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  • Polymer and Materials Science  (12,981)
  • Wiley-Blackwell  (12,981)
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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The properties (squared dimensions, anisotropy, numbers of intra- and intermolecular contacts) of a single five-way cubic lattice chain embedded into an environment (matrix) of chains of the same length n = 50 were evaluated as a function of matrix volume fraction (matrix density) v and intermolecular interaction between the matrix polymer and the minority chain segments, characterized by a parameter φ. No convincing evidence was found for the occurrence of a coil-globule transition in the range of matrix densities (v ≤ 0.7) and repulsive interactions between matrix and minority chain (φ ≤ 0.2) investigated. For moderate attractive interaction (φ ≈ -0.17) a compensation of the chaincompressing action of the matrix and the chain-expanding interaction with the matrix was observed resulting in a zero-dependence of the size and shape of the minority chain on matrix density. It further turned out that there are fixed relations among the various size and shape data irrespective of the specific combination of matrix density and thermodynamic interaction by which a particular polymer dimension is produced. These interrelations are fairly the same as those evaluated for isolated chains the size of which is varied by an intramolecular energy parameter φi.
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  • 2
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New three phases composite materials made of glassbeads as filler, water as liquid dispersed phase and polystyrene as matrix were obtained by polymerization of a water in oil emulsion formed by water dispersed in styrene in which glass beads are added. For this purpose glass beads have to be modified by silanization by a coupling agent 3-(Trimethoxysilyl)propylmethacrylate (TPM) or a silane Octadecyltrichlorosilane (ODMS), in order to prevent the wetting of the glass by water. Only low coverage of the glass surface by the coupling agent (0,05% of TPM) are convenient for the preparation cellular materials having good mechanical properties. At higher coverage ratio, strong hydrophobic glass beads are obtained which destabilize the water / styrene emulsion and lead to macroporous products. Study of the rheology of the filled emulsion appears to be the more simple and more sensitive method to determine the level of wettability of the glass bead by the emulsion which is the most significant parameter for the preparation of such three phases composite materials. Composite materials made of glass beads, air and polystyrene are simply obtained by evaporation of water under vacuum.
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  • 3
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To test the molecular parameters concerning gas sorption in polymers, the concentration of CO2, N2O, CO, N2, CH4 and the noble gases Ne, He in glassy poly(butylene terephthalate) films (PBTP) has been studied gravimetrically with a recording microbalance at 25°C. The sorption isotherms exhibit downward curvature to the pressure axis. As neither solubility nor adsorption can explain the experimental results, analysis was carried out based on the dual-sorption model: gas dissolution and microvoid filling are considered as independent sorption mechanisms. The parameters of the dual-sorption model for the mentioned penetrants are determined. The results indicate that for parameter correlation the Lennard-Jones potential parameters give a rough idea, but size exclusion of gases in small diameter microvoids is proposed and special chemical interactions must be considered.
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  • 4
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 185 (1991), S. 283-292 
    ISSN: 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 ring opening metathesis polymerisation (ROMP) of 5-cyano-2-norbornene with tungsten hexachloride, tungesten oxytetrachloride, bis(dichloralkoxo)tungsten tetrachloride and bis(dichloralkoxo)tungsten oxydichloride as transition metal component was studied. Methylaluminoxan, diethylaluminium ethoxide, tetraisobutyldialuminoxan and tetrabutyltin served as cocatalyst. Toluene, Chlorobenzene and dichloromethane were used as solvents. The concentration of the tungsten components was in the range from 5 × 10-4 to 5 × 10-3 mol/l. Among the catalyst studied, tungsten hexachloride with diethylaluminium ethoxide proved to be the best. The polymerisation was highly selective with this system even at high monomer/tungsten ratios (e.q. 10200:1) and let to high conversions (≥82%).
