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  • Wiley-Blackwell  (25,656)
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  • 1995-1999  (16,247)
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  • 1
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    Electronic Resource
    A contribution to the UV degradation of polyurethanesPaper presented at the 18th Colloquium of Danubian Countries for “Natural and artificial ageing of plastics” in Villach June 24-26, 1987. (Austria) (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 247-263 
    Details
    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.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051580114
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  • 2
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    Beurteilung von hals-verbindungenVortrag anlä-sslich des 18. Donäulandergesprächs über “Natürliche und künstliche Alterung von Kunststoffen” in Villach (Österreich), vom 24. bis 26. Juni 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 283-300 
    Details
    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.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051580116
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  • 3
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    Simulation des natürlichen hagelschlags an transparenten kunststoffplattenVortrag anläßlich des 18. Donäulandergesprächs über “Nattürliche und künstliche Alterung von Kunststoffen” in Villach (Österreich) vom 24. bis 26. Juni 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 301-311 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051580117
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  • 4
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    Electronic Resource
    Specimen temperature as a constant marginal condition and as a variable test parameter during accelerated weatheringVortrag anläßlich des 18. Donauländergesprächs über “Natürliche und künstliche Alterung von Kunststoffen” in Villach (Österreich) vom 24.-26. Juni 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 313-320 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051580118
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  • 5
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    Some special aspects of thermal ageing of isotactic polypropylene (measuring method: Isothermal long-term DTA)Vortrag anläßlich des 18. Donauländergesprächs über “Natürliche und künstliche Alterung von Kunststoffen” in Villach (Österreich) vom 24.-26. Juni 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 321-334 
    Details
    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.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051580119
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  • 6
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    Coupling particle size distribution technique. A new ultracentrifuge technique for determination of the particle size distribution of extremely broad distributed dispersionsDedicated to Prof. Dr. H.-J. Cantow on the occasion of his 65th birthday (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 35-52 
    Details
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051620103
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  • 7
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    Graft copolymerization of methyl methacrylate on poly(vinyl chloride) (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 135-148 
    Details
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051620109
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  • 8
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    Electronic Resource
    Surface sulphonated highly crosslinked styrene-divinylbenzene copolymers (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 162 (1988), S. 193-201 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051620113
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  • 9
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    Studies on the enhancement of separation characteristics of sulfonated poly(phenylene oxide)/polysulfone thin film composite membranes for reverse osmosis applications. I. Effect of chemical treatment (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 1-13 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051630101
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  • 10
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    Studies on the enhancement of separation characteristics of sulfonated poly(phenylene oxide)/polysulfone thin film composite membranes for reverse osmosis applications. II. Effects of nitromethane and the chemical treatment combined with gamma-ray irradiationPart I cf. lit.3. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 15-21 
    Details
    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.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051630102
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  • 11
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    Effect of blending techniques on the curing of elastomer blends (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 37-45 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051630104
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  • 12
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    Modification of starch by graft copolymerisation with methyl methacrylatePresented at 12th National Conference of the Chemical Society of Nigeria, Calabar, Nigeria, Sept. 23-25, 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 93-99 
    Details
    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.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051630108
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  • 13
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    Adsorption of phenols on carbonaceous adsorbents produced from phenol-formaldehyde-resin mixed with olive stones (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 47-61 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051630105
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  • 14
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    Nonlinear programming methods to determine surface free energy components of polymers using harmonic mean approximation (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 101-114 
    Details
    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.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051630109
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    Gemeinsame kondensation von bisphenol A, melamin und formaldehyd (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 169-193 
    Details
    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.
    Additional Material: 13 Ill.
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  • 16
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    Preparation of cyclodextrin membrane-modified electrodes as sensor materials (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 205-207 
    Details
    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.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051630118
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    Antioxidants and stabilizers, 107Part 106 cf. Polym. Degr. Stabil. 17 (1987) 287.. Reaction of N-phenyl-1,4-benzoquinoneimine with the 1-cyano-1-methylethyl-radical (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 91-104 
    Details
    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.
    Additional Material: 2 Tab.
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  • 18
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    Ozoninduzierter Abbau von Polyoxymethylen (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 123-137 
    Details
    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.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051560111
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  • 19
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    On the structure of macroreticular styrene-divinylbenzene copolymers (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 105-121 
    Details
    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.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051560110
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    Heat stability of styrene-zinc acrylate copolymers (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 139-149 
    Details
    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.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051560112
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  • 21
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    Free radical grafting of some hydrophilic monomers onto unsaturated segmented polyurethanes  -  a kinetic study (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 151-162 
    Details
    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.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051560113
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  • 22
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    Highly dispersed Ni catalysts on carbon from thermal decomposition of cellulose-hydrous nickel gel membrane (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 156 (1988), S. 179-185 
    Details
    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.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051560115
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  • 23
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    Ageing of polyethylene filled with a mineral fillerPaper presented at the 18th Colloquium of Danubian Countries for “Natural and artificial ageing of plastics” in Villach (Austria) June 24-26, 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 351-362 
    Details
    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.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051580121
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  • 24
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    Influence of production parameters on ageing processes of thermoplasticsVortrag anläßlich des 18. Donauländergespächs über “Natürliche und künstliche Alterung von Kunststoffen” in Villach (Österreich) vom 24. bis 26. Juni 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 335-349 
    Details
    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.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051580120
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    Solvolytic degradation of aliphatic polyesteroligomers: Poly(tetramethylene adipate) diol (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 1-15 
    Details
    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.
    Additional Material: 11 Ill.
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    Carbon fibre reinforced bismaleimide composites, I (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 17-28 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 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.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600102
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    Structure and aging in the welded bonds of PP- homopolymer with PP- copolymer (PP-R)Vortrag anläßlich des 18. Donauländergesprächs über “Natürliche und künstliche Alterung von Kunststoffen” in Villach (Österreich) vom 24. bis 26. Juni 1987. (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 158 (1988), S. 363-378 
    Details
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051580122
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    Coordination polymers, 1. Magnetic, spectral, and thermal properties of coordination polymers derived from terephthalaldehyde bis(S-benzyldithiocarbazate) (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 67-81 
    Details
    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.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600105
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    Studies on the electrodeposition of polyimides (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 91-106 
    Details
    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.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600107
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    Model of double associates for sorption of binary gas mixtures on polymers (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 107-115 
    Details
    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.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600108
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    Einfluß der polymerisationsbedingungen auf die morphologie von schwefel-styrol-polymerisaten (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 131-140 
    Details
    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.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600110
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    Molecular weight distribution of living polymers in a semi-batch reactor (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 117-129 
    Details
    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.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600109
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    Thermosetting mechanism of polyethersulfone (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 141-154 
    Details
    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).
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600111
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    Synthesis and characterization of resins from 4-ethylphenol and cinnamaldehyde (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 155-162 
    Details
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051600112
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    Studies on electrical and paramagnetic properties of poly(phenylene sulphide) (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 163-173 
    Details
    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.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600113
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    Synthesis and study of the chelating properties of 3-carboxy-4-hydroxyacetophenone-formaldehyde resins (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 175-186 
    Details
    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.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600114
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    Nucleophilic addition to phenylisocyanates: A theoretical study (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 187-192 
    Details
    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.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051600115
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    Mitteilungen (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 160 (1988), S. 211-211 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1988.051600118
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    Modification of epoxy resins with acrylic rubbers containing a pendant epoxy group (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 63-76 
    Details
    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.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051630106
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    Polyurethane ionomers: Effects of emulsification on properties of toluene diisocyanate based polyether polyurethane cationomers (1988)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 163 (1988), S. 77-91 
    Details
    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.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1988.051630107
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    Optimization of mechanical strength of reinforced composites. 1. Study on the effect of reactive bismaleimide on the mechanical performance of CaCo3-filled polypropylene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 9-20 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von 3-Phenylenbismaleimid auf die Werkstoffeigenschaften von CaCO3 gefüllten Polypropylen-Verbundstoffen wurde untersucht. Die Verarbeitungstemperatur spielte eine entscheidende Rolle bei der Herstellung der Verbundwerkstoffe. Bei Verarbeitungstemperaturen oberhalb der Bismaleimid-Zersetzungstemperatur zeigte die Bismaleimid-Verbindung einen positiven Effekt. Die chemische Zusammensetzung der modifizierten Verbunde wurde mit den mechanischen Eigenschaften korreliert. Basierend auf ESCA-Analysen werden Wechselwirkungen zwischen dem Polymeren und CaCO, diskutiert.
    Notes: The effect of 3-phenylene bismaleimide on the mechanical performance of an inorganic filler-based polypropylene composite was studied. The selection of processing temperature played a significant role in the preparation of such composites. A positive effect of the bismaleimide compound was obtained for a processing temperature above the decomposition temperature of bismaleimide. The chemical composition of the modified composite was correlated to its mechanical strength by experimentation involving a rotatable design. An interaction between polymer and CaCO3 has been proposed based on ESCA analysis.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052240102
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    The effect of the processing steps on the oxidative stability of polyethylene tubing crosslinked by irradiation (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 33-48 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Chemische und mechanische Eigenschaften von Zwischenprodukten der PE-Schrumpfschlauch-Produktion wurden bei unterschiedlichen Compound-Zusammensetzungen (PE, ein aromatisches Amin oder Phenolderivat als Antioxidans und in einigen Fällen ein Flammschutzmittel und/oder eine Elastomerkomponente) untersucht.Während der Herstellung, besonders während der durch Elektronenstrahlung initiierten Vernetzung, nimmt die thermooxidative Stabilität des Materials gegenüber der des compoundierten Granulats ab. Das aromatische Amin scheint bei gleicher Zusammensetzung das wirksamere und strahlungsbeständigere Antioxidans im Vergleich zum Phenolderivat zu sein. Die Oxidationsstabilität der hergestellten Schrumpfschläuche wird nicht von der Qualität des eingesetzten PE-Ausgangsgranulats beeinflußt.Durch die Alterung des Materials ändern sich die mechanischen Eigenschaften geringfügig. Die Elastomerzugabe bewirkt keine Änderung von Zugfestigkeit und Reißdehnung. Die Stabilität des Endprodukts ist bei weitem ausreichend, um den Spannungen, die beim Schrumpfen während des Gebrauchs auftreten, standzuhalten. Die gute Zugfestigkeit des Materials wird durch die Alterung ebenfalls nicht beeinträchtigt.Bei der Extrusion des Granulats tritt keine nennenswerte Änderung des Molekulargewichts bzw. der Molekulargewichtsverteilung auf. Durch die Bestrahlung wird das Material vernetzt und zu mehr als 50% unlöslich, und seine thermooxidativen Eigenschaften ändern sich deutlich gegenüber dem ursprünglichen PE und dem daraus compoundierten Material.
