller the higher is the surface polarity. The partially sulphonated copolymers may find an application in hemoperfusion.
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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: Der Einfluß einer chemischen Behandlung von dünnen Filmen einer Composit-Membran aus sulfoniertem Polyphenylenoxid wurde untersucht. Über den Einfluß der Konzentration von wáßrigen Lösungen von Formaldehyd, Schwefelsäure, Salzsäure, Phosporsäure, Natriumhydroxid sowie der Behandlungsdauer auf die Trenncharakteristik der inversen Osmose der Composit-Membranen mit einer Ionenaus-tauschkapazität von 2,14 und 2,50 meq/g in verschiedenen Kombinationen wird ausführlich berichtet. Die Ergebnisse zeigen, daß unter den besten chemischen Behandlungsbedingungen eine Erhöhung der Trenncharakteristik der inversen Osmose der sulfonierten Polyphenylenoxid/Polysulfon-Composit-Membran erreicht wird.
    Notes: The effect of chemical treatment on the reverse osmosis (RO) separation characteristics of sulfonated poly(phenylene oxide) (SPPO) thin film composite membranes was investigated. The effects of the concentrations of aqueous solutions of formaldehyde, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, and treatment time on the RO separation characteristics of the composite membranes with ion exchange capacity (IEC) of 2.14 and 2.50 meq/g in various combinations are reported in detail. The results indicate some enhancement in RO separation characteristics of the SPPO/polysulfone (PS) composite membrane under the best conditions of the chemical treatment.
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  • 10
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bei der Herstellung dünner Filme von sulfonierten Polyphenylenoxid/Polysulfon (SPPO/PS)-Composit-Membranen wurde untersucht, daß ein Zusatz von Nitromethan zu einer Lösung von sulfoniertem Polyphenylenoxidnatrium erhöhte Wirkung auf die Trenncharakteristik der inversen Osmose besitzt. Der Einfluß von gamma-Strahlung auf dünne Filme der Composit-Membran unter nassen und trockenen Bedingungen wurde ebenfalls untersucht. Um die maximal mögliche Verbesserung zu erreichen, wurden die Composit-Membranen einer kombinierten chemischen und Gammastrahlen-Behandlung unter nassen und trockenen Bedingungen unterworfen.Die experimentellen Ergebnisse dieser kombinierten Behandlung zeigen, dalß die SPPO/PS Composit-Membran dabei abgebaut wird.
    Notes: The enhancement effect of the addition of nitromethane into the coating solution of sulfonated sodium poly(phenylene oxide) (SPPONa) polymer for the synthesis of sulfonated poly(phenylene oxide)/polysulfone (SPPO/PS) thin film composite membranes on reverse osmosis (RO) separation characteristic was studied. The effect of gamma-ray irradiation on the SPPO/PS thin film composite membranes was also evaluated when the membrane samples were in the wet and dry conditions. The composite membranes were also subjected to a chemical treatment combined with gamma-ray irradiation in both wet and dry conditions in the hope of obtaining the maximum possible enhancement under each treatment. However, the experimental data of this combined treatment indicated the possibility of some degradation of the SPPO/PS composite membranes.
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  • 11
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 37-45 
    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: Mischungen aus Poly(styrol-co-butadien)/Polybutadien, Naturkautschuk/Poly-(ethylen-co-propylen-co-dien und Naturkautschuk/Poly(butadien-co-acrylnitril)) wurden nach drei unterschiedlichen Verfahren compoundiert und Härtungsverhalten sowie Zugfestigkeit und Bruchdehnung der Vulkanisate wurden verglichen.
    Notes: Compounding of styrene-butadiene copolymer/polybutadiene, natural rubber/ethylene-propylene-diene terpolymer and natural rubber/butadiene-acrylonitrile copolymer blends was done in three different ways and their curing behaviour and the tensile properties of the vulcanizates are compared.
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  • 12
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Methylmethacrylat (MMA) wurde mit Hilfe von Cerammoniumnitrat als Initiator auf Stärke gepfropft. Die Pfropfcopolymeren wurden durch selektive Lösungsextraktion in einem Soxhlet-Extraktor isoliert. Der Einfluß von Reaktionszeit, Initiatorkonzentration, Temperatur sowie der Monomer- und Särekonzentration auf die Pfropfausbeute wurde untersucht. Eine erste Studie der Kinetik dieser Pfropfcopolymerisationsreaktion zeigt, daß sie dem üblichen kinetischen Verhalten einer Radikalpolymerisation folgt.
    Notes: Methyl methacrylate (MMA) was grafted onto starch using ceric ammonium nitrate as initiator. The graft copolymers were isolated by selective solvent extraction in a Soxhlet apparatus. The effects of reaction time, initiator concentration, temperature, monomer, and acid concentrations on the graft yields were investigated. A preliminary kinetic study of the graft copolymerisation reactions shows that they follow the conventional kinetic behaviour of free radical polymerisation.
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  • 13
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 47-61 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Verwendung von Phenol-Formaldehyd-Harz mit gepreßten Olivenkenen im Gewichtsverháltnis 20/80 wurden kleine zylindrische Formkörper durch Härtung hergestellt. Diese wurden pyrolysiert und einige Proben mit Wasserdampf aktiviert. Für diese Formkörper und für zwei kommerzielle Aktivkohlen für Laboratoriumsbzw. Industrie-Anwendungen wurden folgende Eigenschaften bestimmt: die spezifische Oberfláche, die Struktur, die Adsorptionseigenschaften sowie die Adsorptionskapazität. Die Ergebnisse zeigen, daß die hergestellten kohlenstoffhaltigen Materialien durch Aktivierung höhere Werte für die untersuchten Eigenschaften ergeben als die nur pyrolysierten Proben und die zwei kommerziellen Aktivkohlen. Es wurde festgestellt, daß die Adsorption des 4-Nitrophenols für alle untersuchten kohlenstoffhaltigen Materialien gemäß der Freundlich-Gleichung stattfindet. Die Raster-Elektronenmikroskopie zeigt, daß die hergestellten kohlenstoffhaltigen Materialien andere Porenarten aufweisen als die kommerziellen Aktivkohlen. Die experimentellen Ergebnisse werden durch die molekularen Dimensionen der zur Adsorption verwendeten Substanzen und den Polarisationseffekt der Substituenten am Benzolring erklärt.
    Notes: Mixtures of phenol-formaldehyde-resin and pressed olive stones in a weight ratio of 20/80 were cured as small cylinders and then pyrolyzed. Some samples were also activated by steam. For these specimens and for two commercial activated carbons of laboratory or industrial uses the specific surface area, the structure, the adsorption properties, and the adsorption capacity were determined. The results indicate that the carbonaceous material produced by activation has greater values for the examined properties in comparison to the only pyrolyzed and the two commercial activated carbons, respectively. It was found that the Freundlich-equation is valid for the adsorption of 4-nitrophenol on all carbonaceous materials examined. The produced carbonaceous materials have different kinds of pores than the commercial activated carbons. The experimental results are explained with regard to the molecular dimensions of the adsorptive substances and the polarization effect of the substituents of the benzene ring.
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  • 14
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 101-114 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Anwendung der nichtlinearen Programmiermethode basierend auf der mittleren harmonischen Näherung wurden aus den Kontaktwinkeldaten die freie Dispersions- und polare, freie Oberflächenenergie, γSVd und γSVp, sowie die kritische, freie Oberflächenenergie, γc, von Polymeren bestimmt. Die Komponenten der freien Oberflächenergie der zu untersuchenden Flüssigkeiten, γLVd und γLVp, die die Bedingungen für den maximalen Wechselwirkungsparameter, Φ, wiedergeben, wurden ebenfalls mit Hilfe dieser Methode bestimmt.
    Notes: The dispersion and polar surface free energy components, γSVd and γSVp, and the critical surface free energy, γc, of polymers were determined from contact angle data by the application of a nonlinear programming method using harmonic mean approximation.The surface free energy components of the probe liquids, γLVd and γLVp, which reflect the conditions of the maximized interaction parameter, Φ, were also simultaneously determined by this method.
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  • 15
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 169-193 
    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: The condensation reaction of bisphenol A, melamine, and formaldehyde was investigated by gel permeation chromatography, 13C-NMR-spectroscopy, IR-spectroscopy and elemental analysis. Because of the high reaction rates the condensation could be investigated only in the range of pH 6-10. At pH 6 and 7 the reaction of melamine with formaldehyde is dominating.With increasing pH-value the condensation of bisphenol A with formaldehyde is observed preferably. At pH 10 the condensation results in high molecular products. Cocondensation of melamine and bisphenol A through methylene bridges does not take place. But as a separation of the bisphenol A-formaldehyde condensates from the other condensation products was not possible, the three components may be connected through methylene-ether groups and/or intermolecular hydrogen bridges.
    Notes: Die gemeinsame Kondensation von Bisphenol A, Melamin und Formaldehyd wurde mit Hilfe der Gelpermeationschromatographie, der 13C-NMR-Spektroskopie, IR-Spektroskopie und Elementaranalyse untersucht. Wegen der hohen Kondensationsgeschwindigkeit verläuft die Reaktion in Gegenwart der drei Komponenten nur im Bereich von pH 6-10 kontrollierbar. Bei pH 6 und 7 überwigt die Kondensation zwischen Melamin und Formaldehyd. Mit steigendem pH-Wert tritt die Reaktion von Bisphenol A mit Formaldehyd in den Vordergrund und führt bei pH 10 zu hochmolekularen Kondensationsprodukten.Auf direkte Cokondensation hinweisende Methylenverknüpfungen zwischen der phenolischen Komponente und Melamin konnten nicht nachgewiesen werden. Die Kondensationsprodukte des Melamins bzw. des Bisphenol A mit Formaldehyd lassen sich aber nicht mehr vollständig aus den Reaktionsgemischen der Vorkondensation abtrennen, was dafür spricht, daß die Komponenten über Methylenetherbrücken und/oder intermolekularen Wasserstoffbrücken miteinander verknüpft sind.
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  • 16
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 205-207 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclodextrin membrane-modified electrodes as sensor materials have been prepared by dipping platinum electrodes in the water suspensions of an oriented cyclodextrin polymer, followed by drying the polymer layers on the electrodes. The polymer is obtained by the solid-liquid reaction between the crystal of cyclodextrin inclusion complex and hexamethylene diisocyanate in anisole. The thickness (2 - 80 μm) of the cyclodextrin membrane is satisfactorily controlled by changing the concentration of the water suspension of the polymer. The cyclodextrin membranemodified electrodes show a significant response to p-nitrophenolate in water which is highly in contrast with no measurable response to o- and m-nitrophenolates.
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  • 17
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Im Zusammenhang mit dem Studium des Wirkungsmechanismus von industriell hergestellten Antidegradantien vom Typus der N-Phenyl-N′-sek-alkyl-1,Cphenylendiamine wurde die Reaktion von N-Phenyl-1,4-benzochinonimin (I) und 4-Hydroxydiphenylamin (II) mit dem Kohlenstoff-Radikal 1-Cyano-l-methylethyl (R·) studiert. Das Gemisch von I und II reagiert mit R· sehr leicht unter Bildung der Verbindungen III, VI und VIII. I allein reagiert wesentlich langsamer, und das Reaktionsgemisch enthält mehrere Produkte. Neben der Verbindung III wurden auch die Verbindungen IV und VII identifiziert. II allein reagiert bei denselben Bedingungen nicht. Die Verbindung IV bildet die zwei isomeren Strukturen syn und anti. Die Verbindung VIII ist ziemlich unbeständig; aus ihren Umwandlungsprodukten wurde XI isoliert. Bei der Reduktion von IV entsteht die Verbindung V, die ähnlich wie VIII unbeständig ist.
    Notes: The reaction of N-phenyl-1,4-benzoquinoneimine (I)Decoding of abbreviations see p. 103/104. and 4-hydroxydiphenylamine (II) with the carbon centred 1-cyano-1-methylethyl radical (R·) was studied in connection with an investigation of the action mechanism of industrial antidegradants, such as N-phenyl-N′-sec-alkyl-1,4-phenylenediamines. The mixture of I and II reacts very readily with R·, giving rise to III, VI, and VIII. I alone reacts much slowlier, and the reaction mixture contains more products. IV and VII were identified along with III. Under the conditions used, II alone does not react at all. IV exists in two isomeric forms, syn and anti. VIII is very labile; XI was isolated from its transformation products. Reduction of IV gives V, which is labile, similarly to VIII.
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  • 18
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 123-137 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Samples of polyoxymethylene (unstabilized and stabilized with the antiozonants N-isopropyl-N′-phenyl-p-phenylenediamin (IPPD) and bis-(1,2,3,6-tetrahydrobenzaldehyd)pentaerithritylacetal (Vulkazon AFS)) were ozonized under mechanical load in a special climate chamber. Surface damages were determined by IR-spectroscopy and scanning electron microscopy. During the ozonolysis a damaged layer is formed, the thickness of which increases with increasing time of ozonization. During this damaging reaction acetal groups are attacked and oligomers are formed.
    Notes: Proben von unstabilisiertem und mit den Antiozonantien N-Isopropyl-N′-phenyl-p-phenylendiamin (IPPD) und Bis-(1,2,3,6-tetrahydrobenzaldehyd)-pentaerithrityl-acetal (Vulkazon AFS) stabilisiertem Polyoxymethylen wurden unter mechanischer Belastung in einer Klimakammer ozonisiert. Die Schädigungen auf der Oberfläche wurden IR-spektroskopisch und rasterelektronenmikroskopisch untersucht. Während der Ozonisierung von POM bildet sich eine geschädigte Schicht, deren Dicke mit zunehmender Ozonisierungszeit wächst. Hierbei wird das Polymere an den Acetalbindungen angegriffen, wodurch Ketten gespalten werden und Oligomere entstehen.
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  • 19
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 105-121 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mit Hilfe verschiedener Methoden wurde der Einfluß der Entfernung unterschiedlicher porenbildender Verdünner aus porösen Styrol-Ethylstyrol-Acrylnitril-Divinylbenzol-Copolymeren auf die Netzwerkstruktur untersucht. Der günstigste Weg, den ursprünglichen strukturellen Bau des porösen Netzwerkes zu bewahren, welches in Gegenwart von solvatisierenden Verdünnern erhalten wurde, ist das Entfernen des inerten Mediums mit Methanol. Wenn die Wasserdampfmethode angewendet wird, fin det der sog. Kollapseffekt statt, und die aus solchen Harzen hergestellten Anionenaustauscher adsorbieren weniger Farbstoff im Vergleich zu jenen, die aus Perlen hergestellt worden sind, die mit Methanol behandelt wurden; Grund hierfür ist die durch den Kollaps veränderte Porengröße. Es wurde ebenfalls festgestellt, daß die in Anwesenheit von solvatisierenden Verdünnern (Mischungen aus Quellungs- und Fällmitteln) hergestellten Copolymeren in Methanol sehr gut quellen, obwohl dieses ein Fällungsmittel für Polystyrol ist.