    Notes: Die ringöffnende metathetische Polymerisation (ROMP) von 5-Cyano-2-norbornen wurde unter Einsatz von Wolframhexachlorid, Wolframoxidterachlorid, Bis(dichloralkoxo)wolframtetrachlorid und Bis(dichloralkoxo)wolframoxiddichlorid als Übergangsmetallkomponente untersucht. Als Cokatalysatoren dienten Methylaluminoxan, Diethylaluminiumethoxid, Tetraisobutyldialuminoxan und Tetrabutylzinn. Als Lösungsmittel wurden Toluol, Chlorbenzol und Dichlormethan verwendet. Die Konzentration der Wolframkomponente lag im Bereich 5 × 10-4 - 5 × 10-3 mol/l. Unter den geprüften Katalysatoren erwies sich Wolframhexachlorid in Verbindung mit Diethylalumiumethoxid als der geeignetste. Mit diesem System verlief die Polymerisation auch bei großen Monomer/Wolfram-Verhältnissen (10200 :1) hochselektiv und führte zu großen Umsätzen (≥82%).
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  • 5
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of dilution on the chain propagation and termination rate constants was investigated in the polymerization of ethyl acrylate in benzene solution at 50°C, with the rotating sector method. The errors of the above rate constants were determined and, by our method applied to decrease these errors, the errors of the propagation rate constant was reduced to its half value. By the application of our earlier results in polymerization kinetics, we found that in this system the chain propagation step is exclusively responsible for the solvent effects observed. Our experimental results can be quantitatively described in terms of the hot redical theory.
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  • 6
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    Angewandte Makromolekulare Chemie 185 (1991), S. 329-334 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 7
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    Angewandte Makromolekulare Chemie 190 (1991), S. 1-14 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch gemeinsame Reaktion von Benzophenontetracarbonsäuredianhydrid, Maleinsäureanhydrid und Diaminen mit 1,3,5-Triazingruppen wurden niedermolekulare Prepolymere mit Amin-Endgruppen erhalten, die sowohl 1,3,5-Triazingruppen als auch Etherbindungen enthalten. Diese reaktiven Prepolymeren sind in niedrigsiedenden Lösemitteln wie z. B. Chloroform und Tetrahydrofuran löslich. Sie wurden durch Elementaranalyse, IR- und NMR-Spektroskopie, Dampfdruckosmometrie und Viskosimetrie charakterisiert. Beim Erhitzen der Prepolymeren auf Temperaturen zwischen 180 und 190°C tritt Kettenverlängerung durch Michael-Addition auf; gleichzeitig vernetzen sie durch Reaktion der Amin- mit den Maleimid-Endgruppen. Die vernetzten Polymeren sind thermisch stabil; ihr thermisches Verhalten wurde durch TGA, DTA und isotherme Alterung untersucht. Die Biegefestigkeit und interlaminare Scherfestigkeit von aus den Prepolymeren und Carbonfasergeweben hergestellten Laminaten wurden gemessen.
    Notes: Low molecular weight amine-terminated monomaleimide prepolymers containing 1,3,5-triazine groups as well as ether linkages were synthesized by reacting benzophenone tetracarboxylic dianhydride, diamines having 1,3,5-triazine group and maleic anhydride. These reactive prepolymers are soluble in low boiling solvents such as chloroform, tetrahydrofuran etc. They were characterized by elemental analyses, IR and NMR spectroscopy, vapour pressure osmometry, and viscosity. On heating at 180-190°C these prepolymers undergo simultaneous chain extension by Michael addition reaction and crosslinking by mutual reaction between their amine-terminated and maleimide-terminated ends. The cured polymers are thermostable and the thermal behaviour was studied by TGA, DTA, and isothermal aging. Laminates fabricated using these prepolymers and carbon fiber as reinforcing agent were evaluated by their flexural strength and interlaminar shear strength.