    Notes: Some chemical and mechanical properties of intermediate products obtained in the production of PE heat-shrinkable tubes were studied at different compositions of the material containing PE, antioxidant (aromatic amime or phenol) and, in some cases, flame retardant and/or an elastomer.In the course of the production phase, the thermooxidative stability decreases compared to that of compounded granulate. The greatest decrease is caused by irradiation. The aromatic amine seems to be a more effective antioxidant at similar compositions than the phenol derivative, and it shows a better resistance against irradiation. The oxidative stability of the finished shrinkable tubes is not affected by the quality of commercial granulate (initial polyethylene).Mechanical properties change slightly upon ageing, and the introduction of the elastomer did not alter the tensile strength and elongation at break. The remaining stability of the end product was still high enough to bear the stress of shrinking in use, and the good tensile strength of the material did not decrease upon thermal ageing either.In the extrusion of the granulated compound no significant change in the distribution and average molecular weight took place. Irradiation produced more than 50% insoluble fraction and the thermooxidative properties of the crosslinked sample changed significantly compared to the original PE and to the compound prepared from it.
    Additional Material: 4 Ill.
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    Thermogravimetrie als brennbarkeitsbestimmungs-methode für lineare polyurethane (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 89-96 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In the present work oxygen index (OI) measurements and thermogravimetric analysis (TG) for a series of polyurethanes based on diols and isocyanate were conducted. It was found that a correlation exists between some of the thermal degradation parameters obtained from TG and OI-values. Analysis of experimental results confirms that the amount of mass loss at 250°C is directly proportional to the OI-value. It was also found that the logarithmic temperatures of maximal decomposition rates are directly proportional to the OI-values.
    Notes: In der vorliegenden Arbeit wurden für eine Serie von Polyurethanen auf der Basis von Diol und Isocyanat der Sauerstoffindex (SI) gemessen und die thermische Zersetzung mittels thermogravimetrischer Analyse (TG) untersucht. Dabei wurde ein Zusammenhang zwischen einigen Parametern der thermischen Zersetzung und den SI-Werten gefunden. Die Auswertung der experimentellen Ergebnisse zeigte, daß die Höhe des Massenverlustes bei 250°C und die SI-Werte direkt proportional zueinander sind. Derselbe Zusammenhang besteht auch zwischen dem Logarithmus der Temperatur bei der maximalen Zersetzungsgeschwindigkeit und den SI-Werten.
    Additional Material: 5 Ill.
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    Studies on thermal stability of modified polycarboxylate cements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 109-114 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(acrylsäre-co-acrylamid) wurde mit Zinkoxid und Kryolith (Na3AlF6) in unterschiedlichen Verhältnissen gemischt und bei Raumtemperatur zu Zahnzementen ausgehärtet. IPDT, Temperaturen bei maximaler Abbaugeschwindigkeit, Aktivierungsenergien und Frequenzfaktoren des thermischen Abbaus der Proben wurden aus thermogravimetrischen Messungen ermittelt. Die Probe mit 20 Gew.-% Kryolith in der Füllstoffmischung ist thermisch sehr stabil.
    Notes: Dental cement compositions made by mixing poly(acrylic acid-co-acrylamide) and mixtures of zinc oxide and cryolite (Na3AIF6) in various proportions of 10-50 wt.-% (w/w) were cured at room temperature. From thermogravimetric analyses of the samples, the integral procedural decomposition temperatures (IPDT), maximum decomposition temperatures, activation energies and frequency factors were evaluated. The cured cement sample containing 20 wt.-% cryolite in the filler mixture is thermally very stable.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052240111
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    Synthesis and characterization of water-soluble diazonium salts as contrast-enhancement materials (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 133-144 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die wasserlöslichen aromatischen Diazonium-Doppelsalze p-Diazodiphenylaminchlorid/Zinkchlorid (DZS-1) und p-Diazoanisolchlorid/Zinkchlorid (DZS-2) wurden auf ihre Verwendbarkeit als photobleichbare Farbstoffe in der Kontrastverstärkungslithographie untersucht. Nach Untersuchung der Bleicheigenschaften der hergestellten Salze wurde DZS-1 in wäßrigen Lösungen mit Poly(vinylalkohol) als Kontrastverstärkungssystem eingesetzt. Die thermische Stabilität, der Resistkontrast, die Bestrahlungsparameter und andere Bleicheigenschaften wurden untersucht. Im Vergleich zu einem handelsüblichen i-Linien-Photoresist beträgt das Kontrastverhältnis der DZS-1/PVA CEL-Schicht 1,67.
    Notes: Water soluble aromatic diazonium double salts, p-diazodiphenylamine chloride zinc chloride (DZS-1) and p-diazoanisol chloride zinc chloride (DZS-2), have been evaluated as photobleachable dyes for contrast enhancement lithography. After testing the bleaching characteristics, aqueous solutions of DZS-1 and poly(vinyl alcohol) were used as a contrast enhancement material. Thermal stability, resist contrast, exposure parameters and other bleaching characteristics of the photobleachable membranes were investigated. A. commercial i-line photoresist was used to evaluate the contrast ratio of the DZS-1/PVA CEL layer. The contrast ratio obtained in this investigation is 1.67.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052240114
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    Comparison of the coupling behaviour of diisocyanate and bisoxazolines in modification of liquid crystalline poly(ethylene terephthalate-co-oxybenzoate)s (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 167-178 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Methylen-4,4′-diphenyldiisocyanat und zwei unterschiedliche Bisoxazoline wurden für Kopplungsreaktionen in mit Carboxygruppen terminierten flüssigkristallinen Poly(ethylenterephthalat-co-oxybenzoat)en eingesetzt. Um definierte Bedingungen zu gewährleisten, erfolgte die Synthese von Copolyestern mit unterschiedlichen Carboxygruppenkonzentrationen. Die Bestimmung des Carboxygruppengehalts wird beschrieben.Es erfolgt ein Vergleich des Kopplungsverhaltens beider Arten von Kettenverlängerern. Es konnte nachgewiesen werde, daß die Bisoxazoline bedeutend schneller reagieren als das Diisocyanat. Durch einen geringen Überschuß and Bisoxazolin in der Reaktionsmischung konnte einer thermischen Schädigung vorgebeugt werden. Abhängig von der Menge an zugegebenem Koppler wurden bei den modifizierten Copolyestern Oxazolinendgruppen beobachtet. Außerdem werden mögliche Vernetzungsreaktionen und die thermische Stabilität diskutiert.
    Notes: Methylene-4,4′-diphenyldiisocyanate and two different bisoxazolines were used for coupling reactions in carboxy-terminated liquid crystalline poly(ethylene terephthalate-co-oxybenzoate). In order to guarantee defined conditions, copolyesters with different carboxylic group concentrations were synthesized. The determination of the carboxylic group content is described.The coupling behaviour of both types of chain extenders has been compared. It was evidenced that the bisoxazolines reacted significantly faster than the diisocyanate. A slight excess of bisoxazoline in the reaction mixture prevented thermomechanical degradation. Depending on the amount of coupling agent added, an oxazoline termination of the copolyester was observed. Additionally, probable crosslinking reactions and the thermal stability have been discussed.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052240117
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    Announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 224 (1995), S. 201-201 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052240120
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    Optimization of mechanical strength of reinforced composites. 2. Reactive bismaleimide-modified polypropylene composites filled with talc and zeolitePart 1 cf.2. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 11-20 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von 3-Phenylenbismaleimid auf die Werkstoffeigenschaften von mit Talkum und Zeolith gefüllten Polypropylen-Verbundstoffen wurde untersucht. Durch geeignete Planung des Aufbaus kann die Produkteigenschaft optimiert werden. Die Kapazität zur Füllstoffaufnahme schwankt bei Polypropylen je nach Art des Füllstoffs. Ein hochbelastbarer Verbundstoff kann aus einem geeignet modifizierten, mit Zeolith gefüllten Polypropylen hergestellt werden, auch wenn der Füllstoff in der Verbundmatrix dominiert. Als Ursache dieser Verstärkung wird eine verbesserte Wechselwirkung zwischen dem Polymeren und dem Füllstoff angenommen.
    Notes: The effect of 3-phenylene bismaleimide as a modifier for talc and zeolite-filled polypropylene composites has been studied. The usefulness of the experimental design to assure best product properties has also been illustrated. Polypropylene shows a variable degree of filling capacity depending on the type of filler. A high-strength composite can be prepared with suitably modified zeolite-filled polypropylene even if filler is the dominant phase in the composite matrix. An improved interfacial interaction between polypropylene and filler is proposed to be the reason for this improvement of strength.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052250102
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  • 49
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    Oligomerization of 1-decene with Ziegler-Natta catalysts (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 51-61 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die katalytische Oligomerisation von 1-Decen wurde mit Komplexverbindungen mehrerer Übergangsmetalle (Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V)) und Alkyl-aluminiumhalogeniden als Cokatalysatoren durchgeführt. Mit einem Chrom(III)-Et3Al2Cl3-Katalysatorsystem konnten Dimere (C20), Trimere (C30) und Tetramere (C40) von 1-Decen erhalten werden. Die kinematischen Viskositäten und Fließpunkte der hydrierten Oligomere wurden bestimmt und mit den Werten handelsüblicher Proben verglichen. Ein Mechanismus für die Oligomerisation von 1-Decen mit diesem Katalysatorsystem wird vorgeschlagen.
    Notes: The catalytic oligomerization of 1-decene has been carried out employing several transition metal complexes of Co(II), Co(III), Zr(IV), Ti(IV), Cr(III), V(V) in combination with alkyl aluminum halides as cocatalysts. The chromium(III)-Et3Al2Cl3 system exhibits good oligomerizing activity yielding dimers (C20), trimers (C30) and tetramers (C40) of 1-decene. The kinematic viscosities and pour points of hydrogenated oligomers have been determined and compared with those of commercial samples. The probable mechanism of oligomerization of 1-decene on this catalyst is described.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052250105
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  • 50
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    Zur Häurtung von Bisphenol-A-diglycidether mit Dicyandiamid in Gegenwart von Beschleuniger-Addukten (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 99-107 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Single-component formulations of epoxy resins with reactive accelerators must be storable. The preparation of several blocked accelerators is described. The basicity of tertiary amines, which correlates with accelerating effects, as well as acidity and structure of polyphenols and modified novolacs influences the extend of blocking. The curing process was investigated by measurements of gel time and viscosity.