    Notes: The influence of the removal of various diluents, pore forming agents from the porous styrene-ethylstyrene-acrylonitrile-divinylbenzene copolymers on the structure of the matrix was investigated by several methods. The most advantageous pathway to preserve the initial structural edifice of the porous networks performed in the presence of solvating diluents consisted in the removal of the inert media with methanol as it was noticed from the experimental data. If the steam treatment is applied, the collapse effect takes place and the anion exchangers prepared from such matrices exchange/adsorb less dye stuff by comparison with ones formed from beads treated with methanol, because the pore size was changed. It was also noticed that the porous copolymers performed in the presence of the solvating diluents (mixtures of solvatings and precipitants) swell very well in methanol though it is a precipitating medium for the polystyrenic macromolecular chains.
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  • 20
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 139-149 
    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 Styrol-Zinkacrylat-Copolymeren wurde die Abhängigkeit der Glasübergangstemperatur von der Aufheizgeschwindigkeit und der Zusammensetzung mit Hilfe der Differential-Scanning-Calorimetrie untersucht. Die Thermogravimetrie wurde benutzt, um die Pyrolyse dieser Copolymeren an Luft bei drei verschiedenen Aufheizge-schwindigkeiten zu untersuchen. Die thermische Zersetzung von Ionomeren ist ein 3-Stufen-Prozeß. Die Reaktionsordnung und Aktivierungsenergie wurde für jede Stufe der Zersetzung bestimmt unter Verwendung eines Computerprogramms, das auf den Methoden von Kissinger, Freeman-Carrol und Ozawa basiert. Es zeigte sich, daß die thermische Stabilität durch die ionischen Gruppen abnimmt.
    Notes: The dependence of glass temperature on the heating rate and the composition for styrene-zinc acrylate copolymers has been investigated by differential scanning calorimetry. Thermogravimetry was used in order to examine these copolymers undergoing pyrolysis in an atmosphere of air at three different heating rates. Thermal decomposition of ionomers is a three-stage process. The orders and activation energies have been determined for each stage of decomposition using the computer programs based on the methods of Kissinger, Freeman-Carrol, and Ozawa. It was found that the heat stability is lowered by the ionic groups.
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  • 21
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 151-162 
    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 Pfropfung der hydrophilen Monomeren N-Vinylpyrrolidon, 2-Hydroxyethyl-methacrylat und Acrylamid auf ungesättigte segmentierte Polyurethane in N,N-Dimethylformamid mit 2,2′-Azobisisobutyronitril als Initiator wurde untersucht. Die Pfropfcopolymeren wurden von den Homopolymeren durch selektive Extraktion in Soxhlet-Apparaturen abgetrennt. Die kinetische Untersuchung der Pfropfcopolymerisation zeigte, daß die Reaktionen dem gewöhnlichen kinetischen Verhalten radikalischer Polymerisationen folgen. Die Abhängigkeiten der Pfropfungsgeschwindigkeit von der Initiator- und N-Vinylpyrrolidonkonzentration waren von 0,5 bzw. 1,0 Ordnung. Für 2-Hydroxyethylmethacrylat wurden sie zu jeweils 0,5 und 2,0 gefunden. Die Gesamtaktivierungsenergie der Pfropfcopolymerisation des 2-Hydroxyethylmethacrylats und des N-Vinylpyrrolidons betragen jeweilig 21,81 und 16,28 kJ/mol.
    Notes: Grafting of unsaturated segmented polyurethanes with some hydrophilic monomers such as N-vinyl pyrrolidone, 2-hydroxyethylmethacrylate and acrylamide in N,N-dimethylformamide have been studied using 2,2′-azobisisobutyronitrile (AIBN) as initiator. Graft copolymers were isolated from homopolymers by selected solvent extraction using a Soxhlet apparatus. A kinetic study of graft copolymerization reactions showed that the reactions follow the conventional kinetic behaviour of free radical polymerization. The dependencies of the grafting rate on initiator and N-vinyl pyrrolidone concentrations were of 0.5 and 1.00 order, respectively. However, for the 2-hydroxyethylmethacrylate, the dependencies of the grafting rate on initiator and monomer concentrations were found to be of 0.5 and 2.00 order, respectively. The overall activation energy for the graft copolymerization of the 2-hydroxyethylmethacrylate and N-vinyl pyrrolidone were 21.81 kJ/mol and 16.28 kJ/mol, respectively.
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  • 22
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    Angewandte Makromolekulare Chemie 156 (1988), S. 179-185 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultra fine particles were impregnated by using a finely porous cellulose gel membrane. The impregnated gel membrane is a green transparent one and looks like a solid solution. Highly dispersed Ni catalysts on carbon were obtained from thermal decomposition of these gel membranes. The particle size is in the range of several nm to a few ten nm. They show interesting catalytic properties for hydrogenation of olefins such as cyclooctadiene.
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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: The thermo-oxidation resistance and weatherability of LDPE and HDPE compositions, containing up to 45 wt.% calcium carbonate, are investigated. The thermo-oxidation resistance is investigated by dynamic DTA and natural ageing is carried out in an exposure station in a seaside climate. The change in strength and colour after ageing is determined. The behaviours of filled and unfilled polymers are compared. Empirical equations are given, describing the change in the investigated parameters during natural ageing.
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  • 24
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: An Proben aus Polypropylen, die bei sehr unterschiedlichen Einstellungen von Spritzgußmaschinen und Extrudern hergestellt wurden, stellten sich deutliche Abhängigkeiten des Alterungsverhaltens von den thermischen und mechanischen Produktionsparametern ein, die nicht durch unterschiedliche Schmelzetemperaturen bedingt sind. Insbesondere kann ausgesagt werden, daß bei Spritzguß eine hähere Scherbelastung und damit stärkere Orientierungen -eine stärkere Veränderung der Eigenspannungen hervorrufen-einen früheren Glanzabfall und-eine geringere Initialzeit bis zur Rißbildung bewirken.Bei Extrusion fiihrt eine geringere Abkühlgeschwindigkeit und damit ein gröberes Gefüge zu -einer stärkeren Veränderung der Eigenspannungen-einem friiheren und ausgeprägteren Glanzverlust-sowie zu einem früheren Abfall der Reißdehnungen.Unbekannt ist, -ob diese Wirkungen auch bei anderen Thermoplasten als PP auftreten-ob sie auch bei stabilisierten Systemen in relativ gleichem Umfange auftreten-und ob es sich lohnt, die beobachteten Effekte ggf. durch ge zielte Maschineneinstellungen auszunutzen.Auf jeden Fall sollten auf diesem Gebiet weitere Arbeiten durchge-führt werden.
    Notes: Specimens of unmodified polypropylene have been manufactured using extreme adjustings of injection moulding machines and extruders. After artificial weathering, distinct relations of ageing processes to thermal and mechanical production parameters were found, which are not influenced by different melting temperatures. It can be started in particular, that during injection moulding a larger shear stress (resulting in more distinct orientation) results in -a greater change in residual stresses-an earlier gloss reduction-a shorter initial period before cracking.During extrusion a lower cooling rate (resulting in a coarser structure) leads to -a greater change in residual stresses-an earlier and more distinct gloss reduction-an earlier loss of ultimate strain.It remains unknown, whether -these relationships will be similar with other thermoplastic materials than PP-these relationships appear to the same relative extend with stabilized systems-it may be advantageous, to use the observed effects by adjusting the injection moulding and extrusion machines in a special way.It seems to be significant to do more research work in this field.
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  • 25
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    Angewandte Makromolekulare Chemie 160 (1988), S. 1-15 
    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: Poly(tetramethylenadipat)diol mit einer Molmasse von 2000 wurde bei Temperaturen von 60 und 80°C in Gegenwart von Wasser bzw. 1,4-Butandiol sowie den gebräuchlichsten PUR-Katalysatoren (Dabco und Dibutylzinndilaurat) gelagert und die Solvolyse untersucht. Die Geschwindigkeit der Solvolyse nimmt mit steigender Temperatur deutlich zu. Die Alkoholyse wird durch Dibutylzinndilaurat weitaus stärker katalysiert als durch 1,4-Diazabicyclo[2.2.2]oktan. Die Hydrolyse verläuft langsamer, da vermutlich die Katalysatoren bei diesem Prozeß desaktiviert werden. Die mechanischen Eigenschaften von Polyurethanen, die mit den partiell abgebauten Diolen hergestellt wurden, korrelieren gut mit der Abnahme der Molmasse.
    Notes: Poly(tetramethylene adipate)diol having a molar mass of 2000 was stored at temperatures of 60 and 80°C in the presence of water or 1,4-butanediol and a common PUR-catalyst like 1,4-diazabicyclo [2.2.2]octane (DABCO) or dibutyltindilaurate (DBTL) and the solvolysis was investigated. The rate of solvolysis is low at 60°C except for DBTL and shows a drastic increase at 80°C. In the alcoholysis reaction DBTL is a much more active catalyst than DABCO. The rate of hydrolysis is slower probably because the catalysts are deactivated by the acidic products formed in this process. The mechanical properties of polyurethanes made from the degraded polyols are in good correlation with the decrease in molar mass.
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  • 26
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 17-28 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß der Zugabe von Bis(allylphenyl) Typ (TM 120)-Monomeren auf die Eigenschaften von unidirektional mit Carbonfasern verstärkten 4,4′-Bismaleimidodiphenylmethan (BM) - 2,4-Tolylendiamin (A) (1:0,3 Molverhältnis) (BM-A)-Verbundkörpern wird vorgestellt. Das Aushärteverhalten sowie das thermische Verhalten in Luft wurde mit Hilfe der Differentialkalorimetrie (DSC) und der Thermogravimetrie (TGA) untersucht. Die thermische Stabilität nimmt mit ansteigenden Konzentrationen von TM 120 deutlich zu. Demgegenüber steht ein Anstieg der Biegefesigkeit, der interlaminaren Scherfestigkeit sowie der Schlagzähigkeit mit zunehmender Monomerkonzentration. Optimale mechanische Eigenschaften wurden bei etwa 20 Tle./100 Tle. TM 120 erreicht.
    Notes: The paper deals with the effect of addition of bis(allylphenyl) type (TM 120) monomer on the properties of unidirectionally carbon fibre reinforced 4,4′ bismaleimidodi-phenyl methane (BM) - 2,4-tolylene diamine (A) (1:0.3 molar ratio) (BM-A) composites. The curing and thermal behaviour of the blends was investigated by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) in air atmosphere. A marginal decrease in thermal stability was observed with increasing concentration of TM 120. Flexural, interlaminar, and impact strength of the laminates increased in the presence of this monomer. Optimum mechanical properties were observed at ∼ 20 phr of TM 120.
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  • 27
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In dieser Arbeit wurden Veränderungen des verschweisßten Rohr- und Fittingmaterials (isotaktisches Polypropylen Homo- bzw. Copolymer PP-R grau pigmentiert) wührend der für die Praxis relevanten Innendruckversuche untersucht.Bei der technischen Verschweißung von Polyolefinen entstehen charakteristische Gefüigezonen im Schweißnahtbereich, welche vom Fßgematerial und den Fngebedingungen beeinflußt werden. In der vorliegenden Untersuchung wurden sowohl die Materialcbergange im Fiigebereich (mit den Methoden - schichtenweise Differentialkalorimetrie, Polarisations- bzw. Elektronenmikroskopie sowie Fluoreszenzspektroskopie mit extrem hoher Ortsauflösung) als auch die Eigenspannungen hinsichtlich ihrer Verlnderung bei Langzeitpriifung im Innendruckzeitstandversuch bei 95°C bis zu einer Prüfzeit von 18.100h untersucht.Die Abbauvorgänge der Makromoleküle bei der Langzeitprüfung der 364 untersuchten Schweißmuster werden in einer gesonderten Arbeit behandelt (1).Durch die Innendruckversuche bei 950 C findet eine Nachkristallisation und eine Gefügevergrijberung sowohl in der Schweißnaht als auch im Gefüge der Schweißpartner statt. Dabei werden die beim Schweißvorgang eingebrachten Orientierungen und Eigenspannungen unter dem Einfluß von Wärme beim Innendruckversuch weitgehend abgebaut. Durch die unter Druckeinwirkung einsetzenden Flieävorgange jedoch werden neue Eigenspannungen eingebracht.Es konnte gezeigt werden, daß bei guter Verschweißung von PP mit PPCO ein kontinuierlicher Übergang (Mischungsbereich) vom Homopolymeren zum Copolymeren auftritt, der auch beim Langzeiteinsatz im Innendruckversuch erhalten bleibt.
    Notes: The present study deals with changes of welded material of pipes and fittings (isotactic polypropylene homo and copolymer PP-R grey pigmented) during the standardized internal pressure tests, which are commonly used for these products.Technical welding of polyolefines causes characteristic structures, which depend on the natural of the welded material and the welding conditions.In this investigation both the transition of material in the welding seam and the changes of internal stresses during internal pressure tests at 95°C until 18.100h test time were examined. The methods we used were Differential calorimetry of think layers, Polarization- and Electron microscopy, Fluorescence spectroscopy with extreme high local resolution.The effects of decomposition of the macromolecules in the welded samples during the internal pressure tests will be described in a separate paper (1).The internal pressure tests at 95O C cause a recrystallization and an increase of the particle size in the structure of the welding seam and in the structure of the welded parts themselves. Under the above described testing conditions the orientations and internal stresses initiated by the welding procedure will relaxe influenced by heat. However the creep effects that occur in the material when exposed to pressure introduce new internal stresses. It could be shown that in perfectly welded parts a continuous transition from PP to PPCO occurs, which did not change after long time application of internal pressure tests.