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  • 8
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    Angewandte Makromolekulare Chemie 190 (1991), S. 15-32 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Epoxidharz wurde durch Reaktion mit Anilin bzw. Benzylamin in unterschiedlichen molaren Verhältnissen modifiziert. Die modifizierten Harze wurden dann mit Diethylamin und anschließend mit teilblockiertem Toluylendiisocyanat umgesetzt, wobei thermisch vernetzbare Harze mit tertiären Aminen in und am Ende der Polymerkette erhalten wurden. Die partielle Ansäuerung mit Essigsäure lieferte thermisch vernetzbare kationische Harze, aus denen durch Lösen in geeigneten Lösungsmitteln und Zugabe von entionisiertem Wasser Emulsionen hergestellt wurden. Diese wurden hinsichtlich ihrer Eignung zur elektrolytischen Abscheidung untersucht und verglichen. Die Ergebnisse zeigen, daß die Abscheidungsausbeute und das Streuvermögen der Emulsionen aus Benzylamin-modifizierten Epoxidharzen besser sind als die der Anilin-modifizierten Epoxidemulsionen. Ein hohes, vom pH-Wert der Emulsion abhängiges Streuvermögen ist für diese kationischen Harze charakteristisch.
    Notes: Aniline/benzylamine-modified epoxy resins with different molecular weights, which contain tertiary amines in the middle of the polymer chain, were synthesized by the reaction of aniline/benzylamine with epoxy resin at various molar ratios. The resulting aniline/benzylamine-modified epoxy resins were reacted with diethylamine and subsequently reacted with 2-ethylhexanol-blocked toluene diisocyanate to obtain thermally crosslinkable resins which contain tertiary amines at the end and in the middle of the polymer chain. These resins were partially neutralixed with acetic acid to give thermally crosslinkable cationic resins. The resulting cationic resins were dissolved in suitable solvents and mixed with deionized water to form various emulsions. The emulsion and electrodeposition properties of these resins were studied in some detail to compare the properties of these cationic resins. The results show that the deposition yields and throwing power of the emulsions prepared from benzylaminemodified epoxy resins are higher than those of the emulsions prepared from anilinemodified epoxy resins. The emulsion having proper pH values can give a high throwing power. High throwing power is the characteristic property of these modified cationic resins. Factors determining the throwing power and deposition yield of the emulsions were also investigated.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Arylacrylsäuren, wie Furylacrylsäure und Thienylacrylsäure können durch Knoevenagel-Reaktion der Arylcarbaldehyde mit Malonsäure in Pyridin dargestellt werden. Durch einfache Veresterung der Arylacrylsäuren in Methanol/Schwefelsäure werden die entsprechenden Arylacrylsäuremethylester mit guten Ausbeuten erhalten. Diese isomerisieren bei Bestrahlung mit UV-Licht (λ ≥ 280 nm) in methanolischer Lösung. Bei der Photoreaktion in Lösung wurde keine Photodimerisierung beobachtet. Die Reaktionskinetik der Photoreaktionen wurde untersucht.
    Notes: Aryl acrylic acids, e. g. furyl acrylic acid or thienyl acrylic acid are readily formed by the Knoevenagel condensation reaction of arylcarbaldehydes and malonic acid in pyridine. Esterification of these acids with methanol/sulfuric acid gives the corresponding aryl acrylic acid methyl esters in good yields. In methanolic solution these methyl esters isomerize upon irradiation (λ 280 nm). No photodimerization was observed. Kinetic data are given.
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  • 10
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    Angewandte Makromolekulare Chemie 190 (1991), S. 67-80 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Different composite materials, with retified or natural poplar and polyester resin were prepared by molding. The influence of the filler granulometry on certain physicochemical (density, humidity, hardness) or mechanical properties of the materials was studied. The density and the increase of mass in humid atmosphere were always found to be less when the wood was thermally treated. On the other hand, the hardness of the composites made from natural poplar was much higher. The mechanical properties were found to be weak when the wood was retified.When the wood was thermally treated, it was possible to optimise the three parameters, namely, density, water retention capacity and mechanical properties. The optimal granulometry of poplar was determined between 0.75 and 1.5 mm.The results obtained are discussed considering the physico-chemical properties of the different varieties of wood studied and the interactions which exist between the polar resin and the wood.