    Notes: Einkomponentige Epoxidharzsysteme mit effizienten Reaktionsbeschleunigern müssen lagerstabil sein. Daher wurden Versuche unternommen, Beschleuniger auf Basis von tertiären Aminen mit modifizierten Phenolnovolaken zu blockieren. Das Ausmaß der Blockierung ist sowohl von der Basizität der Amine, die mit der beschleunigenden Wirkung korreliert, als auch von der Acidität und dem strukturellen Aufbau der modifizierten Phenole abhängig. Die Bewertung der Härtungseigenschaften erfolgte über Gelzeitbestimmungen und Viskositätsmessungen.
    Additional Material: 2 Ill.
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    Comparison of the crack growth method and the crack stress whitening zone method for the fracture toughness determination of phenolphthalein poly(ether ketone)Key Project of the National Natural Science Foundation of China. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 225 (1995), S. 131-138 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Bruchzähigkeit von Phenolphthalein-Poly(etherketon) bei 190°C wurde mit zwei verschiedenen Methoden bestimmt, der konventionellen Rißwachstumsmethode und der „stress whitening zone“-Methode. Die gute Übereinstimmung der Ergebnisse zeigt, daß letztere Methode zur Bestimmung der Rißinitiierung einiger Polymerer herangezogen werden kann, für die das „blunting line concept“ nicht geeeignet ist.
    Notes: Fracture toughness values of phenolphthalein poly(ether ketone) (PEK-C) at 190°C were determined by two different methods, i.e. the conventional crack growth method and the crack stress whitening zone method, which show consistent results. This indicates that the crack stress whitening zone method can be used to determine the crack initiation of some polymers for which the blunting line concept is unsuitable.
    Additional Material: 7 Ill.
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    Thermodynamic studies on some interpolymer interactions and stability of polycomplexes (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 13-22 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Stabilitätskonstanten und zugehörige thermodynamische Parameter (ΔH°, ΔS°) eines intermakromolekularen Komplexes aus Poly(acrylsäure-co-acrylamid), Poly(methacrylsäure-co-acrylamide) und Poly(N-vinylpyrrolidon) wurden mit bekannten Methoden bei verschiedenen Temperaturen bestimmt. Dabei wurde eine stufenweise Auflösung des Komplexes in Abhängigkeit von der Temperatur beobachtet, die mit den Stabilitätskonstanten und den thermodynamischen Parametern korreliert wurde.
    Notes: Stability constant and related thermodynamic parameters (ΔH° and ΔS°) of a multicomponent intermacromolecular complex consisting of poly(acrylic acid-coacrylamide), poly(methacrylic acid-co-acrylamide) and poly(N-vinylpyrrolidone) have been determined using known methods. A distinct stepwise disintegration of the complex at different temperatures has been observed, and this could be correlated with the stability constant and thermodynamic parameters calculated at various temperatures.
    Additional Material: 2 Ill.
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    The effect of ultrasound in ethyl methacrylate polymerization and depolymerization reactions (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 53-57 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Ultraschall auf die Polymerisation und Depolymerisation von Ethylmethacrylat und der Mechanismus des Kettenabbruchs wurden untersucht. Der Polymerisationsumsatz war unabhängig von den verwendeten Ultraschallbedingungen (800 W, 35 kHz). Depolymerisationsversuche mit Ultraschall bei 20°C zeigten, daß Kettenabbruch im wesentlichen durch Disproportionierung stattfindet; dabei werden Molekulargewichte nicht unter ca. 500000 erreicht.
    Notes: The effect of ultrasound in ethyl methacrylate polymerization and depolymerization and the chain termination mechanism for ethyl methacrylate have been studied. Polymerization conversion at 60°C did not depend on energy (80 W) and frequency (35 kHz) of ultrasound applied. In ultrasound depolymerization studies at 20°C the governing termination mechanism was found to be disproportionation and the lower limiting molecular weight was Mn = 500 000.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052260106
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    Reaktive membrancopolymere auf acrylbasis (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 71-87 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The copolymerization of acrylonitrile with maleic anhydride was investigated to synthesize acylic reactive polymers for manufacture of membranes that serve as support for covalent enzyme immobilization. The free-radical copolymer synthesis was carried out in solution (N,N-dimethylformamide (DMF), dimethylacetamide (DMAC), γ-butyrolactone, ethylene carbonate), by precipitation polymerization (dioxane) as well as bulk polymerization. The polymers were characterized using IR spectroscopy, elementary analysis, NMR spectroscopy, gel permeation chromatography, viscosity measurements, osmometry and potentiometry.The kinetic parameters were followed by dilatometric measurements up to high conversions. The anhydride content in the monomer mixtures showed a significant influence on the rate of polymerization and the molecular weight. With raised concentration of anhydride the polymerization rate and molecular weights decreased. Film forming polymers (M̄η 〉 30 000 g/mol) can be obtained by all copolymerization procedures with exception of solution polymerization in DMF and DMAC, respectively. The content of maleic anhydride in the membrane polymers did not exceed 5 mol-%, even though the maleic anhydride content in the monomer mixtures was raised up to the equimolar mixture. Nevertheless, such low maleic anhydride content of prepared membranes is enough for successful enzyme immobilization with amyloglucosidase (copolymer was prepared in γ-butyrolactone, M̄η = 49 000 g/mol, cPMSA = 0,3 mol-%).
    Notes: Die Copolymerisation des Acrylnitrils mit Maleinsäureanhydrid (MSA) wurde mit dem Ziel untersucht, acylfunktionalisierte Reaktivpolymere mit Filmbildungseigenschaften herzustellen, um diese in der Anwendung als Membran für kovalente Enzymfixierungen zu nutzen. Die radikalinitiierte Synthese der Copolymeren wurde in Lösung (Dimethylformamid (DMF), Dimethylacetamid (DMAC), γ-Butyrolacton, Ethylencarbonat), durch Fällungscopolymerisation (Dioxan) sowie in Substanz durchgeführt.Die Polymercharakterisierung erfolgte durch IR-Spektroskopie, Elementaranalyse, Kernresonanzspektroskopie, Gelpermeationschromatographie, Viskosimetrie, Osmometrie und Potentiometrie.Die Kinetik wurde durch dilatometrische Untersuchungen bis zu hohen Umsätzen verfolgt. Danach weist der Anhydridgehalt im Monomergemisch einen signifikanten Einfluß auf die Bruttopolymerisationsgeschwindigkeit und die Molmasse der Polymeren auf. Mit steigendem Anhydridanteil wird die Bruttopolymerisationsgeschwindigkeit herabgesetzt und eine Verringerung der Molmasse herbeigeführt. Die Copolymerisation von Acrylnitril und Maleinsäureanhydrid führt mit Ausnahme der Lösungspolymerisation in DMF bzw. DMAC zu Polymeren mit Molmassen oberhalb 30 000 g/mol, was ihre Anwendung als Membran ermöglicht. Die Einbaurate an Maleinsäureanhydrid in den Membranpolymeren ist bis einschließlich einer äquimolaren Zusammensetzung des Monomergemischs nicht größer als 5 mol-%. Derartig niedrige MSA-Reaktivgruppenanteile erweisen sich jedoch als ausreichend, um an einer aus einem Lösungspolymerisat (γ-Butyrolacton, M̄η = 49 000 g/mol, cPMSA = 0,3 mol-%) formierten Membran eine Enzymimmobilisierung mit Amyloglucosidase nachzuweisen.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052260108
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    Synthesis and characterization of photopolymers with azo units. Interfacial polyaddition, photolysis, photodegradation (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 143-160 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Synthesen einer Aryl-alkyl-azodiisocyanat-Verbindung und einer Azoharnstoff-Modellsubstanz werden beschrieben. Aus dem Azodiisocyanat wurden durch Grenzflächen-Polyaddition neuartige Azoharnstoff-Polymer hergestellt. Die zahlenmittleren Molekulargewichte, bestimmt mit der Gelpermeationschromatographie (GPC), lagen zwischen 6000 und 9000. Die Photolyse- und Thermolysereaktionen der Modellsubstanzen und der Polymeren wurden mittels UV-Spektroskopie und Differentialkalorimetrie (DSC) verfolgt und mit den Ergebnissen von ähnlichen Azoamiden verglichen. Der photochemische Polymerabbau wurde mittels GPC untersucht.
    Notes: The synthesis of an aryl alkyl azo diisocyanate and a model azo urea is described. From the azo diisocyanate new azo polyureas were created by interfacial polyaddition. Molecular weights Mn in the range of 6000 to 9000 were determined by gel permeation chromatography (GPC). Photolysis and thermolysis of both, model compounds and polymers, were studied by UV-spectroscopy and differential scanning calorimetry (DSC), respectively, and the results were compared with those of similar azo amides. Photochemical polymer degradation was followed by GPC.
    Additional Material: 8 Ill.
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    Announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 226 (1995), S. 219-219 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052260120
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    Molecular structure of liquid-crystalline copolyesters of vanillic acid, 4-hydroxybenzoic acid and poly(ethylene terephthalate) (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 227 (1995), S. 69-85 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Thermotrop flüssigkristalline Copolyester aus Vanillinsäure (V), 4-Hydroxybenzoesäure (B) und Polyethylenterephthalat (E) wurden mittels 1H-NMR-Spektroskopie und Gelpermeationschromatographie (GPC) untersucht. Die neun möglichen Diaden konnten detektiert und zugeordnet werden. Die Abfolge der Grundeinheiten der V/B/E-Copolyester ändert sich mit zunehmendem B-Anteil von statistischer Verteilung zur Blockbildung und ist außerdem geringfügig von der Katalysatorkonzentration und der Polykondensationsdauer abhängig. Die GPC-Ergebnisse deuten darauf hin, daß die V/B/E-Copolyester engere Molekulargewichtsverteilungen aufweisen als die B/E-Copolyester. Mit von 0 bis 5 mol-% steigendem V-Anteil verengt sich die Molekulargewichtsverteilung. Die Gelpermeationschromatogramme der meisten V/B/E-Copolyester weisen im Unterschied zu den Einzelsignalen der B/E-Copolyester Dublett-Peaks auf.
    Notes: Thermotropic liquid-crystalline copolyesters made from vanillic acid (V), 4-hydroxybenzoic acid (B) and poly(ethylene terephthalate) (E) were examined by 1H-NMR and GPC investigations. Nine possible diads could be identified and assigned. The sequence distribution of V/B/E copolyesters tends to change from random to block with an increase of B content in the copolyesters. The sequence distribution also varies slightly with catalyst concentration and polycondensation time. GPC results suggest that the V/B/E copolyesters have narrower molecular weight distribution (MWD) than B/E copolyesters. The MWD of the copolyesters narrows gradually with increasing V content from zero to 5 mol-%. The GPC chromatograms of the most V/B/E copolyesters show double peaks, which is different from the single peak of the GPC chromatograms of the B/E copolyesters.