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  • 28
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    Angewandte Makromolekulare Chemie 160 (1988), S. 67-81 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden neue Coordinationspolymere mit Schiffschen Basen aus Terephthalal dehyd und S-Benzyldithiocarbazol als Liganden in DMF-Lösung hergestellt. Die erhaltenen Coordinationspolymeren wurden durch Elementaranalyse, magnetische Suszeptibilität, elektronische und IR-Spektroskopie charakterisiert. Die durch Thermogravimetrie bestimmte thermische Stabilität der Coordinationspolymeren nahm in der folgenden Reihenfolge ab: \documentclass{article}\pagestyle{empty}\begin{document}${\rm Zn} \simeq {\rm Fe} 〉 {\rm Co} 〉 {\rm Ni} 〉 {\rm Min} \simeq {\rm Cu}$\end{document} Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymere haben eine Oktaederstruktur mit der Koordinationszahl6, während bei den Cu(II)- und Zn(II)-Coordinationspolymeren eine 4-fach koordinierte quadratisch-planare bzw. eine tetraedrische Struktur gefunden wurde. Ligandenfeld- und nephelawetische Parameter wurden aus den Spektren errechnet. Dam wurde die Ligandenfeldtheorie spin-erlaubter Übergänge angewandt, die sich als konsistent mit einer 6-fach koordinierten Struktur für Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymere erwies. Die Elementaranalysen ergaben bei allen Coordinationspolymeren ein Ligand: Metall-Verhältnis von 1 : 1 und deuteten bei den Mn(II)-, Fe(II)-, Co(II)- und Ni(II)-Coordinationspolymeren auf am Zentralatom assoziierte Wassermoleküle hin.
    Notes: New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements.The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm Zn} \simeq {\rm Fe} 〉 {\rm Co} 〉 {\rm Ni} 〉 {\rm Min} \simeq {\rm Cu}$\end{document} Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.
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  • 29
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    Angewandte Makromolekulare Chemie 160 (1988), S. 91-106 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Emulsionen von aromatischen Polyamidsären (PMPE and PBPPM) in DMF und Methanol wurden benutzt, um gleichmäßige Filme auf Leiteroberflächen durch Elektrophorese abzuscheiden. Die Ausbeute und Qualität der abgeschiedenen Filme hängen von der Art der Polyamidsäre, dem Lösemittel, dem Fällungsmittel, dem oberflächenaktiven Mittel, dem pH-Wert und dem Polymergehalt ab. Die Bedingungen zum Erreichen der höchsten Abscheidungsausbeuten wurden bestimmt.
    Notes: The emulsions of aromatic polyamic acids (PMPE and PBPPM) in DMF and methanol were used to coat uniform films on conductor surfaces by electrodeposition. The deposition yield and quality of the deposited films are dependent on sort of polyamic acid, solvent (DMF), precipitant (MeOH), surfactant (TEA), pH value and solid content. To get maximum deposition yields from PMPE and PBPPM, the best conditions of electrodeposition were required as follows: pH value 5.7 and 5.58, MeOH/DMF weight ratio 3.0 and 2.8, solid content 3.5 and 2.4 wt.-%. Deposition yield was found to obey Faraday's law of electrolysis, and the higher the equivalent weight of the polyamic acid, the higher the coulombic yield.
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  • 30
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    Angewandte Makromolekulare Chemie 160 (1988), S. 107-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein einfaches Modell von Doppelassoziaten wurde verwendet, um die Doppelschichtsorption von binären Gasgemischen an flexiblen linearen Polymerketten zu beschreiben. Die Isothermengleichung nach diesem Modell ist ein einfaches Produkt der isothermen Gleichung, die die Doppelschichtadsorption von binären Gasgemischen an einer homogenen festen Oberfläche beschreibt und einer Funktion, die die spezifischen Merkmale der Sorption an Polymeren widerspiegelt.
    Notes: A simple model of double associates is used to represent bilayer sorption of binary gas mixtures on a flexible linear chain of a polymer. The isotherm equation derived in terms of this model is a simple product of the isotherm equation describing bilayer adsorption of binary gas mixtures on a homogeneous solid surface and a function reflecting specific features of sorption on polymers.
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  • 31
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    Angewandte Makromolekulare Chemie 160 (1988), S. 131-140 
    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: For a polymer system sulfur-styrene containing 10 wt.-% styrene the morphologie depending on the polymerization temperature and time is described. Besides the characteristical orthorhombic phase a monoclinic and a pseudoorthorhombic phase were detected. Moreover amorphous material exists, depending on the polymerisation parameters.
    Notes: Für ein Polymersystem Schwefel-Styrol mit 10% Styrol wird die Abhängigkeit der Morphologie von der Polymerisationstemperatur und -zeit beschrieben. Neben der charakteristischen orthorhombischen Phase wurden röntgenographisch eine monokline und eine pseudoorthorhombische Phase nachgewiesen. Außerdem liegt, abhängig von den Polymerisationsparametern, ein amorpher Anteil vor.
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  • 32
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 117-129 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Für eine anionische Polymerisation mit langsamer Start- und schneller Wachstumsreaktion wurde ein analytischer Ausdruck entwickelt, der es erlaubt, mittlere Molekulargewichte und Molekulargewichtsverteilungen von Polymeren vorauszuberechnen, die in einem halbkontinuierlichen Polymerisationsverfahren bei Zulauf einer verunreinigten Monomerlösung zu einer vorgelegten Initiatolösung entstehen. Die Gültig keit des Modells wurde an der Polymerisation von Isopren mit n-Butyllithium in n-Heptan überprüft. Die beobachteten Unterschiede zwischen theoretischen und experimentellen Werten werden auf die Änderungen in den Geschwindigkeitskonstanten von Start- und Wachstumsreaktion zurückgeführt, die dadurch hervorgerufen werden, daß sich die Polarität der Lösung durch die Anreicherung mit polaren Verbindungen ändert. Weiterhin wird gezeigt, daß bimodale Molekulargewichtsverteilungen entstehen, wenn sich an die halbkontinuierliche Verfahrensweise eine diskontinuierliche zur Erhöhung des Monomerumsatzes anschließt.
    Notes: For anionic polymerization with slow initiation and rapid propagation step analytical expressions are presented to calculate average molecular weights and molecular weight distributions for a semi-batch process, in which a monomer solution contaminated by impurities is fed to an initiator solution in the reactor. The validity of the model was checked for the case of the polymerization of isoprene by n-butyllithium in n-heptane. The differences observed between theoretical and experimental values are explained by the changes in the rate constants of the initiation and the propagation step caused by the change in the polarity of the reaction solution by the continuously fed impurities. Furthermore it is shown that polymers with bimodal molecular weight distributions are formed if the semi-batch procedure is followed by a batch one to increase the monomer conversion.
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  • 33
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 141-154 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Wärmehärtungsmechanismus von zu Anstrichen verwendeten Polyethersulfonen wurde unter Verwendung von FTIR/PAS und ESCA untersucht. Als Ergebnis wurde bestätigt, daß der Luftsauerstoff Einfluß auf den Wärmehärtungsmechanismus hat. Das heißt, die Härtung des Polyethersulfonfilms beginnt an der Oberfläche und verläuft entsprechend Reaktion (4) weiter.
    Notes: Thermosetting mechanism of paint-use polyethersulfones was studied by utilizing FTIR/PAS and ESCA. As a result, it was confirmed that the oxygen in the air has an effect on the thermosetting mechanism. That is, the polyethersulfone film were baked from the surface, and proceeded according to reaction (4).
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  • 34
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    Angewandte Makromolekulare Chemie 160 (1988), S. 155-162 
    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 Mechanismus der Reaktion von 4-Ethylphenol mit Zimtaldehyd mittels HET 2DJ 13C-NMR Spektroskopie, 1H-NMR Spektroskopie und GPC untersucht. In der ersten Stufe findet die Addition des 4-Ethylphenols an die Carbonylgruppe und an die Doppelbindung des Zimtaldehyds statt. In der zweiten Stufe reagiert die —CH(OH)-Gruppe mit 4-Ethylphenol und bildet verzweigte Produkte in rötlich gefärbten Harzen mit einem Durchschnittsmolekulargewicht on 600. Die Reaktion verläuft bei Temperaturen über 100°C in stark saurem Medium.
    Notes: The mechanisms of the reaction between 4-ethylphenol and cinnamaldehyde were studied by means of HET 2DJ 13C-NMR spectroscopy, 1H-NMR spectroscopy and GPC. In the first step of the reaction the addition of 4-ethylphenol to carbonyl group and to double bond of cinnamaldehyde takes place. In the second step of the reaction the —CH(OH)-group reacts with 4-ethylphenol to form branched products of red coloured resins with an average molecular weight of 600. The reaction takes place at temperatures above 100°C in strong acid medium.
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  • 35
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 163-173 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die elektrischen und paramagnetischen Eigenschaften des durch eine direkte Methode aus Benzol und Schwefel synthetisierten Poly(phenylensulfid)s wurden untersucht. Die Geichstromdunkelleitfähigkeit dieses Polymeren im nativen Zustand ist 10-10 S/m. Sie nimmt während des Dotierens mit Jod um 8 Größenordnungen zu. Es wurde für undotierte Proben n-Typ- und für die mit Jod dotierten Proben p-Typ-Leitfähigketi beobachtet. Anhand der ESR-Messungen wurden die Zahl der paramagnetischen Zentren und der g-Faktor bestimmt, die entsprechend gleich 0.80 · 1017 Spins/g und 2.0037 für das undotierte Polymere bei Raumtemperatur betragen. Änderungen der Spinkonzentration sowohl für die mit Jod dotierten als auch für die im Temperaturbereich von 513 - 903 K getemperten Proben werden dargestellt. Es wird versucht, die Form der ESR-Linien auf eine quantitative Weise zu diskutieren.
    Notes: Electrical and paramagnetic properties of poly(phenylene sulphide) synthesized by a direct method from benzene and sulphur were investigated. In darkness dc conductivity of the polymer in its pristine state is of the order 10-10 S/m. Upon doping with iodine it increases by 8 orders of magnitude. For undoped samples the n-type conductivity and for those doped with iodine the p-type conductivity was observed. On the basis of ESR experiments the number of spins and g-value were determined, which for undoped polymer at room temperature are equal to 0.80 · 1017 spins/g and 2.0037, respectively. Next, the changes in spin concentration both for the iodine doped samples and these annealed within the temperature range 513 - 903 K were described. An attempt to discuss the ESR lineshape in a quantitative way was also made.
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  • 36
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 175-186 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 3-Carboxy-4-hydroxyacetophenon (CHAP) wurde in verschiedenen Mengenverhältnissen mit Formaldehyd unter Verwendung von Alkali als Katalysator polykondensiert. Die erhaltenen Polykondensate (CHAP-F) wurden durch Elementaranalyse, IR-Spektroskopie, Bestimmung des Zahlenmittels der Molmasse (M̄n), Thermogravimetrie und Bestimmung der Grenzviskosität charakterisiert. Es wurden polymere Metallchelate mit Cu2+ -, Fe3+ -, Co2+ -, Ni2+ - und UO2+2 -Ionen hergestellt und charakterisiert. Mit Hilfe der Batch-Austauschmethode wurden Ionenaustauschereigenschaften eines CHAP-F Harzes gegen Fe3+ - Cu2+ - und Ni2+ -Ionen bestimmt.
    Notes: 3-Carboxy-4-hydroxyacetophenone (CHAP) was polycondensed with various proportions of formaldehyde using alcoholic alkali as catalyst. The resin samples, designated as CHAP-F, have been characterized by elemental analyses and IR spectroscopy, by estimation of their number average molecular weights (M̄n), by measurement of intrinsic viscosity, and by TGA. Polymeric metal chelates of one CHAP-F sample with Cu2+, Fe3+, Co2+, Ni2+, and UO22+ ions have been prepared and characterized.Ion-exchanging properties of one CHAP-F resin sample for Fe3+, Cu2+, and Ni2+ metal ions are studied by the application of the batch-equilibration method.
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  • 37
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    Angewandte Makromolekulare Chemie 160 (1988), S. 187-192 
    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 Reaktionsenthalpien für die Addition von Hydroxidanion an substituierte Phenylisocyanate wurden mit MNDO berechnet. Die erhaltenen Werte stimmen sehr gut mit den Reaktionsgeschwindigkeiten der Addition von 2-Ethylhexanol an Phenylisocyanate überein. Dies ermöglicht eine Abschätzung der Reaktionsgeschwindigkeiten für nucleophile Additionen innerhalb vernünftiger Grenzen, ohne daß experimentelle Arbeiten durchgeführt werden müssen.
    Notes: The enthalpies for the addition of hydroxide anion to substituted phenylisocyanates have been calculated with MNDO. The results obtained correlate well with the rates of addition of 2-ethylhexanol to phenylisocyanates. This allows us to estimate the rates for nucleophilic addition within reasonable limits without the need for experiments.
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  • 38
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    Angewandte Makromolekulare Chemie 160 (1988), S. 211-211 
    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 163 (1988), S. 63-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Copolymerisation von Butylacrylat (BA) mit Vinylbenzylglycidylether (VBGE) wurden neue Acrylkautschuke mit Epoxyseitengruppen hergestellt. Um die Zähigkeit eines gehärteten Epoxidharzes (Bisphenol A/Diglycidylether/p,p′-Diaminodiphenylsulfon) zu erhöhen, wurde dieses mit den erhaltenen Acrylkautschuken modifiziert. Eine Zugabe von 20 Gew.-% eines Copolymeren mit 74% BA und 26% VBGE-Einheiten führte zu einer 30proz. Zunahme der Bruchzähigkeit (KIC) des gehärteten Harzes bei einer minimalen Einbuße an Festigkeit und Steifigkeit. Die modifizierten Harze wiesen eine Zwei-Phasen-Morphologie auf, bei der Kautschukteilchen mit einer mittleren Größe von 2 μm in eine Epoxymatrix eingebettet sind. Das Copolymere ohne Epoxyseitengruppen, das aus BA und Vinylbenzylmethoxyethylether hergestellt wurde, war als Modifier unwirksam, was darauf hindeutet, daß die seitenstándigen Epoxidgruppen zu einer guten Zwischenphasenadhäsion zwischen Kautschukteilchen und Matrix, und damit zu erhöhter Zähigkeit führen. Kautschuke, die 55 oder 86% BA-Einheiten enthielten, waren ebenfalls ungenügende Modifier. Zugabe des ersteren ergab Harze mit einer homogenen Phasenstruktur, während die Zugabe des letzteren zu einer Phasentrennung zwischen Kautschuk und Epoxidharz führte.