    Notes: Divers matériaux composites à base de peuplier rétifié ou naturel et de résine polyester insaturée ont été préparés par moulage. L'influence de la granulométrie de la charge a été étudiée sur quelques propriétés physico-chimiques (densité, reprise d'humidité, dureté) ou mécaniques des matériaux obtenus. La densité et la reprise de masse en milieu humide sont toujours plus faibles si la charge est traitée thermiquement sous atmosphère inerte. Par contre, la dureté des composites issus du peuplier naturel est plus importante. Les propriétés mécaniques sont inférieures si la charge est rétifitée.Si la charge lignocellulosique est traitée thermiquement, il est possible d'optimiser les trois paramètres: densité, reprise d'eau et propriétés mécaniques; la granulométrie optimale du peuplier est ainsi comprise entre 0,75 et 1,5 mm.Les résultats obtenus sont expliqués en tenant compte des propriétés physico-chimiques des charges et des interactions existant entre la résine polaire et le bois.
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  • 11
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die vorliegende Arbeit untersucht das Wasserdurchlässigkeitsverhalten von vier Arten verschieden modifizierter Chitosanmembranen zur Abtrennung von Wasser aus wäßrigen Ethanolmischungen. Chitosan wurde aus Chitin von Krebstierschalen durch Verseifung (Deacetylierung) gewonnen. Die in dieser Arbeit untersuchten modifizierten Chitosanmembranen enthielten Carboxymethyl-, Carboxyethyl-, Cyanethyl- und Amidoxim-Chitosan. Die Einführung hydrophiler funktioneller Gruppen in der 6-O Position des Chitosans erhöht die Selektivität der modifizierten Membranen im Vergleich zu den mit Essigsäure komplexierten Chitosanmembranen. Die Untersuchungen zeigen, daß Chitosanmembranen, die Carboxygruppen enthalten, die höchste Wasserdampfdurchlässigkeit aufweisen. Carboxymethyl-Chitosanmembranen zeigen eine maximale Quellung und den höchsten Ethanoldurchfluß bei einer Ethanolkonzentration von ca. 15 Gew.-% im Zulauf aufgrund von Bindungs- und Weichmachereffekten.
    Notes: The present study investigates the pervaporation performance of four kinds of modified chitosan membranes to separate water from aqueous ethanol solution. Chitosan was prepared from chitin abstracted from the crab shell and subsequently deacetylated with aqueous NaOH solution. Modified chitosan membranes examined in this study include carboxymethyl chitosan, carboxyethyl chitosan, cyanoethyl chitosan, and amidoxime chitosan. The incorporation of hydrophilic functional groups into the 6-O position of chitosan enhances the selectivity of modified chitosan membrane compared to the previously reported chitosan-acetic acid complex membrane. Among the modified chitosan membranes, membranes containing carboxy groups show the best pervaporation performance. Carboxymethyl chitosan membranes show the maximum swelling and ethanol flux at approx. 15 wt.-% feed ethanol concentration due to the coupling and plasticizing effect.
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  • 12
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The tensile properties of self reinforced poly(propylene)/poly(1-butene) composites, obtained by rapid extension of the melt, have been measured and correlated to morphological parameters derived from x-ray experiments. Critical fiber lengths as a function of sample composition and the elastic modulus and yield stress of the fibers could be determined. It is shown, that, applying a load to the system, the forces are fully taken up by the fibers and the system breaks by fail of the fibers. The longitudinal structure of the fibers is found to be independent of sample composition.