    Additional Material: 6 Ill.
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    Effect of pre-irradiation on radiation stability of co-polypropylene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 227 (1995), S. 111-120 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Strahlungsbeständigkeit von vorbestrahltem Polypropylen mit 2,5 Gew.-% Ethylenanteil wurde mitr einem Copolymeren aus Polypropylen und einem nukleierenden Agens im Hinblick auf die Strahlungssterilisation von medizinischen Geräten verglichen. Die Transparenz des Propylen-Ethylen-Copolymeren wurde durch die Vorbehandlung verbessert. Im Vergleich mit der ebenfalls verbesserten Transparenz des Copolymeren aus Polypropylen und dem nukleierenden Agens wurde durch die Vorbestrahlung die Strahlungsbeständigkeit während der Bestrahlung und bei der Lagerung des bestrahlten Materials verbessert. Dies wird auf die geringere Kristallinität des vorbestrahlten Polypropylens aufgrund von bei der Bestrahlung gebildeten Verzweigungen zurückgeführt.
    Notes: The radiation stability of the pre-irradiated copolymer of polypropylene containing 2.5 wt.-% ethylene units is compared with a copolymer of polypropylene with a nucleating agent with regard to radiation sterilization of medical devices. It is found that transparency property of the propylene-ethylene copolymer is improved through pre-irradiation processes. This finding was compared with the co-polypropylene with nucleating agent which also gives a better transparency property. In comparison, it is found that pre-irradiated copolymer exhibits better radiation stability during irradiation and during storage after irradiation. The radiation stability of the pre-irradiated copolymer is due to its lower crystallinity caused by the formation of branches during the pre-irradiation process.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052270111
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    Mitteilungen/Announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 227 (1995), S. 193-193 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052270117
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    Poly(diaryl diazosulfide)s  -  synthesis and photolysisThis topic is part of the Ph.D.-Thesis of A. Lang.. Photopolymers, diazosulfides, interfacial polycondensation, photolysis (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 228 (1995), S. 73-92 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polydiaryldiazosulfide wurden durch Grenzflächenpolykondensation aus aromatischen Bisdiazoniumionen und Benzol-1,3-dithiol erhalten. Auf diese Weise wurden Molekulargewichte Mn von 3400 bis 11700 erreicht (GPC).Die neue Polymerklasse zeichnet sich durch hohe Photolabilität und relativ geringe Thermostabilität aus. Mittels UV-Spektroskopie wurde die Photolyse von Modellver-bindungen und Polymeren verfolgt, wobei in nahezu allen Fällen ein Zerfall 1. Ordnung beobachtet wurde. Der photochemische Kettenabbau konnte durch GPC-Untersuchungen verfolgt werden. Die thermische Stabilität der polymeren Diazosulfide wurde durch DSC-Messungen untersucht.
    Notes: Poly(diaryl diazosulfide)s were synthesized from aromatic bisdiazonium ions and benzene-1,3-dithiol via interfacial polycondensation. Number-average molecular weights Mn in the range of 3400 to 11700 were determined by gel permeation chromatography (GPC).The new polymer class is distinguished by high photosensitivity and low thermostability. First order kinetics during photolysis of nearly all polymers and model compounds under investigation was observed by means of UV spectroscopy. Polymer degradation upon irradiation was verified by GPC measurements. Thermal decay was followed by differential scanning calorimetry (DSC).
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052280107
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    Methoden zur bestimmung des maleinsäureanhydridgehaltes in acrylnitril-copolymeren in gegenwart initialer carboxygruppen (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 228 (1995), S. 161-178 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Three different titration methods were proved with respect to accuracy, reproducibility and handling for the determination of maleic anhydride (MSA) content in acrylonitrile (AN) copolymers in form of poly(AN-co-MSA) and poly(AN-co-styrene-co-MSA). The comparison comprises (i) the combined method A/H characterized by the reaction of anhydride groups (AG) with aniline and titration of the formed monoacid with methanolic KOH (A) and the complete hydrolysis of AG and titration of acid groups (SG) with aqueous NaOH (H), (ii) method B based on the conversion of AG with n-butylamine (BA) and back-titration of unreacted amine with HClO4 in glacial acetic acid and (iii) method C consisting of the reaction of AG with p-chloroaniline (pCA) followed by Cl-determination after the Schöniger-decomposition. Whereas all mentioned methods are suitable for the determination of AG in the presence of initial SG, the combination of A/H additionally allows the simultaneous determination of AG and SG. In comparison with the other methods the combination of A/H is to be favoured due to the possibility to obtain additional information about SG and because of the better results in accuracy, reproducibility and handling. By means of FTIR spectroscopy the content of AG and SG was estimated qualitatively and a correlation between the spectroscopic and potentiometric data of AG was discovered.
    Notes: Zur Bestimmung des Maleinsäreanhydrid(MSA)-Gehaltes in Acrylnitril(AN)-Copolymeren des Typs Poly(AN-co-MSA) bzw. Poly(AN-co-Styrol-co-MSA) wurden drei verschiedene Titrationsmethoden hinsichtlich ihrer Richtigkeit, Reproduzierbarkeit sowie ihres Zeitaufwandes geprüft. Miteinander verglichen wurden (i) eine Methodenkombination A/H bestehend aus dem Teilschritt A, einer Umsetzung der Anhydridgruppen (AG) mit Anilin einschließlich der Titration der Monosäuregruppen mit methanolischer KOH, und dem Teilschritt H, einer vollständigen Hydrolyse der AG und Titration der Säuregruppen (SG) mit wäßriger NaOH, (ii) Methode B basierend auf der Reaktion der AG mit n-Butylamin (BA) und der Rücktitration des nicht umgesetzten Amins mit Perchlorsäure (HClO4) in Eisessig und (iii) Methode C, beruhend auf der Umsetzung der AG mit p-Chloranilin (pCA) und nachfolgender Chlorbestimmung durch Schöniger-Aufschluß. Während sich alle genannten Methoden prinzipiell für die AG-Bestimmung in Gegenwart initialer SG empfehlen, ist darüber hinaus über A/H eine simultane Bestimmung von AG und SG möglich. Wegen dieses zusätzlichen Informationsgewinns, ihrer besseren Reproduzierbarkeit, der erhöhten Richtigkeit sowie des geringeren zeitlichen und apparativen Aufwandes ist die Kombination A/H zu favorisieren. Mit Hilfe der FTIR-Spektroskopie wurde der Gehalt an AG und SG qualitativ verfolgt und eine Korrelation zwischen den Bandenintensitäten der AG und den potentiometrisch erhaltenen Werten gefunden.
    Additional Material: 6 Ill.
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    Curing of unsaturated polyester resins with low exotherm peak (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 15-27 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Härtung eines ungesättigten Polyesterharzes mit niedrigem Exotherm-Peak wurde mit der Standardmethodik und der Differential-Kalorimetrie (DSC) untersucht. Ein Kupfersalz und α-Methylstyrol wurden als Polymerisationsverzögerer benutzt. Der Einfluß der Verzögerer auf die Temperatur des exothermen Peaks, die Gelzeit, die Härtungsenthalpie und die Polymerisationskinetik wurden untersucht.
    Notes: The curing behavior of an unsaturated polyester resin with low exotherm peak was studied by a standard procedure and by differential scanning calorimetry (DSC). A copper salt and α-methylstyrene were used as the polymerization retarders. The influence of the retarders on the exotherm peak temperature, gelation time, exothermic heat and the polymerization kinetics was investigated.
    Additional Material: 8 Ill.
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    Modified syndiotactic polypropene: Poly(propene-co-octene) and blends with atactic oligopropene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 93-112 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Propen und 1-Octen wurden mit dem syndiospezifischen Metallocen-Katalysator Me2C(Cp)(Flu)ZrCl2/MAO copolymerisiert. Es wurde ein hoher, statistischer Octeneinbau beobachtet. Niedrige Octenkonzentrationen beeinflußten die Aktivität des Katalysators nur wenig; Molekulargewicht, Kristallinität, E-Modul und Glastemperatur wurden dagegen mit ansteigendem Octengehalt erniedrigt. Blends aus ataktischem Oligopropen und syndiotaktischem Polypropen bzw. Poly(propen-co-octen) wurden aus einer Toluol-Lösung hergestellt. Diese Lösungsblends wurden mit einem Reaktorblend verglichen, der mit einem Hybrid-Katalysator bestehend aus einer Mischung von syndiospezifischem Me2C(Cp)(Flu)ZrCl2/MAO und unspezifischem Cp2ZrCl2/MAO hergestellt wurde. Das ataktische Oligopropen wirkte als Weichmacher, der E-Modul und Glastemperatur der Blends erniedrigte.
    Notes: Propene and 1-octene were copolymerized with the syndiospecific homogeneous metallocene catalyst Me2C(Cp)(Flu)ZrCl2/MAO. Large amounts of octene were incorporated randomly. While catalyst activity was not affected markedly by low octene content, molecular weight, crystallinity, Young's modulus, and glass transition temperature were reduced with increasing octene content. Blends of atactic oligopropene with syndiotactic polypropene and poly(propene-co-octene) were prepared from toluene solution and compared with a reactor blend prepared with a hybrid catalyst containing a mixture of syndiospecific Me2C(Cp)(Flu)ZrCl2/MAO and non-specific Cp2ZrCl2/MAO. Atactic oligopropene acted as plasticizer reducing Young's modulus and glass transition temperature of the blends.
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    Inner surface and void system of regenerated cellulose fibers (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 175-184 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die innere Oberfläche und das Hohlraumsystem von verschiedenartigen Celluloseregeneratfasern werden mit Röntgenkleinwinkelstreuung untersucht. Dabei wird gefunden, daß alle Fasern ein Hohlraumsystem von 0,01 bis 0,1% (Volumenanteil 10-4-10-3) aufweisen. Es zeigt sich jedoch, daß die Größe des Hohlraumsystems für die mechanischen Eigenschaften wenig Bedeutung hat. Es ist vielmehr die Gestalt der Hohlräume und ihre Orientierung, die hier wesentlich sind. Es wird gefunden, daß langgestreckte Hohlräume, vermutlich orientiert, für gute mechanische Eigenschaften verantwortlich sind. Damit können auch verbesserte textile Eigenschaften von Lyocellfasern des NMMO-Typs erklärt werden.