    Notes: New acrylic rubbers with a pendant epoxy group were prepared by copolymerization of butyl acrylate (BA) with vinylbenzyl glycidyl ether (VBGE). The modification of an epoxy system (bisphenol-A diglycidyl ether/p,p′-diaminodiphenyl sulfone) with the acrylic rubbers was carried out in order to increase the toughness of the cured epoxy resin. The addition of 20 wt.-% of the copolymer containing 74% of BA and 26% of VBGE units resulted in a 30% increase in the fracture toughness (KIC) of the cured resin at minimal expenses of strength and modulus of the resin. The modified epoxy resin had two-phase morphology in which the rubber particles with average diameter of 2 μm are dispersed in the epoxy matrix. The copolymer without the pendant epoxy group, prepared from BA and vinylbenzyl methoxyethyl ether, was ineffective as a modifier, indicating that the reaction of the pendant epoxide with the epoxy matrix resulted in good interfacial adhesion between the rubber particles and the matrix, and in the increased toughness. The epoxide-containing copolymers with 55 or 86% of BA units were also insufficient modifiers. The addition of the former yielded cured resins with homogeneous structure, whereas that of the latter resulted in macroscopic phase separation between the rubber and the epoxy resin.
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  • 40
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    Angewandte Makromolekulare Chemie 163 (1988), S. 77-91 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Lösungen von Polyether/Polyurethan-Kationomeren, die auf Toluoldiisocyanaten basieren, wurden hergestellt und durch Zugabe von Wasser emulgiert. Die Eigenschaften von aus diesen Lösungen und Emulsionen gegossenen Filmen werden mit Hilfe der Infrarot-Spektroskopie, dynamisch-mechanischer Messungen, der Differentialkalorimetrie, der Weitwinkel-Röntgendiffraktometrie und von Zug-Dehnungsmessungen untersucht. Der Einbau eines asymmetrischen, kettenverlängernden Bausteins, wie N-Methyldiethanolamin, führt zu einem Polyurethan (PU), das, ßhnlich wie das mit symmetrischem, kettenverlängerndem 1,4-Butandiol aufgebaute Polyurethan, eine meßbare Ordnung innerhalb der Hartsegmente aufweist. Nach der Quarternisierung mit Glykolsaure haben die PU-Kationomeren erhöhte Werte für Reißdehnung, Zugmodul und -festigkeit. Dies kann auf die Coulomb-Wechselwirkung zwischen benachbarten Hartsegmenten zurückgefiihrt werden. Das Emulgieren der PU-Ionomer-Lösung führt zu einer verstärkten Mischung der Weich-und Hartsegmente, wodurch die ursprünglichen Hartsegmentbereiche mit asymmetrischen 2,4-Urethanisomeren eine höhere Konzentration an 2,6-Isomeren enthalten. Die Hartsegmentbereiche erreichen dadurch höhere Ordnung. Diese erhähte Ordnung und Phasenmischung führt zu einer Verbesserung der mechanischen Eigenschaften. Die Veränderung der Leitfähigkeit und Viskosität wahrend dem Emulgieren zeigt, daß das Wasser zuerst auf der Oberfäche des Mikroionengitters der Hartsegmente adsorbiert wird und dann in die ungeordneten und geordneten Hartsegmentbereiche eindringt.
    Notes: Toluene diisocyanate based polyether polyurethane cationomer solutions are prepared and then emulsified by adding water. Properties of films cast from the solutions and emulsions are studied using infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, wide-angle X-ray diffraction, and tensileelongation testing. It is found that the use of the asymmetric chain extender, N-methyl-diethanolamine, also leads to a polyurethane (PU) with detectable order in the hard domains as in the PU with symmetric chain extender such as 1,4-butandiol. After quaternization with glycolic acid, the PU cationomers have increased elongation and tensile strength and modulus. These can be attributed to the proper Coulomb interaction between two neighboring hard segments. The emulsification of the PU ionomer solution results in an increased mixing between the soft segments and the hard segments with asymmetric 2,4-urethane isomers originally located in the hard domains, and therefore make the hard domains containing a higher concentration of symmetric 2,6-isomer. The hard domains then become more ordered. Such increased order and phase mixing leads to an increase of the three tensile properties. During the emulsification conductivity and viscosity variations show that water is firstly adsorbed on the surface of the hard segment microionic lattices and then enters into the disordered and ordered hard domains successively.
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  • 41
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die künstliche Bewitterung von PVC-Proben liefert nicht unter allen Bedingungen gleichartige Ergebnisse, wie im Freien. Gut bewährt haben sich die Xenotest-Prüfungen bei weißen Fensterprofilmustern, sowie bei grau eingestellten Dachfolien. Die Bewitterung im QUV-Gerät, unabhsngig von der Bestückunq, gibt eine wesentlich schnellere Veränderung als im Freien, wobei manche Effekte die im Freien auf-treten, im QUV durch den Zeitraffereffekt nicht erkennbar werden.
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  • 42
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydroperoxides formed on thermal oxidation of polyethylene have been used to examine their photolysis. The kinetics and mechanisms of the photolytically induced decomposition of these hydroperoxides are considered. The difficulties encountered with the mechanism based on homolysis of the hydroperoxy bond are discussed. New mechanisms of hydroperoxide photolysis based on bimolecular reactions are proposed. They are in agreement with the products found experimentally - mainly ketones and trans-vinylene groups - and with the kinetics of the product formation. The mechanisms envisaged are easily adapted to polyolefins other than polyethylene and polymers in general.
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  • 43
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The influence of humidity on the light-fastness and the dark time yellowing of white PVC and special changes of the irradiated surfaces are described. The results show, that the boundary surface climate at the irradiated specimen surfaces has a decisive influence on the ageing results.
    Notes: Der Einfluß der relativen Luftfeuchte auf die Lichtechtheit und beim Nachdunkeln von weißem PVC und besondere Veränderungen der bestrahlten Oberflächen werden beschrieben. Die Ergebnisse zeigen, daß das Grenzflächenklima an der bestrahlten Probenoberfläche einen entscheidenden Einfluß auf das Alterungsergebnis hat.
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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
    Notes: The variations of molecular spectra, colours and characteristic viscosity of modified and unmodified PVC compounds during the polymerization process in various periods of time of natural ageing have been investigated.The PVC types modified during synthesis by 0,25 % vol. plasticizers or plasticizers' mixture are characterized by 10 - 12°C lower glass transition temperature, higher thermal stability, long-term behaviour and better physical and mechanical properties. The Charpy-impact resistance is increased by 50 to 85%. The rate of the relative UV-sorption variation during outdoor exposure was lower for compounds based on the modified PVC types.The polyene parts amount of chain length n = 13, evaluated by means of Raman spectra, was increased during the first and second month, both on non-irradiated and irradiated surface. The total colour variation ΔEab of the new PVC grades in a 10-month poriod of weathering was of 10-30% less compared to the unmodified PVC grades.By means of IR-spectroacopy the variations of the hydroxyl- and carbonyl groups were .valuated and the diffemncee in the oxidation kinetica were establiehed.
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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
    Notes: Die Aufgabe der hier vorliegenden Arbeit ist es, die atmosphärische Alterung der schlagfesten Zweiphasen-Styrol-Copolymere in Abhängigkeit von der Monomerzusammensetzung der Matrix sowie der Art und Menge des Kautschuks zu untersuchen. Zu diesem Zweck wurden BS, ABS, MBS und PS, SAN untersucht, die in der Zusanmensetzung des Monomers der Matrix zveim der Zweiphasensysteae entsprechen (BS und ABS).Aus der Interpretation tier aufgenoi;mienen Daten wurde festgestellt, der eine ßorrelation zwischen den Strukturveränderungen, der Kerbschlagezähigkeit und der ßiegefestigkeit besteht. Die durchgeführten Untersuchungen zeigen den deutlich schwierigen Charakter der Alterungsprozesse der phasenheterogenen Systeme im Vergleich zu den Homopolyneren und homogenen Copolymeren. Die Schlußfolgerungen können zur Vorauswahl des Typs und der Henge des Stabilisators in Abhängigkeit von der Honomer- und Phasenzusammensetzung der Systeme herangezogen werden.
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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
    Notes: Antioxidants acting in polymers by chain-breaking and hydroperoxide decomposing mechanisms are chemically transformed during the stabilization process as a consequence of trapping radicals R•, RO• or RO•2 and/or reactivity with hydroperoxides. New chemical compounds with typical structures characteristic of the starting stabilizer are formed stepwise in the polymer mass. Most of these transformation products participate actively in consecutive steps of polymer degradation. Finally observed phenomena depend on the concentration of individual transformation products. Generally, autocooperative effects with starting stabilizers take place. Important data regarding properties of transformation products have been summarized.
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  • 47
    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 Differentialthermoanalyse ist als Methode zur Abschätzung der thermooxidativen Beständigkeit von Polyolefinen seit längerem bekannt. In der vorliegenden Arbeit wird über isotherme DTA-Messungen an Proben aus Polybuten-1 im Temperaturbereich von 260°C bis 130°C berichtet, wobei Oxidationsinduktionszeiten bis 7000 Stunden gemessen wurden. Die Auftragung der Oxidationsinduktionszeiten in Arrhenius-Diagrammen zeigte für Polybuten-1 keine für Extrapolationszwecke geeignete Linearität des Logarithmus der Oxidationsinduktionszeiten über der reziproken absoluten Temperatur über weitere Bereiche der Meßzeiten bzw. Prüftemperaturen. Die thermoanalytisch bestimmten Oxidationsinduktionszeiten stimmten mit dem Steilabfall der Reißdehnung und der molaren Masse in Ofenalterungsversuchen überein. Damit können aufwendige Ofenalterungsversuche durch experimentell einfache isotherme DTA-Versuche ersetzt werden. Die Messung der thermooxidative Restbeständigkeit im isothermen DTA-Versuch bei erhöhter Prüftemperatur ermöglicht einen wesentlich deutlicheren Einblick in den thermooxidativen Schädigunqszustand eines Polyolefins während der Induktionsperiode des thermooxidativen Abbaus als die Messungen der molaren Masse oder der Reißdehnung. Bei hohen Ofenlagerungstemperaturen erfolgte die Abnahme der thermooxidativen Restbestandigkeit linear uber der Alterungszeit, bei Alterungstemperaturen unterhalb von 160°C nahm die thermooxidative Restbeständiqkeit degressiv in Abhängigkeit von der Ofenalterungszeit ab. Schließlich konnte mit Hilfe der isothermen Differentialthermoanalyse die Extraktion von Stabilisatoren aus Polybuten-1 in einfacher Weise beobachtet werden.
    Notes: Isothermal differential thermal analysis (DTA) is a well known method of testing thermooxidative stabilities of polyolefins. Oxidation induction times, measured up to 7000 hours and over a temperature range from 260°C to 130°C has been used to study the stability of polybutene-1 in the melt state.The Arrhenius plots of DTA results show that straight line extrapolation from high to low temperatures is not possible. Thermoanalytically measured oxidation induction times and mechanical failure in oven ageing experiments agree well for polybutene-1. Measurements of molecular weight and of mechanical properties of polybutene-1 during the induction period of oven ageing experiments revealed that molecular weight and tensile properties are not sensitive indicators for the beginning of ageing. The state of deterioration can be estimated easier by measurement of residual lifetime in the isothermal DTA experiment. At high ageing temperatures the residual lifetime decreased linearly during the induction period, at ageing temperatures below 160°C the decrease of residual lifetime was found degressive.Finally the extraction of stabilizer by not water could be measured by isothermal DTA.
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  • 48
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    Angewandte Makromolekulare Chemie 156 (1988), S. 1-20 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: By model reactions of partially substituted melamine- and urea-compounds with formaldehyde the cocondensation of melamine and urea with formaldehyde was studied. Investigations on the model systems urea/benzoguanamine/formaldehyde and dimethylurea/2-amino-4,6-di-(N-methylanilino)-1,3,5-triazine/formaldehyde with gelchromatography, IR-spectroscopy, and thermogravimetry showed bridges between urea- and melamine-compounds.Also in urea-melamine-formaldehyde-resins it was possible to prove the occurrance of cocondensates by precipitation the melamine derivates with picric acid and analysis of the precipitates by urease-decomposition.
    Notes: Anhand von Modellreaktionen von teilweise blockierten Melamin- und Harnstoff-derivaten mit Formaldehyd wurde die gemeinsame Kondensation von Harnstoff, Melamin und Formaldehyd studiert. An den Modellsystemem Harnstoff/Benzoguanamin/Formaldehyd und Dimethylharnstoff/2-Amino-4,6-di-(N-methylanilin)-1,3,5-triazin/Formaldehyd konnten mit Hilfe der Gelchromatographie, IR-Spektroskopie und Thermogravimetrie chemische Brücken zwischen den Triazin- und Harnstoffkomponenten, also Cokondensate, festgestellt werden.Auch beim System Harnstoff/Melamin/Formaldehyd konnten durch Pikratfällung der Triazinkomponenten und Urease-Spaltung dieses Niederschlages Cokondensate nachgewiesen werden.
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  • 49
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    Angewandte Makromolekulare Chemie 156 (1988), S. 21-27 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden Polyester basierend auf 1,4,5,6,7,7-Hexachlor-5-norbornen-2,3-dicarbonällureanhydrid (I), Tetrachlorphthalsäureanhydrid (II), Dibromneopentylglykol (II), ein Polyesterblend (V) bestehend aus dem Polyester (III) und einem Polyester (IV) für allgemeine Zwecke, ein Polyester (VI) basierend auf 1,4,5,6,7,7-Hexachlor-5-norbornen-2,3-dicarbonsäureanhydrid und dem Polyester III und ein Polyesterblend (VII) bestehend aus den Polyestern I und III hergestellt. Ihre chemische Resistenz und ihre Feuchtigkeitsaufnahme bei Temperaturen von 25 und 65°C wurden in Säuren, 20% NaOH und Wasser untersucht. Hierbei wurde gefunden, daß der Polyester (III) von den Säuren am wenigsten angegriffen wird. Verglichen mit unbehandelten Poly meren fand bei beiden Temperaturen in 20% NaOH eine Gewichtsabnahme bei allen Polyestern statt, mit Ausnahme des Polyesters VII. Erne Gewichtszunahme aller Polyester wurde beobachtet durch Feuchtigkeitsaufnahme sowohl bei 25 als auch bei 65°C, wobei die Zunahme bei der höheren Temperatur größer war. Der Polyester III zeigte die geringste Feuchtigkeitsaufnahme.