    Notes: Mechanische Parameter wie Elastizitätsmodul, Fliß- und Bruchspannung von aus der hochorientierten Schmelze hergestellten nadelkristallinen Mischungen aus Poly(propylen) und Poly(1-bute) wurden mit morphologischen Parametern, die aus Röntgenmessungen abgeleitet wurden, korreliert. Es wird gezeigt, daß der Elastizitätsmodul des Verbundes aus den E-Moduln der Fasern und der Matrix berechnet werden kann (Mischungsregel). Die an der Probe angreifenden Kräfte werden voll auf die Fasern übertragen; der Verbund kann daher als eigenfaserverstärktes System angesehen werden. Die Abschätzung der kritischen Faserlänge ergibt, daß die Festigkeit der FAsern voll ausgenutzt wird; der Bruch des Systems bei Belastung ist daher auf das Versagen der Fasern zurückzuführen. Das mechanische Verhalten des Verbundes wird stark beeinflußt durch die Komponentenzusammensetzung. Die longitudinale Struktur der Nadeln beider Komponenten bleibt unbeeinflußt von der jeweiligen Co-Komponente.
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  • 13
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    Angewandte Makromolekulare Chemie 192 (1991), S. 199-211 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Lösliche kationische Polyelektrolyte mit quartären Stickstoffatomen in der Hauptkette wurden durch Polykondensation von Epichlorhydrin (ECH) mit Dimethylamin (DMA) und N,N-Dialkylaminoakylaminen erhalten. Die Reaktionsparameter, die die Polymereigenschaften hauptsächlich beeinflussen, sind: Molverhältnis DMA/asymmetrische Diamine, Ausgangskonzentration der Aminlösung, Molverhältnis ECH/Amine und die Struktur der asymmetrischen Diamine. Das viskosimetrische Verhalten verdünnter wäßriger Lösungen mit oder ohne Zugabe neutraler Salze veranschaulicht die flexible Natur der Polyelektrolyten.
    Notes: Water soluble cationic polyelectrolytes containing quaternary nitrogen atoms within the main chain were prepared via condensation polymerization of epichlorohydrin (ECH) with dimethylamine (DMA) and N,N-dialkylaminoalkylamines. The main parameters of the reaction that influence the polymer properties are: DMA/asymmetrical diamine molar ratio, the initial concentration of amine solution, NaOH/amine molar ratio, ECH/amine molar ratio, and asymmetrical diamine structure. The feature of flexible polyelectrolyte own to the investigated polymers was emphasized by the viscosimetric behaviour in dilute aqueous solutions with and without salt presence.
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  • 14
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    Angewandte Makromolekulare Chemie 192 (1991), S. 213-213 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 15
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    Angewandte Makromolekulare Chemie 193 (1991), S. 1-11 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Antioxidantien wurden in einer modifizierten Friedel-Crafts-Reaktion mit wasserfreiem Zinkchlorid als Katalysator an Flüssig-Naturkautschuk mit Hydroxy-Endgruppen gebunden. Die immobilisierten Antioxidantien waren weniger flüchtig und extrahierbar als konventionelle Antioxidantien. Sie wurden sowohl einem Latex als auch trockenem Kautschuk zugesetzt; die daraus hergestellten Vulkanisate zeigten eine bessere Alterungsbeständigkeit als Vulkanisate mit konventionellen Antioxidantien.
    Notes: Antioxidants were attached to hydroxy-terminated liquid natural rubber by modified Friedel-Crafts alkylation reaction using anhydrous zinc chloride as catalyst. The rubber bound antioxidants were found to be less volatile and less extractable compared to conventional antioxidants. The bound antioxidants were tried both in latex compounds and dry rubber compounds. The vulcanizates showed improved ageing resistance compared to vulcanizates based on conventional antioxidants.