    Notes: Both the inner surface and the void system of different cellulose regenerate fibers are investigated with X-ray small angle scattering. Thereby it turns out that all fibers have a void system of 0.01 to 0.1% (volume fraction 10-4-10-3). However, the amount of the void system has little influence on the mechanical properties. Rather, it is the shape of the voids and their orientation which proves essential. It is found that elongated voids, probably well oriented, are responsible for superior mechanical properties. This explains also improved textile properties of lyocell fibers of the NMMO type.
    Additional Material: 6 Tab.
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    Radiation-induced copolymerization of methacrylic and acrylic acid with acrylamide (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 230 (1995), S. 1-12 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die mit γ-Strahlen induzierte Polymerisation von Methacrylsäure (MA) und Acrylsäure (AA) mit Acrylamid (AAm) (M2) in Substanz wurde untersucht. Die nach Kelen-Tüdős berechneten Copolymerisationsparameter betragen r1 = 1.35 und r2 = 0.22 für MA-AAm bzw. r1 = 1.75 und r2 = 0.10 für AA-AAm. Die Polymerisationsgeschwindigkeit hängt sowohl von der Temperatur als auch von der Comonomerzusammensetzung ab. Die differentialkinetischen Kurven sind unimodal, was darauf hinweist, daß nur der Copolymerisationsprozeß abläuft. Ein zweites Maximum in diesen Kurven wird mit Vernetzung und der Bildung wasserunlöslicher Bestandteile erklärt. Die Copolymeren sind weiße Pulver; die wasserlöslichen Fraktionen sind im Gegensatz zu den wasserunlöslichen nicht giftig, aber als Immunmodulatoren weniger aktiv.
    Notes: A study was made of the γ-radiation-induced bulk copolymerization of the methacrylic acid-acrylamide (M2) (MA-AAm) and acrylic acid-acrylamide (M2) (AA-AAm) monomeric pairs. The copolymerization reactivity ratios deterined according to the Kelen-Tüdő method were: r1 = 1.35, r2 = 0.22 for the MA-AAm pair, and r1 = 1.75, r2 = 0.10 for the AA-AAm pair. It has been established that the polymerization rate depends both on the composition of the starting reaction mixture and on the reaction temperature. The differential kinetic curves obtained are unimodal ones, suggesting the occurrence of only one process, i.e. copolymerization. A second maximum in these curves, appearing at elevated temperature, is explained by crosslinking and formation of a water-insoluble fraction. The copolymers obtained are white powders; in contrast to their water-insoluble fractions, the water-soluble ones are not toxic but they are less active as immunomodulators.
    Additional Material: 11 Ill.
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    Synthesis and hydrolytic stability of model poly(ester urethane ureas) (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 228 (1995), S. 201-219 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Hydrolyse von Poly(ester-urethan-harnstoffen) (PURUs) wurde untersucht. Es handelt sich dabei um einen komplexen Vorgang, der die Analyse der Beziehung zwischen der Zusammensetzung der PURUs und ihrer Hydrolysebeständigkeit erschwert. Es wurde gefunden, daß die Hydrolysebeständigkeit mit Zunahme (i) der Polyol-Acidität, (ii) des Estergruppen-Gehaltes, (iii) der Beweglichkeit der Hauptketten und (iv) deren Hydrophilie abnimmt; die Molmasse des Polyols scheint keinen merklichen Einfluß darauf zu haben. Der negative Einfluß von Ethergruppen (obwohl hydrolysebeständiger als Estergruppen) ist möglicherweise auf eine Zunahme der Hauptkettenbeweglichkeit und den dadurch leichteren Zugang von Wassermolekülen zu Estergruppen zurückzuführen. Der positive Effekt von aromatischen Ringen in Polyolen kann einer erhöhten Steifigkeit der Hauptkette als auch einer ansteigenden Hydrolysebeständig-keit benachbarter Estergruppen durch Resonanzeffekte zugeschrieben werden. Insgesamt kann angenommen werden, daß die beschriebenen Effekte sich überlagern und gleichzeitig die resultierende Hydrolysebeständigkeit vorherbestimmen. Es sollte daher möglich sein, qualitative Vorhersagen bezüglich der Hydrolysebeständigkeit in Abhängigkeit von der Zusammensetzung der PURUs zu treffen.
    Notes: Hydrolysis of poly(ester urethane ureas) (PURUs) is a complex phenomenon which impedes the analysis of the relationships between their composition and hydrolytic stability. Hydrolytic stability of PURUs decreases due to rising (i) polyol acidity, (ii) content of ester groups, (iii) flexibility and (iv) hydrophilicity of the backbones; molar mass of polyols does not seem to have any appreciable effect on it. Negative influence of ether groups (which have better hydrolytic stability than ester groups) is probably linked to the increase in the backbone flexibility and, consequently, to easier access of water molecules to ester groups. Positive effect of aromatic rings in polyols can be ascribed to enhanced rigidity of the backbones as well as to increased hydrolytic stability of adjacent ester groups due to the resonance effect. It can be presumed that the mentioned effects will superpose and simultaneously predestine the resulting hydrolytic resistance. Considering the observed tendencies, it is possible to qualitatively predict the trends how the hydrolytic stability will respond to changes in PURUs composition.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052280116
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    Synthesis and characterization of a naphthoquinonediazide positive photoresist derived from bis(hydroxymethyl)phenol (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 63-72 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine neuartige lichtempfindliche Naphthochinondiazid-Verbindung (NQD) wurde aus 2,6-Bis(hydroxymethyl)-3,4-dimethylphenol und Toluoldiisocyanat synthetisiert und mit IR-, NMR- und Elementaranalyse identifiziert. Die Bleicheigenschaften unter Lichteinwirkung wurden mit UV-Spektrophotometrie bestimmt. Die Anwendung von NQD in der Photolithographie als positiver Photoresist sowie einer wäßrigen Lösung von NQD, Novolak, Cellosolve-Acetat und DMF als lichtempfindliches Material wurde untersucht. Das hergestellte NQD erwies sich als effektive Komponente in positiven Photoresists. Die optimalen Bedingungen der UV-Dosis, Schichtdicke und Resistzusammensetzung wurden abgeschätzt. Die Auflösung des positiven Photoresists wurde durch Rasterelektronenmikroskopie bestimmt. Außerdem wurde der Einfluß von UV-Dosis und -Wellenlänge, Einwirkungsdauer und Entwicklungszeit auf die Empfindlichkeit und die Auflösung des Photoresists untersucht.
    Notes: A new photosensitive naphthoquinonediazide (NQD) was synthesized from 2,6-bis-(hydroxymethyl)-3,4-dimethylphenol and toluene diisocyante. NQD was identified by using IR, NMR and elemental analyses. Photobleachable characteristics were evaluated by UV spectrophotometry. Applications of the NQD on the photolithography as a positive working photoresist were investigated. The aqueous solution of NQD, novolak, cellosolve acetate, and DMF was used as a photosensitive material. It was found that NQD synthesized in this investigation can be used as an effective component in a positive photoresist. Optimal conditions of the UV dose, coating thickness, and development of the resist system were estimated. Resolution of the positive resist was evaluated by SEM technique. Effects of UV dose, exposure time, development time, and exposure UV wave length on the sensitivity and resolution of the photoresist were investigated.
    Additional Material: 6 Ill.
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    Investigations on free radical polymerization of phenyl-substituted 2-methylene-1,3-dioxanes (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 123-132 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die radikalinduzierte Polymerisation von phenlysubstituierten 2-Methylen-1,3-dioxanen wurde untersucht. Es kann gezeigt werden, daß die grundlegende Polymerisationstendenz derartiger Ketenacetale darin besteht, über die Doppelbindung zu hochmolekularen Polyacetalen ohne eine nennenswerte Ringöffnung zu polymerisieren. Einflußfaktoren, wie z. B. resonanzstabilisierte Kettenenden oder sterische Hinderungen während des Wachstumsschrittes sind nicht in der Lage, die Polymerisation in die Richtung der gewünschten Ringöffnung zu lenken.Mittels Dichtemessungen wurden Informationen über das Schrumpfungsverhalten gewonnen. Es konnte gezeigt werden, daß raumerfüllende Substituenten am 2-Methylen-1,3-dioxansystem bei der Homopolymerisation grundsätzlich eine geringe Volumenschrumpfung bewirken und die Schrumpfung von herkömmlichen Monomeren bei der Copolymerisation herabsetzen können.
    Notes: We have investigated the free radical polymerization of phenyl-substituted 2-methylene-1,3-dioxanes. It was shown that there is a basic tendency of such ketenacetals to undergo exclusively a vinyl polymerization forming high-molecular polyacetals without any detectable ring opening. The polymerization with the desirable ring opening reaction cannot be controlled by factors like resonance stabilized chain ends or steric hindrance in the growing step.From densitometric measurements we got new information about the shrinkage behaviour. It was demonstrated that bulky substituents attached to the 2-methylene-1,3-dioxane system result in a significant low shrinkage in homopolymerization and the shrinkage of common comonomers can be decreased by copolymerization.
    Additional Material: 5 Ill.
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    Acrylamide polymerization in concentrated bicontinuous systems (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 133-143 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Polymerisation von Acrylamid (AAM) in einer konzentrierten bikontinuierlichen Mikroemulsion wurde studiert. Die Initiierungsstelle bei Verwendung von radikalischen Initiatoren mit verschiedener Wasserlöslichkeit wurde untersucht. Es wurde festgestellt, daß ein vollständig oder teilweise wasserlöslicher radikalischer Initiator die Acrylamidpolymerisation in der untersuchten Mikroemulsion effektiv initiieren kann. Die dadurch entstandenen Polymeren weisen eine Spezialstruktur auf, die von der Zusammensetzung der ursprünglichen Mikroemulsion abhängig ist.
    Notes: The polymerization of acrylamide (AAM) in concentrated bicontinuous microemulsion systems was studied. The locus of initiation using radical initiators with various water-solubility was investigated. It was found that water-soluble and partially water-soluble initiators initiate the AAM polymerization in the reaction systems under investigation very effectively. The polymers thus formed have special structures dependent on the composition of the original concentrated bicontinuous microemulsion.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052290109
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    Mitteilungen/announcements (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 209-209 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052290115
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    Orientierung von Bacteriorhodopsin in einer Polymermatrix (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 185-198 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bacteriorhodopsin is a component of the purple membrane of Halobacterium halobium. It shows photochemical activity and undergoes a series of photocyclic-associated conformational changes. Incorporated in a matrix it is suitable as a light energy/electrical current transducer. Very important is an orientation of purple membrane fragments.The reaction between solutions of a polyelectrolyte and multivalent ions leads to a ionotropic gel, that is a gel with an ordered structure. If the gel formation was carried out in the presence of purple membrane fragments, the Bacteriorhodopsin is highly oriented and produces a photoelectrical signal. It consists a correlation between the light direction and the orientation of the purple membrane due to the gel formation.