    Notes: Chlorendic anhydride based polyester (I,) tetrachlorophthalic anhydride based polyester (II), dibromoneopentyl glycol based polyester (III,) general purpose polyester (IV,) blend of dibromoneopentyl glycol based polyester with general purpose polyester (V,) chlorendic anhydride and dibromoneopentyl glycol based polyester (VI), and a blend of chlorendic anhydride based polyester and dibromoneopentyl glycol based polyester (VII) were prepared and their chemical resistance and moisture absorption studied in various reagents, acid, alkali, and water, at 25 and 65°C. It is found that the polyester (III) is the least affected in the presence of the acids. In 20% NaOH, there was a decrease in weight for all polyesters at both the temperatures compared to the control except the polyester (VII). Increase in weight of all the polyesters was observed during the absorption of moisture both at 25 and 65°C. The increase was higher at higher temperature. Polyester (III) thus shows the least absorption of moisture.
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  • 50
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    Angewandte Makromolekulare Chemie 156 (1988), S. 29-35 
    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: Polymere mit Urethaneinheiten wurden durch Lösungspolymerisation der Bisphenole A, C und F mit Diisocyanaten wie Toluol-2,4-diisocyanat, Hexamethylendiisocyanat, Isophorondiisocyanat bzw. Diphenylmethandiisocyanat hergestellt. Die erhaltenen Polymeren waren blaßgelbe Pulver. Diese Polymeren wurden durch IR-Spektroskopie und Bestimmung des Stickstoffgehalts charakterisiert. Die zahlenmittleren Molekulargewichte (M̄n) wurden durch Leitfähigkeitstitration und Bestimmung der Grenzviskositätszahl in Dimethylformamid ermittelt. Mittels Thermogravimetrie wurde das thermische Verhalten untersucht. Die kinetischen Parameter des Abbaus wurden berechnet.
    Notes: Polymers containing urethane units were synthesized by solution polymerization of bisphenols A, C, and F with diisocyanates viz. toluene-2,4-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate, respectively. Thus obtained polymers were pale yellow amorphous powders. These polymers were characterized by infrared spectral studies and nitrogen content. The number-average molecular weights (M̄n) were estimated from conductometric titration and limiting viscosity number [η] in dimethyl formamide. From thermogravimetric analyses, the thermal behaviour was studied. Kinetic parameters for their degradation were computed.
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  • 51
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    Angewandte Makromolekulare Chemie 156 (1988), S. 37-48 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Neue Diglycidylester wurden in Gegenwart von quaternären Ammoniumsalzen als Katalysator aus ihren entsprechenden Dicarbonsäuren und Epichlorhydrin hergestellt. Die neuen unsymmetrischen Produkte wurden durch spektroskopische Methoden identifiziert und als Monomere in einer Aushärtungsreaktion eingesetzt. Der Reaktionsverlauf wurde mittels IR-Spektroskopie verfolgt. Die Struktur einiger 1öslicher Zwischenprodukte wurde durch 13C-NMR-Spektroskopie ermittelt. Das thermische Verhalten dieser ausgehärteten Epoxidharze wurde ebenfalls untersucht.
    Notes: New diglycidyl esters coming from the corresponding diacids and epichlorohydrin were synthetized using a quaternary ammonium salt as a catalyst. The new asymmetric compounds were characterized by spectroscopic methods and employed as starting monomers in a crosslinking process. The course of the reactions was followed by IR spectroscopy. Some intermediate species were identified in the onset of the reactions by recording 13C-NMR spectra until the products became insoluble in the usual deuterated solvents. The thermal behaviour of these cured epoxy resins was also studied.
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  • 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: Carboxymethylcellulose (CMC) wurde bei 80°C unterschiedlich lange (15 - 60 min) mit HCl behandelt. Sowohl die hydrolysierten CMC-Proben als auch die ursprüngliche Probe wurden mit Acrylamid unter Verwendung von K2S2O8 als Initiator gepfropft. Es zeigte sich, daß mit zunehmender Hydrolysezeit die Kupferzahl der CMC anstieg, während der Carboxylgehalt dagegen abnahm. Die saure Hydrolyse erhöhte die Empfindlichkeit der CMC gegenüber Pfropfung bedeutend. Die Pfropfung reduziert die Kupferzahl der hydrolisierten CMC-Proben, höchst wahrscheinlich durch Umwandlung der aldehydischen in carboxylische Gruppen unter Mitwirkung von K2S2O8, wiährend der Pfropfung. Pfropfen reduziert ebenfalls den Carboxylgehalt der ursprünglichen CMC-Probe, aber es erhöht dagegen die Carboxylgehalte der hydrolysierten CMC-Proben. Durch Methylolierung der Polyacrylamid-CMC-Pfropfcopolymeren erhält man ein Appreturmittel für Textilien. Die Anwendung dieser Pfropfcopolymeren auf Baumwollgewebe gemäü der herkömmlichen „pad-dry-cure“- Methode lieferte folgende Ergebnisse: 86% der Appretur blieben auf dem Gewebe haften, wenn man CMC-Copolymere benutzte, 92% dagegen bei Verwendung von Copolymeren der hydrolysierten CMC.
    Notes: Carboxymethyl cellulose (CMC) was treated with HCl at 80°C for different time periods (15 - 60 min). The hydrolyzed CMC samples as well as the original sample were graft copolymerized with acrylamide using K2S2O8 as initiator. It was disclosed that the increasing duration of acid hydrolysis is accompanied by a progressive increment in the copper number of CMC, meanwhile its carboxyl content decreases. Acid hydrolysis enhances significantly the susceptibility of the CMC toward grafting. The latter reduces the copper number of the hydrolyzed CMC samples most probably via conversion of the aldehydic to carboxylic groups under the action of K2S2O8 during grafting. Grafting also reduces the carboxyl content of the original CMC sample while increasing those of the hydrolyzed CMC samples. Methylolation of the polyacrylamide-CMC graft copolymers results in reactive finishes. When the latter were applied to cotton fabric according to the conventional pad-dry-cure method followed by a thorough washing, the fabric retained ca. 86% of the finish derived from the copolymer of CMC and 92% of finishes derived from the copolymers of hydrolyzed CMC.
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  • 53
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    Angewandte Makromolekulare Chemie 157 (1988), S. 123-136 
    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 Porengröße von porösen, vernetzten Polystyrolen wurde mit einer Intrusionsmethode untersucht. Hierbei wurde der Druck gemessen, der nötig war, um das Quecksilber in die Poren zu pressen. Die verschiedenen Nachbehandlungen dieser Polymeren lieferten interessante Ergebnisse über das Verhalten der mit der oben genannten Methode untersuchbaren „stationären Poren“, im allgemeinen Makroporen genannt. Es wurde gefunden, daß die Makroporen sich verkleinern oder ganz verschwinden, wenn man die porösen, vernetzten Polystyrole entweder in dem guten Lösungsmittel Ethylendiclorid (EDC) quellen läßt oder über ihre Glastemperauren (Tg) erhitzt. Weiterhin wurde beobachtet, daß diese wieder erscheinen, wenn man die so behandelten Polymeren wieder quellen läßt, und zwar zuerst in EDC und anschließend in dem schlecten Lösungsmittel Methanol. Diese Ergebnisse legen nahe, daß die Struktur der Makroporen memoriert wurde ähnlich den Legierungen mit Strukturerinnerungsvermögen.
    Notes: Porosity of porous crosslinked polystyrenes was examined by the pressurized-mercury intrusion method. Various aftertreatments of those polymers revealed interesting results of behaviors of “fixed pores”, whichS indicates pores measurable by this method: (1) fixed pores were found to diminish or vanish by swelling them with ethylene dichloride (EDC) as a good solvent or by heating them above the glass transition temperature (Tg), but (2) those pores were observed to reappear after the polymers treated above were swollen again with EDC, followed by replacing EDC with methanol as a poor solvent. This implies that the fixed-pore structure has been memorized like a shape-memory alloy.
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  • 54
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    Angewandte Makromolekulare Chemie 157 (1988), S. 137-151 
    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: Styrol-Acrylsäure (St-AA)-Copolymere mit niedrigen Molekulargewichten (M̄w 〈 15000) wurden bei hohen Temperaturen (230 - 300°C) in einem kontinuierlichen Rührkesselreaktor hergestellt. Diese wurden dann in Lösungsmittel/Nichtlösungsmittel-Systemen fraktioniert ausgefällt. Um Monomerreste und Oligomere mit niedrigsten Molekulargewichten zu entfernen, wurden die Fraktionierungsexperimente mit dem Methanol-Dichlormethan/Hexan-System ausgeführt (1. Schritt). Im zweiten Fällungsschritt wurden unter Benutzung des gleichen Lösungsmittel/Nichtlösungsmittel-Systems die Ldslichkeitsgrenzen der St-AA-Copolymeren als Funktion der Copolymerzusammensetzung (mit Hilfe der Triibungspunktmethode) bestimmt. Zur Charakterisierung der Copolymeren wurden die Gelchromatographie (mit Styragelsaulen), die Kleinwinkellaserlichtstreuung (LALLS) und die volumetrische Titration der Carboxygruppen angewendet. Zur Bestimmung des Ldslichkeitsdiagramms der niedermolekularen St-AA-Copolymeren wurden die beiden Ldsungsmittelparameter S, und Polaritatsindex P′ benutzt.
    Notes: Styrene-acrylic acid (St-AA) low molecular weight copolymers (M̄w 〈 15,000) synthesized at high temperatures (230 - 300°C) in a continuous stirred tank reactor were fractionally precipitated in solvent/nonsolvent systems. Fractional precipitation experiments were done in the system methanol-dichloromethane/hexane to remove residual monomers and the lowest molecular weight oligomers (1st step). Solubility limits of St-AA copolymers as a function of copolymer composition were determined using the same solvent/nonsolvent system in the 2nd step of precipitation tests (cloud point base). GPC on Styragel-type columns, low-angle laser light scattering (LALLS), and volumetric titration of carboxylic groups were applied for copolymer characterization. Two solvent-derived parameters the total solubility parameter δT and the polarity index P′ are used to determine the solubility diagrams of St-AA low molecular weight copolymers.
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  • 55
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    Angewandte Makromolekulare Chemie 157 (1988), S. 177-187 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kinetik der alkalischen Hydrolyse von Glimmer-Acrylnitril-Pfropfcopolymeren wurde untersucht. Die Abhängigkeit des Verseifungsgrades von der Alkalikonzentration und der Hydrolysezeit wurde bestimmt. Chemische und spektroskopische Techniken wurden zur Bestimmung des Hydrolysemechanismus herangezogen.
    Notes: Kinetics of alkaline hydrolysis of mica-acrylonitrile graft copolymers was studied. The dependence of alkali concentration and the time of hydrolysis on the degree of saponification was determined. Chemical and spectroscopical techniques were used to determine the mechanism of hydrolysis.
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  • 56
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    Angewandte Makromolekulare Chemie 157 (1988), S. 153-163 
    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 Behandeln von Baumwollgewebe mit Schwefelkohlenstoff in Gegenwart von NaOH ergibt Cellulosethiocarbonat, welches mit Cerammoniumnitrat (CAN) einen Komplex bildt. Nach ausgiebigem Waschen war das CeIV-Cellulosethiocarbonat fähig, die vinylische Pfropfpolymerisation auf Baumwollgewebe ohne Homopolymerbildung zu initiieren. Die Pfropfausbeute wuchs im Falle von Methylmethacrylat mit wachsenden CAN-Gehalt (0 - 50 mmol/l) und steigender Temperatur (60 - 80°C). Bei pH 2 war die Pfropfung besonders begünstigt. Dagegen wurde die Pfropfung im alkalischen Bereich gestoppt. Die Zugabe von bis zu 7% Methanol, Ethanol oder Isopropanol zum wäßrigen Polymerisationsmedium erhöhte die Pfropfausbeute bedeutend; hierbei wurde mit Isopropanol die hdchste Steigerung erhalten. Hdhere Alkoholmengen dagegen erniedrigten die Ausbeute. Die Pfropfgeschwindigkeit ist anfangs hoch, spater wird die Pfropfungsreaktion langsamer. Unabhingig von den verwendeten Reaktionsbedingungen war eine Reaktionszeit von 60 Minuten ausreichend. Es wurde die Fahigkeit des Cdv-Cellulosethiocarbonats untersucht, die Pfropfung mit Methylmethacrylat, Acrylnitril und Acrylamid zu initiieren. Dabei ergab sich fur die Pfropfgeschwindigkeit folgende Reihenfolge: Methylmethacrylat 〉 Acrylnitril 〉 Acr ylamid.
    Notes: Treatment of cotton fabric with carbon disulphide in presence of NaOH resulted in cellulose thiocarbonate. The latter formed a complex when treated with ceric ammonium nitrate (CAN). After being thoroughly washed, the CeIV cellulose thiocarbonate was capable of initiating vinyl graft polymerization onto cotton fabric without homopolymer formation. The graft yield obtained with methyl methacrylate was found to increase by increasing CAN from zero to 50 mmol/l at temperatures from 60 to 80°C. Grafting was greatly favoured at pH 2; alkaline pH offset grafting. Incorporation of up to 7% of methanol, ethanol, or isopropanol in the aqueous polymerization medium enhanced grafting significantly with the certainty that the highest graft yield was obtained with isopropanol; using higher alcohol percentages decreased grafting. The rate of grafting showed an initial fast rate followed by a slower rate; 60 minutes reaction time proved appropriate for grafting irrespective of the condition used. In addition to methyl methacrylate the ability of CeIV-cellulose thiocarbonate to induce grafting of acrylonitrile and acrylamide was also examined. The rate of grafting followed the order methyl methacrylate 〉 acrylonitrile 〉 acrylamide.
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  • 57
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    Angewandte Makromolekulare Chemie 157 (1988), S. 165-176 
    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 der Röntgenkleinwinkelstreuung von aus der orientierten Schmelze kristallisierten Legierungen aus isotaktischem Polypropylen und Poly(1-buten) wurden Grenzflächenverteilungsfunktionen berechnet. Die Proben enthalten Nadelkristalle, die in Bezug auf ihre Abstandsverteilung ein „verdünntes System“ darstellen. Es wird gezeigt, daß die Berechnung von Grenzflächenverteilungsfunktionen aus jeweils nur zwei Grenzflächen möglich ist. Der Vergleich der erhaltenen Nadeldicken mit Ergebnissen aus anderen Auswertemethoden ergibt eine gute Übereinstimmung.