    Notes: Bacteriorhodopsin ist Bestandteil der sogenannten Purpurmembran des Mikroorganismus Halobacterium halobium. Es zeigt photochemische Aktivität und kann als biologischer Lichtwandler fungieren. Voraussetzung hierfür ist eine orientierte Anordnung der Purpurmembran in einer Matrix.Das Prinzip der ionotropen Gelbildung, d. h. die geordnete Strukturbildung einer Polyelektrolytlösung infolge eines gerichteten Diffusionsstromes von mehrwertigen Ionen gestattet die orientierte Anordnung der Purpurmembran. Durch Lichteinwirkung werden elektrische Signale induziert. Es besteht ein Zusammenhang zwischen der Richtung des Strahlungseinfalls und der durch die Gelwachstumsrichtung festgelegten Orientierung der Purpurmembran.
    Additional Material: 10 Ill.
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    Stabilizer consumption and lifetime prediction in ageing of crosslinked polyethylenePaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 1-12 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal oxidation of β ray-crosslinked polyethylene (XLPE) was studied in temperatures ranging from 90 to 180°C. Various analytical methods were used for determination of an end of the induction period on bulk samples: gravimetry, ultimate tensile properties, density and color change. On microtome slices of ∼30 μm thickness the depth distribution of oxidation products, phenolic antioxidant, density and tensile ultimate properties were followed as a function of exposure time by respectively IR and UV spectrophotometry, densitometry and Microfoil Tensile Testing.Depending on the testing method different durations of induction period (DIP) were obtained. They increase in following order:Phenol depletion 〈 Ultimate elongation 〈 Density 〈 Carbonyl build-up ≤ Color change 〈 Weight loss.The difference between phenol depletion DIP and carbonyl build-up DIP can be considered as negligible at temperatures higher than the melting point (about 30%) but it reachs more than 100% at T〈 Tm.Different kinetic regimes of phenol consumption were observed depending on the exposure temperature. A mechanistic interpretation is proposed explaining the role of the stabilizer system in initially homogeneous and later heterogeneous oxidation of the bulk material.The Arrhenius law was applied to different durations of induction period. A discontinuity appeared in the melting point region (120-130°C) which is tentatively interpreted in terms of different stabilizer concentration in amorphous phase of semicrystalline material (T 〈 Tm) and in melt material (T 〉 Tm). On the basis of the presented complex study of polyethylene thermo-oxidation, different aspects of lifetime predictions are discussed.
    Additional Material: 10 Ill.
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    Pyrolysis with respect to recycling of polymerPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 151-165 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Most plastics are produced from oil and have a high potential as hydrocarbon sources for the chemical industry. Pyrolysis is a practicable way to pyrolyze mixed plastics. The fluidized bed pyrolysis has turned out to be particularly advantageous. 25 to 45 percent of product gas with a high heating value and 30 to 50 percent of an oil rich in aromatics, could be recovered. The oil is comparable to that of a mixture of light benzene and bituminous coal tar. Up to 60 percent of ethene and propene are produced by using mixed polyolefins as feedstock. Under appropriate conditions the pyrolysis could be successful on the market.
    Additional Material: 1 Ill.
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    Photodegradation of UV absorbers: Kinetics and structural effectsPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 229-238 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When poly(methyl methacrylate) films containing UV absorbers are exposed to UV light, the absorbers undergo photodegradation resulting in loss of absorbance. If the data extend for less than one half-life, both zero and first order kinetic treatment give fairly linear fits, but the rate constants so derived are dependent on the initial absorbance of the films. When the zero order rate constants are corrected to account for the higher rate of degradation near the surface compared with the bulk that occurs in highly absorbing films, consistent “infinite absorption” zero order rate constants are derived. The inhomogeneous degradation is due to only the highly absorbed, higher energy light contributing significantly to the degradation. For the benzophenone and benzotriazole classes of absorber, at least 65% of the degradation is due to light with wavelengths 〈 350 nm. Structural variations generally caused only small differences in the rates of degradation of these classes of absorbers unless the substitutions disrupted the intramolecular hydrogen bonds that are critical for stability. If the hydrogen bond is weakened, the absorber is less stable.
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    Polymers from renewable resources, VI. Synthesis and characterization of thermosetting resins derived from cashewnut shell liquid/formaldehyde/substituted aromatic compounds (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 233 (1995), S. 1-13 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aus Cardanol, einem Bestandteil der Schale der Cashewnuß, wurde durch Kondensation mit Formaldehyd und substituierten aromatischen Verbindungen unter saurer oder basischer Katalyse eine Reihe von Harzen hergestellt und anhand ihrer IR-Spektren charakterisiert. Sie lassen sich als selektive Ionenaustauscher für bestimmte Ionen verwenden, was mittels einer Gleichgewichtsmethode geprüft wurde. Das thermische Verhalten der Harze wurde untersucht, und ein plausibler Abbaumechanismus wird vorgeschlagen.
    Notes: A large number of resins have been synthesized by reacting cardanol, a constituent of cashewnut shell liquid, with formaldehyde and substituted aromatic compounds in the presence of acidic and basic catalysts. The resins have been characterized by IR spectra. They were shown to be selective ion exchangers for certain metal ions. A batch equilibrium method was used for studying the selectivity of the metal ions. The thermal behaviour of the resins has been studied and a plausible degradation mechanism has been suggested.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052330101
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    Search for the sources of color in thermally aged, weathered and γ-ray irradiated bisphenol a polycarbonatePaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 27-43 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bisphenol A polycarbonate (BPA-PC) is an important high performance engineering thermoplastic well known for its outstanding combination of toughness, transparency and heat resistance. These properties make it an idel material for demanding applications where it is exposed to external stresses such as elevated temperatures, ultraviolet light and γ-ray sterilization. However, on extended exposure to these conditions, BPA-PC slowly degrades, turning progressively more yellow, eventually leading to a decrease in its physical properties. Over the years, there has been numerous studies made to understand these degradative processes so as to better design more stable BPA-PC formulations. In this paper, this chemistry is briefly reviewed along with more recent work in this area with a special emphasis on the efforts made to identifying the actual chemical species responsible for the observed yellow color and the chemistry responsible for their formation.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052320103
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    Model studies on the mechanism of hals stabilizationPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 65-83 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hindered Amine Light Stabilizers (HALS) are know to inhibit the photo-oxidation of polymers. A key reaction in their stabilization mechanism is believed to be the conversion of a hindered aminoether into a nitroxyl radical. Several different possible mechanisms for this conversion were explored. One, the elimination of the aminoether to form an olefin and hydroxylamine (an intermediate in the formation of a nitroxyl), while possible at high temperatures, cannot account for the inhibitory activity we observed for secondary and primary aminoethers. Direct radical displacement by peroxy radicals was also considered. However, the products predicted by this reaction pathway were not observed. Finally, oxidation of the nitrogen by a peroxy radical, by either electron transfer or a radical attack on the nitrogen, was investigated. While electron transfer was shown to be unlikely, direct oxidation of the aminoether nitrogen was supported by our results. A detailed mechanism for the reaction of both alkyl- and acyl-peroxy radicals with aminoethers is proposed.
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    Physical, dynamic-mechanical and thermogravimetric analysis of aromatic and cycloaliphatic-based poly(urethaneurea)s (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 79-89 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die thermischen und dynamisch-mechanischen Eigenschaften einiger linearer kautschukelastischer Polyurethane mit chemisch unterschiedlichen starren Segmenten wurden untersucht und zur chemischen Zusammensetzung in Beziehung gesetzt. Interessante Zusammenhänge wurden zwischen der Kristallinität der elastischen Polyurethanharnstoffe und der aromatischen oder cycloaliphatischen Natur der Diisocyanat-Komponenten gefunden. Darüber hinaus scheinen die Ergebnisse bei einem bestimmten Verhältnis zwischen starren und flexiblen Segmenten und bei gegebener Zusammensetzung der flexiblen Gruppen auf eine bessere Phasenseparation bei den Polyurethanharnstoffen mit cycloaliphatischen starren Segmenten als bei solchen mit aromatischen, starren Einheiten hinzuweisen.
    Notes: Experimental batches of linear rubber-like polyurethanes characterized by the presence of chemically different hard segments are studied and their thermal and dynamic-mechanical properties are related to the differences in chemical compositions. Interesting correlations are found between the development of crystallinity in such elastomeric poly(urethaneurea)s and the aromatic or alicyclic nature of the diisocyanate. Moreover, for a fixed ratio between hard and soft segments, and for a given composition of the soft segment, the results seem to indicate a better degree of phase separation in cycloaliphatic-based hard segment poly(urethaneurea)s than in aromatic-based hard segment poly(urethaneurea)s.
    Additional Material: 7 Ill.
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    Dispersion polymerization of styrene and methyl methacrylate initiated by poly(oxyethylene) macromonomeric azoinitiators (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 135-144 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Makromonomere Polyethylenoxid-Azoinitiatoren (Makroinimere) MIM-400 und MIM-1500 wurden synthetisiert und IR- und NMR-spektroskopisch sowie mit Hilfe der DSC-Analyse charakterisiert. Die mit diesen Makroinimeren initiierte Dispersions-polymerisation von Styrol bzw. Methylmethacrylat (MMA) in Ethanol/Wasser bei 60°C wurde untersucht. Dabei wurde gefunden, daß die Polymerisationsgeschwindig-keit mit zunehmender MIM-Konzentration ansteigt, wobei der Anstieg im Styrolsystem ausgeprägter war. Im Bereich von mittleren Umsätzen konnte gezeigt werden, daß die Polymerisationsgeschwindigkeit von MMA proportional der Potenz 1,7 bzw. 1,6 von [MIM-400] bzw. [MIM-1500] ist, während für Styrol eine Potenz von 2,5 bezüglich [MIM-400] gefunden wurde.
    Notes: Macromonomeric poly(oxyethylene) azoinitiators (macroinimers) MIM-400 and MIM-1500 were synthesized and characterized by IR and NMR spectroscopy and DSC techniques. The dispersion polymerizations of styrene and methyl methacrylate (MMA) initiated by poly(oxyethylene) macroinimers (MIM-400 and MIM-1500) in water/ethanol were investigated at 60°C. The rate of polymerization was found to increase with increasing concentration of MIM and the increase was more pronounced in the styrene system. In the range of medium conversions the rate of polymerization was found to be proportional to the 1.7th and 1.6th power of [MIM-400] and [MIM-1500] for MMA and to the 2.5th power of [MIM-400] for styrene, respectively.