    Notes: Interface distribution functions have been evaluated from the equatorial small angle x-ray scattering of blends of isotactic polypropylene and poly(1-butene) crystallized in the shear field of the oriented melt. The samples contain core fibrils which represent a diluted system with respect to their distance statistics. It is shown, that interface distribution functions can be calculated from only two interfaces (diffuse phase boundaries between fibrils and amourphous phase). The calculated thicknesses agree well with values determined from other methods.
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  • 58
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    Angewandte Makromolekulare Chemie 157 (1988), S. 199-199 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abrstract.
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  • 59
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper accumulates the mechanism and kinetics of oxidation and the inhibition mechanism of oxidation processes using preventive antioxidants, chain-breaking antioxidants and deviations from the simple inhibition mechanism.
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  • 60
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    Angewandte Makromolekulare Chemie 160 (1988), S. 83-90 
    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 Reaktion von Poly(methylvinylketon) und acetyliertem Polystyrol mit Phenol in Gegenwart von HCl oder H2SO4 wurde untersucht, um Polymere mit Strukturen ähnlich dem Bisphenol A zu erhalten. Die Reaktion an Poly(methylvinylketon) führt zu intramolekularer Aldol-Kondensation, während acetyliertes Polystyrol die gewünschte Bisphenol A-Struktur liefert.
    Notes: The reaction of polymers containing carbonyl groups such as poly(methyl vinylketone), poly(methyl vinyl ketone-co-styrene) and acetylated polystyrene with phenol in the presence of HCI or H2SO4 has been studied in order to produce bisphenol A type structure on the polymer chain. Poly(methyl vinyl ketone) shows intramolecular aldol condensation and acetylated polystyrene results in bisphenol A type structure.
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  • 61
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    Angewandte Makromolekulare Chemie 160 (1988), S. 29-39 
    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 der vorliegenden Arbeit wird der Einfluß der Verformungsamplitude, der Temperatur und der Frequenz auf die dynamischen Eigenschaften von SBR-Faserverbundstoffen untersucht. Der Einbau von Kurzfasern erhöht den Speichermodul bei beliebiger Verformungsamplitude. Je nach Fasertyp verringert sich die lineare Reaktionszone des Moduls auf die Verformung oder verschwindet vollkommen. Der Verlustfaktor tan δ ist größer bei Faserverbundstoffen, obwol die Signale größenmäßig sich nicht verändern, lediglich die entsprechende Verformung.Bei Temperaturanstieg verringert sich der Modulwert, jedoch ist dieser Abfall weniger stark ausgeprägt im Faser-SBR-Verbund. Die Relaxationsspektren zeigen eine maximale Dämpfung, die der Hauptrelaxation in der Elastomermatrix entspricht. Die Temperatur,bei der dieses Maximum auftritt, verlagert sich zu höheren Werten mitsteigender Anregungsfrequenz. Dadurch wird die Ermittlung der scheinbaren Relaxationsaktivierungsenergie möglich, die im Verbund Faser-Haftmittel-SBR höher ist (225-275 kJ/mol) als in dem faserfreien Stoff (194.6 kJ/mol) als Folge einer stärkeren Faser-Matrix-Wechselwirkung.
    Notes: This paper examines the effects of deformation amplitude, temperature and frequency on the dynamic properties of SBR-short fiber composites. The presence of the fiber increases the storage modulus at any deformation amplitude. Depending on the nature of the fiber, the linear response zone of the modulus versus deformation either diminishes or disappears. The loss factor tan δ is higher in fiber composites. Although the peaks do not vary in magnitude, they occur at different deformation amplitudes.Temperature increase causes the moduli to decrease, the gradient, however, being less pronounced for fiber composites. The relaxation spectra show a damping peak which correlates to the principal relaxation process in the elastomeric matrix. The temperature at which this peak appears is displaced towards higher values with increasing excitation frequency. This allows the determination of the apparent relaxation activation energy, which is higher in fiber plus adhesive composites (225 - 275 kJ/mol), as compared to the fiber-free composite (194 kJ/mol), as a consequence of stronger fiber-matrix interaction.
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  • 62
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    Angewandte Makromolekulare Chemie 160 (1988), S. 41-66 
    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 neuer Typ eines UV-härtbaren Polyurethanacrylatharzes synthetisiert, das auf hydroxyterminierten Polydimethylsiloxan (PDMS)-Weichsegmenten mit einem Molekulargewicht von 1800 und 2,4-Toluoldiisocyanat (TDI)/2-Hydroxyethylmethacrylat (HEMA) Hartsegmenten basiert. Die Reaktivität von 2,4-TDI mit den Hydroxygruppen von Silanol und HEMA wurde anhand von IR-Messungen diskutiert. Die charakteristischen Absorptionspeaks der NCO-Gruppen von 2,4-TDI in para- und ortho-Stellung sollten mit zunehmender Reaktionszeit abnehmen.Die Meßmethodik der wesentlichen physikalischen Eigenschaften dieser Art von UV-härtbaren Materialien wurde ebenso wie auch der Einfluß verschiedener reaktiver Verdünnungsmittel und einiger Pigmente untersucht. Dieses Harz mit guten optischen, elektrischisolierenden und Hafteigenschaften an verschiedenen Matrizes konnte in den chemischen Eigenschaften verbessert und die Viskosität reduziert werden, während die Beschichtungsverarbeitbarkeit durch Mischen mit verschiedenen reaktiven Verdünnern gefördert wurde. Die hervorragenden Hafteigenschaften auf Glasplatten wurden der ähnlichen Struktur zwischen den PDMS Weichsegmenten und Glas zugeschrieben, was eine breite Anwendung in der Beschichtungsindustrie erschließt.
    Notes: A new type of a UV-curable polyurethane acrylate resin based on hydroxyterminated polydimethylsiloxane (PDMS) soft segments with molecular weight 1800 and 2,4-toluene diisocyanate (TDI)/2-hydroxyethyl methacrylate (HEMA) hard segments were synthesized. The reactivity of 2,4-TDI with the hydroxy groups of silanol and HEMA was discussed by means of IR measurements. The characteristic absorption peaks of the  - NCO groups of 2,4-TDI in the para- and ortho-position should decline with increasing the reaction time. The measurements of fundamental physical properties of this type of UV-curable materials had been widely studied in addition to the effects of using various reactive diluents and some pigments. This kind of resin with good optical, electrical insulating, and adhesive properties on various matrices, could be improved in chemical properties and reduced in viscosity while promoting the coating processability by mixing with various reactive diluents. The excellent adhesive properties on glass plates can be attributed to the similar structure between the PDMS soft segments and glass which makes the application in the coating industry possible.
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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
    Notes: A typical intumescent fire retardant additive for polypropylene, which is a mixture of ammonium polyphosphate and pentaerythritol, does not sensibly modify the photooxidative behaviour of unstabilized polypropylene whereas it modifies that of polypropylene stabilized with a substituted o-hydroxybenzophenone and a sterically hindered amine. The photostabilizing effectiveness of the amine is probably decreased owing to protonation by polyphosphoric acid. On the contrary, the photo-protection effectiveness of the o-hydroxybenzophenone is increased in the presence of the intumescent fire retardant. This might be due to a photoinhibition effect of pentaerythritol.
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  • 64
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Beginning with the current theories concerning the solid state structure of bisphenol-A-polycarbonate, the effect of chemical substitution of the bisphenol upon the thermal, mechanical, and dynamic mechanical properties will be discussed in detail. The observed mechanical properties of the various polycarbonates is considerably influenced by their chemical structure. Among all of the polycarbonates, bisphenol-A-polycarbonate is unique, particularly with respect to its low temperature properties. The ductile-to-brittle transition as a function of temperature correlates to the high temperature region of Gamma relaxation (G′′). Any theoretical approach to completely characterize and describe the experimentally observed phenomena must take into consideration as a fundamental parameter the conformational flexibility of the polycarbonate chain.
    Notes: Ausgehend von den bisher erarbeiteten Vorstellungen über die Festkörperstruktur des Bisphenol-A-Polycarbonats wird die Auswirkung einer chemischen Substitution des Bisphenols auf die thermischen, mechanischen und mechanisch-dynamischen Eigenschaften diskutiert. Innerhalb der Substanzklasse der Polycarbonate zeigt sich dabei hinsichtlich der beobachteten mechanischen Phänomene ein erheblicher Einfluß der chemischen Struktur. Vor allen Polycarbonaten ist das Bisphenol-A-Polycarbonat besonders hinsichtlich seiner Tieftemperatur-Eigenschaften ausgezeichnet. Der Spröd/Zäh-Übergang als Funktion der Temperatur korreliert mit der Hochtemperaturflanke des mechanischen Nebenrelaxationsgebietes. Eine die experimentell beobachteten Phänomene vollständig charakterisierende Theorie muß als wesentlichen Parameter die konformative Beweglichkeit der Polycarbonat-Ketten berücksichtigen.
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  • 65
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Mischungen von Elastomeren wie Naturkautschuk und Styrol-Butadien-Kautschuk werden bei verschiedenen Temperaturen vulkanisiert und die Behandlungscharakteristika und Vulkanisateigenschaften verglichen. Die optimale Behandlungszeit bei einer bestimmten Vulkanisationstemperatur konnte empirisch durch eine Exponentialbeziehung dieser Temperatur ausgedrückt werden. Die Vernetzungsdichte der Vulkanisate nimmt mit steigender Vulkanisationstemperatur ab. Für eine vorgegebene Mischung gibt es eine bestimmte Vulkanisationstemperatur, bei der die Materialien die besten Eigenschaften für spezifische Anwendungen besitzen.
    Notes: Gum compounds of natural rubber (NR) and styrene-butadiene rubber (SBR) are vulcanized at different temperatures and the cure characteristics and vulcanizate properties are compared. The optimum cure time at a particular vulcanization temperature could be expressed empirically in terms of that temperature using an exponential relation. The crosslink density of the vulcanizates is found to decrease with an increase in the vulcanization temperature. For a given compound there is a particular vulcanization temperature which gives the best compromise of properties for specific applications.
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  • 66
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Thermisch polymerisierte Proben von linearen Additionspolymeren des Bisphenol-A-Diglycidylethers (DGEBA) mit den drei unterschiedlichen Aminen, (A) Benzylamin (BA), p-Chloranilin (PCA) und Cyclohexylamin (CHA), wurden mittels Gelpermeationschromatographie (GPC) unter Verwendung von THF als Elutionsmittel untersucht.Bei der Eichung des Systems und der Interpretation der Chromatogramme wurde der Solvatationseffekt der Hydroxylgruppen durch THF berücksichtigt. Der Vergleich der Chromatogramme weist darauf hin, daß das Polymere mit CHA schon im Bereich kleiner Molmassen (einschließlich der Dimeren) und in einem frühen Reaktionsstadium cyclisiert. Der Vergleich der mittleren Molmassen der Proben, die nach zwei unabhiingigen Methoden  -  Dampfdruckosmometrie (VPO) und GPC  -  gemessen wurden, zeigt, daß die Cyclisierung der Polymeren mit BA und PCA in einem geringeren Umfang stattfindet. Die beiden letztgenannten Polymeren neigen also weniger zur Cyclisierung.
    Notes: Thermally polymerized samples of linear addition polymers of bisphenol-A-diglycidyl ether (DGEBA) and the following three different amines (A): benzylamine (BA), p-chloroaniline (PCA), and cyclohexylamine (CHA) were chromatographed by gelpermeation chromatography (GPC) using THF as eluent. The solvation effect of hydroxyl groups by THF has been taken into consideration when calibrating the system and interpreting the chromatograms. The comparison of the chromatograms suggests that the polymer with CHA is cyclized already in the range of small molecular masses (including dimers) and in an early stage of reaction. The comparison of average molecular masses of the samples as measured with independent methods - vapour pressure osmometry (VPO) and GPC - shows that the cyclization of the polymers with BA and PCA takes place to a lower extent, the latter polymer being less capable of cyclization.
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  • 67
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Graft copolymers P(E-g-MMA) were prepared by ozonisation of low density polyethylene (LDPE) and grafting of methyl methacrylate (MMA) in bulk onto the peroxides and hydroperoxides thus obtained (Mn graft PMMA = 7700 and 21400). The emulsifying effect of P(E-g-MMA) copolymers on PE-PVC mixtures was examined. With added quantities of 5.0% copolymers the braking strength value σB for the mixture PE-PVC 50-50 is varying between 0.60 to 1.10 kg/mm2; the variation of the elongation at break point εB is more difficult to explain. The alloy fractographs were also examined under the scanning electron microscope. We observed PE modules of 20 to 30 in average diameter, without copolymer, and 1 to 2 after adding 5% of copolymers. This underlines the emulsifying role played by the copolymer. These results are compared with those of other teams. The P(E-g-MMA) that we prepared, can be considered as a suitable emulsifier for LDPE-PVC mixtures and presents the advantage of being more accessible for industrial synthesis of new alloys PE-PVC.
    Notes: Les copolymères greffés P(E-g-MMA) sont préparés par réaction du méthacrylate de méthyle (MMA) en masse sur le polyéthylène basse densité ozonisé. La masse moyenne des greffons de PMMA variable suivant la température et le temps de réaction est de 7700 et 21400. Ces copolymères sont testés comme émulsifiants de mélanges de PE et de PVC dont les propriétés mécaniques, la contrainte à la rupture σR, l'allongement à la rupture εR% et le module d'élasticité E sont mesurées avant et après l'addition de 5% en poids de copolymère. Pour le mélange PE-PVC 50-50 σR passe de 0,60 à 1,10 kg/mm2, la variation de εR est plus complexe. La visualisation, au microscope électronique à balayage, des fractographies de ces divers mélanges, montre une diminution d'au moins un facteur 10 de la taille des phases après addition de copolymère et confirme bien le rôle d'émulsifiant d'émulsifiant de ceux-ci permettant d'obtenir ainsi de nouveaux alliages PE-PVC dont les propriétés sont comparées avec celles d'alliages préparés par d'autres auteurs avec d'autres émulsifiants.