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    Modell zur beschreibung der glasübergangstemperaturen binärer und ternärer mischungen von poly(styrol-co-n-butylmethacrylat)en (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 187-198 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Glass transition temperatures of binary and ternary blends of chemically uniform poly(styrene-co-n-butyl methacrylate)s with a mean content of 30.8 wt.-% of n-butyl methacrylate and number-average molar masses in the range of 4900 and 67000 g/mol have been investigated in relation to their composition. The blends showed significant deviations from an ideal behaviour with reference to a linearity between glass transition temperature and composition.This phenomenon is described by a mathematical model where polynoms are particularly well suited to represent the glass transition temperatures of the blends, partly exceeding those of the pure components. Finally, various reasons of these deviations were discussed. Here, energetical interactions seem to be of considerable importance combined with a nonadditivity of volumes.
    Notes: Die Glasübergangstemperaturen binärer und ternärer Mischungen chemisch einheitlicher Poly(styrol-co-n-butylmethacrylat)e mit einem mittleren n-Butylmethacrylat-Anteil von 30,8 Gew.-% und unterschiedlichen zahlenmittleren Molmassen im Bereich von 4900 bis 67000 g/mol wurden in Abhängigkeit von der Zusammensetzung untersucht. Es wurden wesentliche Abweichungen vom idealen Verhalten bezüglich einer linearen Abhängigkeit zwischen Glasübergangstemperatur und Zusammensetzung festgestellt.Dieses Verhalten konnte mit einem mathematischen Modell dargestellt werden, wobei sich insbesondere Polynome zur Beschreibung der teilweise über den Werten der Ausgangskomponenten liegenden Glasübergangstemperaturen der Mischungen als geeignet erwiesen. Schließlich wurden verschiedene Ursachen für diese Abweichungen diskutiert, wobei offensichtlich energetische Wechselwirkungen verbunden mit einer Nichtadditivität der Volumina von wesentlicher Bedeutung sind.
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    Zur bildung von polyepoxid-polyamid-netzwerken. Modelluntersuchungen am system phenylglycidether-ε-caprolactam (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 233 (1995), S. 133-148 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: ε-Caprolactam (CL) and phenyl glycidyl ether (PGE) were homopolymerized using the initiator/accelerator-systems Na-caprolactam/N-acetyl-caprolactam (NaCL/AcCL) and Na-caprolactam/N-acetyl imidazole (NaCL/AcImi). In a one-pot reaction both monomers gave different oligomeric reaction products depending on the reaction temperature (100°C to 140°C, max. 240°C) but no regular copolymers. Soluble products were separated by HPLC and identified by means of spectroscopic methods. In acetone insoluble products were investigated by IR- and NMR-spectroscopy, mass spectrometry and elemental analysis.
    Notes: Es wurden Versuche zur Homopolymerisation von ε-Caprolactam (CL) und Phenylglycidether (PGE) mit den Initiator/Beschleuniger-Systemen Na-Caprolactam/N-Acetylcaprolactam (NaCL/AcCL) und Na-Caprolactam/N-Acetylimidazol (NaCL/AcImi) durchgeführt, um die für eine mögliche Copolymerisation von CL und PGE geeigneten Reaktionsbedingungen zu ermitteln. CL und PGE wurden in unterschiedlichen molaren Verhältnissen (CL : PGE = 1 : 5 bis 1 : 0,05) und bei Temperaturen zwischen 100°C und 140°C (max. 240°C) in einer Eintopfreaktion polymerisiert.Die löslichen Produkte wurden mittels HPLC getrennt und spektroskopisch identifiziert. Die in Aceton unlöslichen Produkte wurden mit IR- und NMR-Spektroskopie, Massenspektrometrie (MS) und Elementaranalyse untersucht.
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    Synthesis and characterization of copolymers from acrylic and methacrylic acid with 2-methylaziridine by spontaneous copolymerization (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 199-211 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: 2-Methylaziridin (MAz) wurde als nukleophiles Monomeres mit den elektrophilen Monomeren Acrylsäure (AA) bzw. Methacrylsäure (MA) in unterschiedlichen Verhältnissen ohne Initiator copolymerisiert. Die Copolymeren wurden mittels Elementaranalyse, FT-IR- und 1H-NMR-Spektroskopie charakterisiert. Die Copolymerisationsparameter wurden mit den Methoden nach Fineman-Ross bzw. Kelen-Tüdős bestimmt. Für r1 und r2 wurden die Copolymerpaare MAz-AA und MAz-MA jeweils Werte 〈 1 ermittelt, was auf statistische Copolymere mit einer Tendenz zu alternierenden Copolymeren hinweist. Thermische Zersetzung mit einem Gewichtsverlust von 10% tritt bei den Copolymeren erst oberhalb 430 K auf. Der thermische Abbau verläuft nach einer Reaktion nullter Ordnung. Die kinetischen Parameter der Zersetzung der Copolymeren wurden bestimmt.
    Notes: 2-Methylaziridine (MAz) as a nucleophilic monomer and acrylic acid (AA) and methacrylic acid (MA), respectively, as electrophilic monomers were copolymerized in the absence of initiator at various feed ratios. Copolymers were characterized by elemental analysis, FT-IR and 1H-NMR spectroscopy. The monomer reactivity ratios were determined by the Fineman-Ross and Kelen-Tüdős methods. Values of r1 and r2 were found to be less than unity for MAz-AA, and MAz-MA, corresponding to random copolymers with the tendency to the alternance. For all the copolymers the thermal decomposition with 10% weight loss is higher than 430 K. The reaction order for degradation of all copolymers was zero. The kinetic parameters of the decomposition were determined for all copolymers.
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    URL: http://dx.doi.org/10.1002/apmc.1995.052310117
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    New trends in epr and epr kinetics studies in the stabilization mechanism by N-oxyl radicalsPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland), June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 45-63 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of the solid state oxidation of isotactic polypropylene films and the the mechanism of inhibition by HALS have been investigated by kinetic-ESR and kinetic modelling with derivation of the rate constants for the sensitive steps in the reaction scheme. The results have shown the inadequacy of the Denisov cycle to account for the observed experimental kinetics of the intermediate nitroxyl radicals. The molecular dynamics associated with the oxidation inhibited by HALS in the polypropylene matrix has been investigated by applying the Liouville stochastic method to the analysis of the temperature effects of the ESR spectra of the intermediate nitroxyl radicals used as spin probes. The investigation on the nature and characteristics of the molecular motions available at the oxidation sites has also been carried out with nitroxyl spin labels bound to the PP chains. For this application a novel method of spin labelling was developed based on reactions with some of the oxidation products, namely the terminal and intrachain ketones (keana method), alcohols, peroxides and macroalkyl radicals.
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    Aspects of stabilization with phosphorous antioxidants in polymersPaper presented at the “16th International Conference on Advances in the Stabilization and Degradation of Polymers” in Luzern (Switzerland). June 14-17, 1994. (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 232 (1995), S. 119-131 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: As plastics are being used in a variety of applications, demands on a greater level of processing stability are increasing. Phosphites are noteworthy as effective processing stabilizer and the performance of phosphite antioxidants can be correlated to the chemical structure of phosphites. Cyclic phosphite esters derived from 2, 2′ methylene bis-2, 4-di-tert-butylphenol and some commercially available phosphites were submitted to comparative studies. Decomposition of cumene hydroperoxide, melt flow of polypropylene and consumption of additives after multiple extrusions were investigated to understand the activity of phosphites as process stabilizers in polypropylene.This study suggests that phosphites play an important role in process stabilization when used in combination with sterically hindered phenols, and that the activity of phosphites may be predicted by their reactivity on hydroperoxide.
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    Conformational studies of nucleic acids. V. Sequence specificities in the conformational energetics of oligonucleotides: The homo-tetramers (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 59-77 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational energetics of the tetranucleoside triphosphates d(ApApApA), d(GpGpGpG), d(CpCpCpC), d(TpTpTpT), ApApApA, GpGpGpG, CpCpCpC, and UpUpUpU are thoroughly examined using a classical potential energy function. The sugar modeling method and multiple correlation functions derived in previous papers of this series are utilized in these examinations. The data are analyzed and compared in terms of the energy profiles for rotation about the conformation-determining torsion angles in the tetramers. Overall, the predictions are in reasonable qualitative agreement with the existing experimental data. It is found that the base type does not greatly affect the locations of the important minima in these profiles, but rather exerts a large influence on the relative depths of the minima and the barriers to conversion between them. Conformational sequence dependence is manifest to a greater extent by the DNA tetramers than the RNA tetramers. Of the DNA tetramers, d(CpCpCpC) appears, from the results presented herein, to have the greatest potential for polymorphism. This and other findings are analyzed in terms of the preferences of particular DNA sequences for either the A-, B-, or Z-conformation.
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    A simplified analysis of scatchard plots for systems with two interacting binding sites (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 79-86 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple graphical method for calculating stoichiometric and site binding constants for systems with two initially equivalent interacting sites is derived from a modified Scatchard equation. The binding constants can be calculated from Scatchard plots (r/[A] as a function of r) using the values of r/[A] (r is the molar ratio of bound ligands to total protein and [A] is the equilibrium concentration of free ligand) when r = 0 and r = 1 (half-saturation). The applicability of the method to the adsorption of bilirubin by peptide pendants immobilized on a polyacrylamide support is demonstrated.
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    Application of the augmented theory of α-helix-to-random-coil transitions of two-chain, coiled coils to extant data on synthetic, tropomyosin-analog peptides (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 87-96 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The statistical mechanical theory for the helix-to-random-coil transition in two-chain coiled coils is applied to extant data for two synthetic coiled-coil polypeptides. These peptides have the primary structure K(LEALEGK)n, in which n = 4, 5. This repeating heptet sequence mimics the pattern of hydrophobic, acidic, and basic residues characteristic of the 284-residue tropomyosin molecule, the prototypical coiled-coil protein. Theoretical calculations for single chains show that such model peptides cannot be directly compared to proteins like tropomyosin because of differences in chain length (29 and 36 residues vs 284) and in intrachain interactions, the latter caused by the differences in amino acid composition and seqeunce between protein and model. Application of the theory to extant data on the two synthetic peptides provides a semiquantitative fit and results in an assessment of the interhelix interaction in the model peptides. The value obtained, ∼ 2000 cal · (mol of turn pairs)-1, is four to five times larger than has been obtained for tropomyosin. This probably is a result of greater regularity in the structure of the synthetics and of the exclusive presence of leucine in the hydrophobic interface. The theory employed here insists that this powerful interhelix interaction in the synthetic is the principal reason that such short chains can be so highly helical at moderate and low temperatures. Theory predicts, indeed, that a tropomyosin-length chain with a sequence homologous to these synthetics would be completely thermally stable in the entire temperature range accessible in aqueous solutions. Theory also predicts a much more pronounced effect of concentration on the 29- and 36-residue synthetic polymers than is predicted or observed in the case of tropomyosin, and it also predicts a pronounced stabilizing effect of pH-reduction on the thermal curves. On the last two points, sufficient data are not yet available with which to test the theory.