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  • 68
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    Angewandte Makromolekulare Chemie 162 (1988), S. 163-173 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In dieser Arbeit wird die Effizienz einer neuen modifizierten Säulenfraktionierungsmethode durch Vergleich von theoretischen Modellen und experimentell erhaltenen Molmassenverteilungen vorgestellt. Fünf theoretische Funktionen wurden zur Anpassung der experimentellen Daten benutzt: die Log-normal-, Tung-, Schulz-, Polynomial- und Flory-Verteilungsfunktion. Die Kurvenanpassung wurde durch die mittlere quadratische Abweichung abgeschätzt. Die mittlere quadratische Abweichung war in allen theoretischen Modellen von der gleichen Größenordnung. Mit der Polynomial- und Flory-Funktion wurden die kleinsten Werte für die mittlere quadratische Abweichung und somit die beste Anpassung der aus der Gelpermeationschromatographie erhaltenen Verteilungskurven erreicht. Diese Kurven geben die wahre Verteilung der benutzten Polymeren wieder. Diese theoretischen Modelle dienten auch als Referenzverteilungsfunktionen. Die experimentell mit zwei verschiedenen LCIsungsmittelpaaren bestimmten Fraktionswerte wurden dann den ausgewlhlten Referenzmodellen angepdt. Die Fraktionswerte der beiden benutzten Lösungsmittelpaare stimmten gut mit dem Polynomial- und Flory-Modell überein. Dies bestätigt die hohe Effizienz der vorgeschlagenen Fraktionierungsmethode.
    Notes: In this paper the efficiency of a new modified column fractionation method was presented through the comparison of theoretical models and experimentally obtained molecular mass distribution. Five theoretical functions were used for fitting the experimental data: log-normal, Tung, Schulz, polynomial, and Flory distribution function. The curve fittings were estimated by the mean square deviation. The mean square deviations in all the theoretical models were of the same order. The least values of mean square deviation and consequentely the best fitting of the gel permeation chromatography (GPC) distribution curve, which deals as a true distribution of the applied polymer sample, were achieved with polynomial and Flory model. These theoretical models were further chosen as a reference distribution function. The experimental fractionation data in two quite different solvent pairs were afterwards fitted to the chosen referent models. Fractionation data of the both applied solvent pairs have been in close agreement with Flory and polynomial model. This confirms the high efficiency of the proposed fractionation method.
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  • 69
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    Angewandte Makromolekulare Chemie 163 (1988), 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: Die Chlorierung von ataktischem Polypropylen (APP) wurde thermisch gestartet und in Tetrachlorkohlenstoff durchgeführt. Es wurde gefunden, daß mit zunehmender Verdünnung der Chlorierungsgrad steigt, was in % Gewichtszunahme gemessen wurde. Grund für dieses Verhalten ist eine größere Aufweitung und Beweglichkeit der APP-Ketten, wodurch die durch Chlor zu ersetzenden Stellen besser zugänglich werden. Die Reaktionsordnung in Abhängigkeit von der APP-Konzentration beträgt 0,84 und die Aktivierungsenergie (Er) 5,29 kcal/mol. Die Erhöhung der Strömungsrate führt zu einem höheren Chlorierungsgrad. Dieser steigt bis zu einer Strömungsrate von 1 l/h linear an, um dann ein konstantes Nivoau anzustreben. IR-Spektroskopie und 13C-NMR-Untersuchungen weisen darauf hin, daß die Chlorierung an allen drei ersetzbaren H-Atomtypen vorkommt. Der Startschritt des Mechanismus ist wahrscheinlich die Substitution des tertiären H-Atoms durch freie Chlorradikale und nachfolgendem Austausch der sekundären und primären H-Atome durch entweder fortschreitende Substitution oder den Eliminierungs-Additions-Mechanismus.
    Notes: Chlorination of atactic polypropylene (APP) was thermally initiated and carried out in carbon tetrachloride (CCl4) solution. It was found that with the increase in dilution, there is an increase in the extent of chlorination, as measured in terms of % weight-gain. The reason for this behaviour has been ascribed to a greater degree of opening up and mobility of APP chains thus increasing the accessibility of the replaceable sites to chlorine. The order of the reaction with respect to APP concentration was found to be 0.84, the overall activation energy (Er) being 5.29 kcal/mol. Increase in flow rate leads to an increase in the extent of chlorination and was found to be increasing linearly with a flow rate up to 1 l/h beyond which it levels off. IR spectroscopy and 13C-NMR studies indicate the chlorination occurring in all the three types of replaceable H-atoms in APP. The mechanism appears to be initial substitution of tertiary H-atom by free chlorine radical followed subsequently by replacement of secondary and primary H-atoms via either progressive substitution or elimination-addition mechanism.
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  • 70
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    Die Makromolekulare Chemie 189 (1988), S. 1-7 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An alternative method for the preparation of the cyclic dimer 3 of 2-pyrrolidone is presented, which is based on hydrolysis of 1-(1-pyrrolin-2-yl)-2-pyrrolidone (4, x = y = 3), and some physicochemical properties of 4 and its hydrolytical products are discussed.
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  • 71
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    Die Makromolekulare Chemie 189 (1988), S. 45-51 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new catalytic complex was developed by reacting 1,1-diphenylethylene with metallic calcium and submitting the resulting derivative [designated as (Ar)2Ca] to chemical modifications with 1-chloro-2,3-epoxypropane (epichlorohydrin; ECh). From these reactions a series of (Ar)2Ca · x ECh catalysts resulted differing by the mole ratio ECh/Ca. A value of 0,7 was found to be the optimal one with regard to the catalytic efficiency of polymerizing epichlorohydrin. The poly(epichlorohydrin)s (PECh), obtained with yields of 46, 5 to 82, 4%, are distinguished by their chlorine content and cover a range of molar masses from 0,35 · 105 to 2,23 · 105 g/mol. The catalysts were characterized by elemental analyses and thermogravimetry. According to X-ray patterns, PECh obtained by means of (Ar)2Ca · 0,7 ECh as catalyst displayes no crystallinity like PECh prepared in the presence of appropriate aluminium systems.
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  • 72
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    Die Makromolekulare Chemie 189 (1988), S. 53-65 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The free-radical terpolymerization of maleic anhydride, styrene, and acrylic monomers such as acrylonitrile, methyl acrylate and methyl methacrylate was studied. The alternating copolymerization of maleic anhydride with styrene was found to be favored in those systems. Contrary to theoretical predictions, maleic anhydride is more reactive than styrene in ternary systems. The relative reactivity of the acrylic monomers studied was found to decrease in the order: methyl methacrylate ≥ methyl acrylate 〉 acrylonitrile. In the presence of a Lewis acid, such as ZnCl2 or C2H5AlCl2, the relative reactivity of acrylic monomers increases and at the respective complexing agent concentration the copropagation of the acrylic monomer with styrene can dominate. On the basis of the results obtained, some aspects of the mechanism of alternating propagation in systems comprising an electron-donor monomer and two electron-acceptor monomers are discussed.
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  • 73
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    Die Makromolekulare Chemie 189 (1988), S. 103-110 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coupling reaction of ampicillin with the polysaccharide xanthane in DMSO, using dicyclohexylcarbodiimide as activator, was studied. To find the conditions for maximum yield a regression equation was established, describing the dependence of the yield of coupling product on the reaction parameters (drug/support mole ratio, activator/support mole ratio and duration), starting from an experimental, centrated rotable complex, second order program. The coupling product was spectroscopically characterized and the in vitro release rate of ampicillin in a weakly basic medium was established along with the determination of its antimicrobiological activity.
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  • 74
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reactions of diisocyanatodiketenes, 3-(ω-isocyanatoalkyl)-4-(ω-isocyanatoalkylidene)-2-oxetanones (3a-c), with oligomeric diols (4 or 5) as well as 1,4-butanediol afforded linear polyurethanes containing reactive diketene moieties. From these poly(diketene-urethane)s polymeranalogues products were prepared by reaction with ethanol, ammonia, water or acetic acid. The resulting polyurethanes containing ß-ketoester, ß-ketoamide or keton moieties were characterized by IR spectroscopy, viscosimetry, differential scanning calorimetry and size exclusion chromatography. The properties of the products based on diols 4 or 5 are mainly determined by the oligomeric diols, whereas the (modified) diisocyanate part has a great influence e.g. on the thermal behaviour of the polyurethanes.
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  • 75
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel synthetic route to (2E,4E)-6-amino-2,4-hexadienoic acid (1) and related ω-aminodiene compounds is reported. These substances form layer perovskites, CdCl4(NH3 - R)2, that furnish stereoregular 1,4-polybutadienes upon γ-irradiation in a topochemical solid state reaction. The synthesis of a chiral derivative is also described, that can be crystallized in a perovskite structure and polymerized by γ-rays. An ambivalent solid state reactivity is observed for the hydrochloride of 1: γ-rays induce a chain reaction leading to a polymer of identical chemical structure and stereochemistry as reported for the perovskite, but with higher molecular weight. Upon UV-irradiation, however, the hydrochloride undergoes a stereoselective (2+2)-cycloaddition to a cyclobutanoic dimer as main product and oligomers after prolonged irradiation. In the case of γ-irradiation at 273 or 300K significant contributions from postpolymerization are found both for the hydrochloride and the perovskite of 1.
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  • 76
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Temperature depenences of the pitch of cholesteric helix in solutions of poly(y-benzyl-L-glutamate) in N,N-dimethylformamide and N-methyl-2-pyrrolidone were measured for various molar masses of poly(γ-benzyl-L-glutamate). It was found that in N-methyl-2-pyrrolidone inversion of the cholesteric helix takes place, i. e., that the right-handed helix changes to the lefthanded one. By using an equation derived by Kimura, the temperatures at which the system has a nematic order were determined. The results obtained allow the statement that an important role in the inversion of the cholesteric helix in poly(γ-benzyl-L-glutamate) solutions is played by conformational changes in side chains of the polypeptide molecule.
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  • 77
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to calculate the interference effects from liquid-crystalline block copolymers, Biswas and Blackwell have presented an elegant matrix method. For the cases where an analogous, analytical approach can be made, we show that the matrix method leads to the same result as the analytical method. In addition to the conventional reciprocal lattice with reciprocal lattice points at h2π/〈c〉, where 〈c〉 is the average periodicity, one has to consider three further reciprocal lattices with reciprocal lattice points h′2π/cA, h″2π/cB, and h″′2π/(cB + cB). cB and cB are the lengths of the comonomer units. This method will be illustrated by model calculations for p-benzoate/biphenyl-4,4′-diylisophthalate copolyestersPoly[(isophthalic acid-alt-biphenyl-4,4′-diol)-co-4-hydroxybenzoic acid].. Further, interesting possibilities of the matrix method will not be treated here.
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  • 78
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    Die Makromolekulare Chemie 189 (1988), S. 251-261 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Total solvent sorption and preferential adsorption by networks of poly(methylphenylsiloxane) (PMPS) and of poly(dimethylsiloxane) (PDMS) were determined in the mixture chloroform/diethyl ether. This liquid mixture has a negative GE. The swelling degree of the networks was found to vary linearly with mixed solvent composition (Cl3CH volume fraction φ), contrary to what is expected in view of GE 〈 0. The preferential adsorption by PDMS shows an inversion which is of the divergent type (preferential adsorption of the liquid in major proportion in the mixture). With PMPS no inversion was observed, Cl3CH is always preferentially adsorbed, but the trend is also divergent (with the inversion point displaced to φCl3CH = 0). The unexpected behaviour of the swelling degree and the displacement of the inversion in preferential adsorption are attributed to strong attractive interactions of the siloxane backbone with the two solvents, and of phenyl groups (in PMPS) with Cl3CH. The intrinsic viscosity of linear PMPS at infinite dilution was determined in the same mixed solvent, in order to check the possible influence of the polymer concentration. Comparison with network swelling shows a similar behaviour.
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  • 79
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: δ Valerolactone and ∊-caprolactone were reacted with BBr3, AIBr3, TiBr4, SnBr4 or Bu2SnBr2 in dichloromethane or chloroform in a 1 : 1 mole ratio. When these exothermic reactions were conducted with cooling, complexation of the lactones at the exocyclic oxygen was detectable by means of IR and 1H NMR spectroscopy as the first reaction step. However, heating to 60°C causes in all cases ring cleavage, and after hydrolytic removal of the metal bromides ω-bromocarboxylic acids or oligomers with ω-bromoalkanoyl end groups were obtained. SnBr4, Bu2SnBr2 and ZnBr2 proved to be good initiators of the polymerization of both lactones. At low monomer/initiator (M/I)-ratios (high initiator concentrations) most of the initiator remained unchanged, and the average degrees of polymerization of the resulting polylactones largely exceeded the value expected for the M/I-ratio. By means of viscosity and GPC measurements weight-average molecular weights up to 70 000 were found. All polylactones obtained by initiation with these three metal bromides contain ∊-bromoalkanoyl end groups. Furthermore, high-molecular-weight poly(∊-caprolactone) could be prepared at polymerization temperatures up to 150°C. The results do not indicate a cationic polymerization mechanism, but an insertion mechanism involving the metal-O bond formed after the first cleavage of the lactone rings.
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  • 80
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The emulsion copolymerization of acrylonitrile and butyl acrylate initiated by potassium peroxodisulfate (K2S2O8) in the presence of an anionic, cationic, or nonionic emulsifier has been kinetically investigated at 60°C under batch conditions by gas chromatography (GLC) and gravimetric methods. It is found convenient to define three stages of emulsion polymerization. In the range of low conversion (interval 1) are generated particles and the rate of polymerization increases with increasing polymer particle concentration. In interval 2 (ca. from 15 to 70% conversion) the number of polymer particles and the rate of polymerization (maximum) are constant. At very high conversion (above ca. 70% conversion) the monomer concentration within polymer particles decreases abruptly and the polymerization rate slows down (interval 3). The rate of polymerization in interval 2 was found to be proportional to the 0,41, 0,48, and -0,42 power of the emulsifier concentration for the anionic, nonionic, and cationic emulsifier, respectively. The dependence of the final particle number on the emulsifier concentration deviates from simple micellar theory predictions. The exponent of the emulsifier concentration decreases with increasing emulsifier concentration (for the anionic and nonionic emulsifiers). These results were explained by a coagulative nucleation mechanism. The unexpected polymerization behaviour in the presence of the cationic emulsifier was explained by the formation of a product (due to interaction of the initiator with the emulsifier).
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  • 81
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    Die Makromolekulare Chemie 189 (1988), S. 733-742 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cationic transannular oligomerization of cis-cis-1,5-cyclooctadiene (1), initiated by AlEtCl2 and Al2Et3Cl3, was studied. Several cationic catalysts were examined, and the order of activities of these catalysts was found to be the following one: BF3 · OEt2 〈 AlCl3 〈 AlEtCl2 〈 Al2Et3Cl3. The number-average molecular weights of the resultant polymers are ≈ 1000 - 2000, and the softening temperature ranges 130 - 160°C. By means of NMR, IR and PC-MS spectral analyses, the structure of poly(1,5-cyclooctadiene), proposed earlier by Marvel et al., could be corroborated.