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    The source of energy for bacteriophage dna packaging: An osmotic pump explains the data (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 165-169 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Masthead (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360270201
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    The combined use of NMR, distance geometry, and restrained molecular dynamics for the conformational study of a cyclic somatostatin analogue (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 323-338 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A cyclic peptide analogue of somatostatin, including the o-aminomethylphenylacetic acid spacer, was studied by the combined use of two-dimensional nmr spectroscopy, distance geometry, and restrained molecular dynamics. Analysis of distances determined from nuclear Overhauser effect (NOE) buildup rates revealed that these were inconsistent with a unique backbone conformation near the spacer. Assuming that the conformational heterogeneity is localized to the spacer, the NOE distances measured for the remaining part of the molecule were used to generate a large number of structures with the distance geometry algorithm, which were then refined by restrained energy minimization. Four classes of structures emerged, which together account for all observed NOEs. A representative structure of each class was further refined with the restrained molecular dynamics technique, and shown to be stable on a 20-ps time scale. The flexibility of the spacer was examined by simulating interconversions induced by an appropriate restraining potential. As a result, the explanation for the lack of somatostatin activity of the analogue studied was reconsidered.
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    Masthead (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.360270301
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    Optical activity of saccharides - the vacuum-uv origin of sodium-D rotation (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 415-421 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A semiempirical theory of saccharide optical activity indicates that the dominant source of NaD rotation is a vacuum-uv CD band near 150 nm, a band observed experimentally in polysaccharide film CD spectra. The model is a modification of polarizability theory in which high-energy electronic excitations are coupled by degenerate perturbation theory, giving rise to “molecular excitons.” The existence of an excitation mode well separated in energy from even higher energy modes arises from the local symmetry of tetrahedral carbon atoms in a puckered ring structure. Calculated NaD rotations correlate well with experimental values.
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    Prediction of protein helix content from an autocorrelation analysis of sequence hydrophobicities (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 451-477 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is demonstrated that protein α-helix content can be predicted from an autocorrelation analysis of the protein hydrophobicity sequence. The Fourier transform of the autocorrelation function yields the spectral densities or weights of the various frequencies contributing to the autocorrelation function. Using sequence and secondary structure data from more than 160 proteins and domains, a linear relationship was found between spectral density at periodicity 3.7 and protein α-helix content (r = 0.83). This relation permits prediction of the helix content (x) of proteins of known sequence to within ± 15%, i.e., as (x ± 15)%. Predictions based on the autocorrelation procedure are compared with values obtained by other methods.
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    Induced CD provides evidence for helical solution conformation in cellulosic chains (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 479-491 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Evidence for a helical contribution to the conformation of methylcellulose in dilute solution is given by CD measurements. Congo red binds to methylcellulose in dilute aqueous solution and becomes optically active. The shape of the induced CD spectra is as predicted by exciton coupling for a helical arrangement of chromophores. The magnitude of the induced CD changes reversibly with temperature, decreasing upon heating. The dimer analogue of the polymer, prepared by acid methanolysis, does not show this effect. These observations suggest that the induced optical activity reflects the conformational dissymmetry of the polymer. Analogous experiments with the cellulose oligomers (cellotriose through cellohexaose) show that five anhydroglucose units are necessary before asymmetry is induced upon dye binding.
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    Polarized raman scattering from oriented single microcrystals of d(A5T5)2 and d(pTpT) (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 493-507 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polarized Raman spectra have been obtained from single microcrystals of the duplex of the decamer d(A5T5)2 using a Raman microscope. This is the first report of Raman spectra from a crystal of a deoxyoligomer that contains only long, nonalternating sequences of adenine and thymine. Sequences containing d(A)n and d(T)n are of interest in view of recent suggestions that they induce bends in DNA and that they might exist in a nonstandard B-conformation. Polarized Raman spectra of a crystal of d(pTpT) have also been obtained. Both crystals display Raman bands whose intensities are very sensitive to the orientation of the crystal with respect to the direction of polarization of the incident laser beam. These spectra indicate that the helical axes of the oligonucleotides are parallel to the long axes of the crystals and that the d(A5T5)2 is not appreciably bent in the crystal. The Raman spectrum from the d(pTpT) crystal indicates that all of the furanose ring puckers are in a C2′-endo configuration since only the C2′-endo marker band at 835 ± 5 cm-1 is present. Crystals of d(A5T5)2 show measurable Raman intensities in both the 838- and 816-cm-1 bands. This indicates the presence of both the C2′-endo and C3′-endo, or possibly other non-C2′-endo, furanose conformations. The 816-cm-1 band is weak so that only a small fraction of the residues are estimated to be in the non-C2′-endo conformation. In both the d(pTpT) and d(A5T5)2 crystals the intensity of the bands due to vibrations of the backbone show only a small dependence on orientation of the crystals. This result is explained by the low symmetry of the puckered sugar rings. It is concluded that Raman spectra obtained from oligonucleotide crystals in which the orientation of the crystal axes to the laser polarization is not carefully controlled may contain intensity artifacts that are due to polarization effects.
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    A critical review of the nucleosidic vibration modes appearing in the 800-500-cm-1 spectral region, based on new harmonic dynamics calculations (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 605-616 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the basis of a harmonic dynamics calculation, it is shown that in the 800-500-cm-1 spectral region of DNA vibrational spectra, the characteristic Raman peaks and ir bands do not arise from the same nucleosidic motions. The Raman spectra involve mainly the ring-breathing modes of nucleic bases while the ir spectra reveal essentially their out-of-plane vibrations. Moreover, the calculated results show the splitting of the guanine- and adenine-residue breathing modes upon their coupling with the sugar-pucker motions. This fact is in agreement with the poly[d(G-C)] and poly[d(A-T)] Raman spectra.
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    A type II β-turn in a flexible peptide: Proton assignment and conformational analysis of the α-factor from saccharomyces cerevisiae in solution (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 431-449 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-dimensional 1H-nmr spectra of the α-mating factor [in dimethyl sulfoxide-d6 (DMSO) and in water] and several dodecapeptide analogues (in DMSO) were obtained. Homonuclear correlated spectroscopy resulted in the complete and unequivocal assignment of all backbone and side-chain resonances of the peptides. The solution conformation of the pheromones was probed using two-dimensional (2D) nuclear Overhauser effect spectroscopy (NOESY) and rotating frame nuclear Overhauer effect spectroscopy (ROESY). The 2D NOE results, and results of complementary one-dimensional experiments, suggest that a type II β-turn is assumed by the central portion of active pheromones in both DMSO and water. Inactive analogues of the α-factor do not exhibit this structural feature. Except for this one β-turn, the nmr parameters for α-factor are indicative of a conformationally flexible molecule in both solvents. This conclusion is in contrast to that of other researchers who have proposed a highly structured conformation of α-factor in aqueous solution.
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    Quantitative analysis of the three regimes of DNA electrophoresis in agarose gels (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 509-524 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An extensive series of experiments has been performed to study the mobility of DNA fragments ranging in size from 2.0 to 48.5 kilobose pairs. By varying the agarose concentration in the gels and the electric field strength, three DNA electrophoresis regimes were clearly identified: the Ogston regime (small DNA fragments in large pores of agarose), the reptation regime without DNA chain stretching (small pores of agarose and weak electric fields), and the reptation regime with DNA chain stretching (small pores of agarose, strong electric fields, and large DNA fragments). Here we report on the experimental identification of these regimes and on the conditions governing the transition between each of them. The onset of reptation and of stretching of DNA chains in gel electrophoresis are described quantitatively for the first time, and a phase diagram for the dynamics of DNA during electrophoresis is presented.
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    Conformations and mitochondrial uncoupling activity of synthetic emerimicin fragments (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 683-701 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several amino terminal fragments of the emerimicins (Ac-Phe1-Aib2-Aib3-Aib4-Val5-Gly6-Leu7-Aib8-Aib9-Hyp10-Gln11-D-Iva12-Hyp13-Ala/Aib14-Phol15) ranging in length from five to ten residues have been synthesized. Nuclear magnetic resonance studies have been carried out on the 1-5, 6-10, 1-6, 1-7, 1-8, 1-9, and 1-10 fragments. The number of solvent-shielded NH groups in CDCl3 solutions for 1-5, 1-6, 1-7, 1-8, 1-9, and 1-10 indicate that 310-helical structures are favored in this solvent. In (CD3)2SO, an additional NH group, assigned to Aib(3) NH is solvent exposed in the fragments longer than six residues, suggesting partial unfolding of the N-terminal β-turn or transition to an α-helical conformation. The data for fragment 6-10 are consistent with a conformation having a single Leu-Aib β-turn. Infrared studies suggest an increase in the number of intramolecular hydrogen bonds with increasing peptide chain length. Appreciable mitochondrial uncoupling activity is observed for peptides with a chain length of at least seven residues. The order of efficiencies of the fragments is 1-7 〈 1-8 ∼ 1-10 〈 1-9, with the decapeptide exhibiting anomalously low uncoupling activity.
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    Molecular and crystal structures of three monothiated analogues of the terminally blocked ala-aib-ala sequence of peptaibol antibiotics (1988)
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 747-761 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular and crystal structures of three monothiated analogues of the blocked L-Ala-Aib-L-Ala sequence of peptaibol antibiotics, t-Boc-L-Ala-Aib-ψ(CSNH)-L-Ala-OMe, Ac-L-Ala-Aib-ψ(CSNH)-L-Ala-OMe, and Ac-ψ(CSNH)-L-Ala-Aib-L-Ala-OMe, determined by x-ray diffraction analyses, are reported. In all cases the peptide chain is folded with ϕ,ψ angles close to or slightly distorted from those expected for a type II β-bend conformation. However, the 4 → 1 H-bond distance falls within the accepted limits only for Ac-L-Ala-Aib-ψ(CSNH)-L-Ala-OMe. The structures are compared with those already published for their two oxygenated analogues.
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    URL: http://dx.doi.org/10.1002/bip.360270504
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