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  • 82
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    Die Makromolekulare Chemie 189 (1988), S. 755-760 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A lecithin-type macromonomer 1 was synthesized from natural egg phosphatidylcholine (lecithin). The macromonomer has an olefinic polymerizable group at the hydrophilic site, and is characterized by its chemical structure resembling lecithin. It could be polymerized in a liposome system by UV irradiation, giving polymers with a maximum molecular weight of 98 000. Polymers with molecular weights above 48 000 form thin and flexible membranes with a few 10 μm in thickness. The polymers can also be redispersed in water and the liposomes can be reconstituted.
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  • 83
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    Die Makromolekulare Chemie 189 (1988), S. 761-764 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A thin film (thickness: 200 nm) of metal-free polyphthalocyanine, which is insoluble in organic solvents, was prepared by an evaporation-polymerization process under mild conditions developed by us. The thin film is not only though, but it also resists chemicals and heat. Its conductivity is 1,1 · 10-4 S · cm-1, and it increases to 0,15 S · cm-1 on I2-doping.
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    Die Makromolekulare Chemie 189 (1988), S. 791-796 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crosslinkable and crosslinked liquid-crystalline polymers with elastic properties were prepared from main-chain and combined main-chain/side-group polymers. These polymers exhibit nematic, smectic A, and smectic C phases. Polymers of these types with azoxybenzene as mesogen do not crystallize upon cooling. As a consequence, the liquid-crystalline phases are frozen in glassy around room temperature.
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    Die Makromolekulare Chemie 189 (1988), S. 797-804 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Combined liquid-crystalline polymers containing azobenzene and azoxybenzene as the mesogenic groups and 2-octanol as the chiral end-group were synthesized and characterized. These polymers exhibit cholesteric, smectic A, and chiral smectic C* phases with monolayer and doublelayer structures. The polymers with azoxy groups do not crystallize upon cooling. Therefore, some of the liquid-crystalline phases can be frozen in in the glassy state.
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  • 86
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    Die Makromolekulare Chemie 189 (1988), S. 805-813 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methylallyl ethers of 1,2:3,4-di-O-isopropylidene-D-galactopyranose and 1,2:3,4-di-O-cyclohexylidene-D-galactopyranose were synthesized as new monomers containing saccharide moieties and copolymerized with maleic anhydride. The hitherto unknown 6-O-(2-alkoxycarbonylallyl)-1,2:3,4-di-O-isopropylidene-D-galactopyranoses (8a and 8b; alkyl: methyl and ethyl, respectively) were prepared and polymerized under free radical conditions. The substances were characterized by 13C NMR, elemental analyses and molecular weight determinations. Water solubility of these polymers was obtained by removing the isopropylidene protecting groups. The inherent viscosities of these polymers, measured in 0,1 M Na2SO4 aqueous solution, were of the same order of magnitude as those of polyacrylamides of the corresponding degrees of polymerization.
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  • 87
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    Die Makromolekulare Chemie 189 (1988), S. 823-832 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gordon and Temple's scheme of rate equations for ring-chain competition reactions in condensation polymerization has been solved analytically (for very small rates of ring formation) and numerically over a wide range of conditions. The numerical method was computationally efficient. Except in extreme cases, the distribution of ring sizes was found to be practically the same as that predicted for equilibrium conditions by Jacobson and Stockmayer, viz. that the number concentration of rings with a degree of polymerization i is proportional to i-5/2 at the end of the reaction.
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  • 88
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    Die Makromolekulare Chemie 189 (1988), S. 815-821 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Preliminary results regarding the physical behaviour of a stereoblock-isotactic polypropylene are reported. The polymer was obtained using a soluble Ziegler-Natta catalyst and films were prepared by pressure molding. The particular steric configuration is responsible of low crystallinity and small crystal size; the bulk structure can be represented by a fringed micellar model in which small crystallites act as physical crosslinks. The observed behaviour being typical of a thermoplastic elastomer well agrees with the suggested model.
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  • 89
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    Die Makromolekulare Chemie 189 (1988), S. 833-843 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cellulose nitrates with nitrogen contents in the range 11,2 to 13,3 mol-% are characterized with gel permeation chromatography (GPC) using various detectors, membrane osmometry, static low angle laser light scattering (LALLS) and solution viscosity measurements. The molecular weight data from GPC-LALLS are generally in good agreement with those obtained by static LALLS and membrane osmometry. GPC-infrared is used to analyze the nitrogen content. These techniques are also used to characterize cellulose nitrate in propellants. A comparison between two different column packings in GPC-LALLS analysis is integrated into this study.
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  • 90
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    Die Makromolekulare Chemie 189 (1988), S. 911-925 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melting, crystallization, and solution behavior of n-alkanes with fluorocarbon segments of twelve carbon atoms on one end, F(CF2)12(CH2)nH, or on both ends, F(CF2)12(CH2)n(CF2)12F were investigated by DSC, MAS 13C NMR, light scattering, and birefringence studies. Both triblock F(CF2)m(CH2)n(CF2)mF and diblock F(CF2)12(CH2)nH compounds with 4 ≦ n ≦ 14 melt by a two-step process. In the first step, the alkyl segment conformations gain nearly liquid like trans/ gauche ratios, while the perfluorinated segments remain ordered. “Gels” which incorporate the entire solvent are formed by crystallization from even dilute solutions of hydrocarbon and fluorocarbon solvents. The gels are built up of extremely long, interdigitated needles of the pure solute. Due to the bilayer structures and different degrees of ordering of the hydrocarbon and the fluorocarbon segments, the crystals grow preferentially in the direction parallel to the lamellar surface. Light scattering experiments in octane demonstrated the formation of micelle type associates.
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  • 91
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    Die Makromolekulare Chemie 189 (1988), S. 927-937 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the electric birefringence of aqueous polyelectrolyte solutions in the very dilute regime ( ≈ 10-5 g · mL-1) reveal that the macroions are fully extended. However, this rod-like conformation is easily altered towards a more coiled conformation when a strong static electric field is applied, particularly in the case of very high molar-mass polymers. With the application of rectangular dc pulses, as ordinarily used in Kerr-effect measurements, the change of molecular shape interferes with the transient rise and decay of the birefringence signal, because the rotational mobility as well as the optical anisotropy of the macroions become time-dependent. As a result, the mean relaxation time for the rise curve is considerably smaller than that of the field-free decay, and the steady-state birefringence is much lower than expected for the unperturbed macroions. The change of the molecular shape can be avoided if the orientation of the macroions is induced by high-frequency ac pulses. This experimental technique is therefore suitable to obtain the unperturbed shape and size of the macroions. A molecular interpretation for the dependence of the birefringence function on the pattern of the electric field is proposed.
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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 Heck reaction allows the synthesis of monomers in a one-step reaction. Catalyzed by Pd, bromoarenes are reacted with ethylene to form substituted styrenes and symmetrical stilbenes. Unsymmetrical stilbenes are obtained from substituted bromoarenes and styrenes. Substituted hydroquinones and terephthalic acids are also available in high yields. Poly(1,4-phenylenevinylene) is obtained starting from 4-bromostyrene.
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  • 93
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    Die Makromolekulare Chemie 189 (1988), S. 153-162 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The 1H NMR parameters (chemical shift and coupling constant) of ß(1→4)-linked polysaccharides xylan, cellulose, and chitin are compared in solutions of aprotic solvents. The following NMR parameters are analyzed: (1) Chemical shifts of labile protons, (2) their variation with temperature, (3) coupling constants through the H—C—O—H moiety  -  for monomers, dimers, and the corresponding polymers. It is observed that the OH-3 hydroxyl group for cellulose and chitin oligomers and polymers present a particular behaviour, which is in agreement with the existence of an intramolecular hydrogen bond between this hydroxyl of one monomeric unit, and the heterocyclic oxygen atom of the adjacent monomeric unit. This kind of intramolecular hydrogen bond is not observed in case of the xylan series. It can be concluded that substitution of an equatorial hydrogen atom at the C-5 position of the sugar ring by a CH2OH group  -  when passing from xylan to cellulose and chitin  -  induces a rotation restriction around the glycosidic bond. This places the OH-3 hydroxyl group in a favourable position to be hydrogen-bonded. The consequent implication on the respective conformations of the chains in solution is discussed.
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    Die Makromolekulare Chemie 189 (1988), S. 195-200 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscosity-average relative molecular masses have been determined for a series of chitosans having the same relative molecular mass and relative molecular mass distribution but differing extents of N-acetylation. The results obtained show that the same viscometric constants in the Mark-Houwink equation [η] = Km ·Ma are applicable to chitosans over the range between 0 and 40% N-acetylation Comparison of literature values for number- and weight-avepge rela-tive molecular masses Mn, and Mw, with the viscosity-average relative molecular mass M, values calculated using the related viscosity data and each of the three sets of viscometric constants that have been proposed for chitosan, confirms that the most accurate values currently available are km = 1,81 · cm-3 · 10-1 and a = 0,93, using 0,l M acetic acid/0,2M NaCl as solvent.
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  • 95
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    Die Makromolekulare Chemie 189 (1988), S. 221-226 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Colloidal particles of three-block copolymers polycaprolactam-block-polystyrene-block-polycaprolactam, formed in a solvent mixture toluene/2,2,3,3-tetrafluoropropanol as a good solvent of polycaprolactam, were studied by static and dynamic light scattering and transmission electron microscopy. Two kinds of spherical multimolecular particles differing in size were found in the solution. The smaller particles containing tens of copolymer molecules were interpreted as regular copolymer micelles, and the larger particles formed from thousands of copolymer molecules were interpreted as associates of these micelles.
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  • 96
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric and viscometric behaviour of poly(dibenzyl itaconate) (1) in 1,4-dioxane is studied as a function of temperature. The dipole moments at 25°C and at 33°C are determined by measuring the dielectric constant as a function of polymer concentration at fixed temperature. Also, the variation of the dielectric constant for a fixed concentration is determined at several temperatures in the temperature range between 15 and 39°C. The dipole moment is by 10% higher at 33°C than at 25°C, and the variation of the dielectric constant with temperature shows a stepwise increase between 25°C and 30°C. Viscosity measurements demonstrate an anomalous behaviour of 1 in 1, 4-dioxane at approximately the same range of temperatures. At ca. 25°C the value of the Huggins constant drops to practically zero. By measuring samples with different molecular weights the unperturbed dimensions, interaction parameter, and Mark-Houwink-Kuhn-Sakurada exponent are obtained. All of these parameters exhibit a discontinuity at ca. 25°C. The variations in the dielectric and viscometric behaviour with temperature are attributed to a conformational change of the macromolecules of 1 in 1, 4-dioxane.
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  • 97
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    Die Makromolekulare Chemie 189 (1988), S. 293-298 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Unliving chains of aliphatic polyester were transformed into dicationically living poly(THF)-block-polyester-block-poly(THF) chains, and four different telechelic triblock co-oligomers with primary, secondary, tertiary amine, and hydroxyl end-groups were synthesized. A novel approach to the exchange of hydroxyl or carbonyl ends of polyester for amino end-groups is described. The primary amine-terminated telechelic triblock was used to modify an epoxy resin to give a toughened product with high strength.
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  • 98
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    Die Makromolekulare Chemie 189 (1988), S. 299-315 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Negatively charged lipid molecules were converted into polymerizable lipids by introduction of polymerizable mono- or bifunctional counterions. As an attempt to mimic the cytoskeleton of biomembranes, unsymmetrical polymeric vesicles were prepared, where the polyelectrolyte is attached either only to the inner or to the outer bilayer surfaces. Polymerizable cations were introduced to the outer surface of preformed small unilamellar vesicles via ion-exchange. The outer counterions of vesicles bearing polymerizable counterions at both sides of the membrane were replaced by Na+. Polymerization of these systems leads to unsymmetrical vesicles. The introduction, separation and polymerization of the organic counterions was monitored by UV-spectroscopy. Due to polymerization of the counterions, the phase transition temperature of the membranes is shifted remarkably to higher temperatures. For a comparison of ionically attached and covalently bound polymers, two cationic lipids were synthesized, which have a bifunctional polymerizable headgroup. In contrast to the lipids with “ionic” spacers, the polymerization of the covalently bound methacrylic units resulted in a decrease of the phase transition temperature. Thus, by application of ionically bound polymerizable units, unsymmetrical polymerized vesicle membranes are readily available. These systems may serve as models for mimicking the cytoskeleton of living cells.
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  • 99
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The factors relating to measuring the position of the methyl deformation mode at about 1378 cm-1 with sufficient precision to permit its use for the identification of the different branches present in the various types of “linear” low density polyethylene(as manufactured by the copolymerization of ethylene and a 1-alkene) have been examined systematically. With a data density of eight points per wavenumber, and the well established subtraction procedure with polymethylene or with a near-linear polyethylene to remove the overlapping methylene deformation band, it is possible to achieve a precision of ±0,15 cm-1. This is ample to distinguish between methyl, ethyl, and butyl or hexyl branches, but not to characterise uniquely these last two. The use of Fourier self-deconvolution to separate the methyl band has also proved very effective. The precision obtainable when these methods are applied to spectra measured with one data point per wavenumber is somewhat lower, but is still adequate for characterisational purposes. The results for a series of polymers containing ethyl branches at various concentrations suggest a small difference for the peak position for branches present in crystalline and amorphous regions.
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  • 100
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    Die Makromolekulare Chemie 189 (1988), S. 351-360 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrisic viscosity [η] of poly(vinyl alcohol) (PVA) was determined in aqueous solutions with various concentrations cb of borax (Na2B4O7) as functions of molecular weight M and concentration cs of NaCl as an added salt. Polyelectrolyte viscosity behaviour was observed for the systems containing both borax and NaCl, due to the complexation with negatively charged borate ions B(OH)-4 · [η] changes depending on the ionic strength I. It was found that the Stock-mayer-Fixman treatment for the molecular-weight dependence of [η] is valid in the lower molecular-weight range (M 〈 105), even though the present PVA chain contains some intrachain crosslinks. Theta conditions can be attained at an appropriate concentration cs Θ of NaCl. The value of cs Θ is dependent on cb, but the conformational parameter from the Stockmayer-Fixman treatment K0 is almost independent of cb. The effect of intrachain crosslinks becomes evident only as a considerably large negative value for the excluded volume parameter B at infinite ionic strength. In addition, the electrostatic part of the expansion factor α3e was found to be linearly correlated to a reduced parameter (M/I)1/2 for all cb systems, from the slope of which the charge density was estimated.
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