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  • 16
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    Angewandte Makromolekulare Chemie 193 (1991), S. 13-20 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Strom-Spannungs-Charakteristik eines Bisphenol-A-Polycarbonats im Span-nungsbereich 50-1000 V und der Einfluß von UV-Bestrahlung (λ = 225 und 300 nm) und Tempern auf die elektrische Leitfähigkeit (σ) des Polycarbonats wurden untersucht. Die Abhängigkeit von σ gegen 1/T deutet auf zwei verschiedene Leitfähigkeits-mechanismen hin. Aus den Ergebnissen wurden die Aktivierungsenergien der Leitfähigkeit und die Sprungdistanzen berechnet.
    Notes: Current-voltage characteristics of polycarbonate samples (PC) have been studied in the voltage range 50-1000 V. The effect of UV-irradiation at λ = 225 and 300 nm, and thermal annealing on the electrical conductivity (σ) of PC was studied. The σ vs. 1/T relationship shows two slopes, i.e. two possible conduction mechanisms. The obtained results made it possible to determine a complete set of conduction parameters including activation energy and jump distance.
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  • 17
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    Angewandte Makromolekulare Chemie 193 (1991), S. 21-28 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Suspensionspolymerisation wurden Terpolymere aus Acrylnitril (AN), Vinylacetat (VA) (7,5-30 mol-%, bezogen auf AN) und Divinylbenzol (DVB) (10 Gew.-%) hergestellt. Als Verdünner wurden Mischungen von Toluol oder Cyclohexanol (90 Vo1.-%) mit Hexadecan, Octan, Dodecan, 2-Ethylhexanol oder Benzylalkohol (jeweils 10 Vo1.-%) verwendet.Die Porosität der AN-VA-DVB-Terpolymeren ist mit 0,61-0,68 größer als die der entsprechenden AN-DVB-Copolymeren. Die übermolekulare Struktur der Terpolymeren hängt vom verwendeten Verdünner ab, obwohl sich die Porositäten nicht sehr voneinander unterscheiden. Die beim Erhitzen der Terpolymeren auf Temperaturen über 200°C auftretenden thermischen Effekte sind signifikant größer als die bei der Cyclisierung von AN-Polymeren gemessenen.
    Notes: Terpolymers of acrylonitrile (AN), vinyl acetate (VA) (7.5-30 mol-%, related to AN), and divinylbenzene (DVB) (10 wt.-%) were prepared by suspension polymerization. The diluents used were mixtures of toluene or cyclohexanol (90 vol.-%) with solvents (10 vol.-%) such as hexadecane (HD), octane (O), dodecane (D), 2-ethylhexanol (E) or benzyl alcohol (B).It has been found that AN-VA-DVB terpolymers have a higher porosity, about 0.61-0.68, than corresponding AN-DVB copolymers. The terpolymers obtained with mixtures of various diluents differ in their supermolecular structure although they had similar porosity characteristics.The thermal effects accompanying heating of the terpolymers above 200°C significantly exceed that of nitrile groups cyclization observed of the other AN polymers.
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  • 18
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    Angewandte Makromolekulare Chemie 193 (1991), S. 39-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die rheologischen und mechanischen Eigenschaften von Blends aus PE-HD und zwei verschiedenen PE-LLD-Typen wurden im gesamten Mischungsbereich gemessen. Die Polymeren sind im festen Zustand und in der Schmelze ausreichend verträglich, so daß ihre vorteilhaften Eigenschaften genutzt werden können.
    Notes: A high density polyethylene grade is blended with two selected grades of linear low density polyethylene and the mechanical and rheological properties of the blends are evaluated over the entire composition range. The blends show sufficient compatibility in the solid phase and in the melt and hence they can be advantageously used to capitalize on their useful properties.
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  • 19
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    Angewandte Makromolekulare Chemie 192 (1991), S. 51-55 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: N,N-Dimethylacrylamid (DMA) und Isopropylmethacrylat (IPM) wurden in Dimethylformamid mit Azoisobutyronitril als Initiator copolymerisiert. Die Copolymerzusammensetzung wurde 1H-NMR-spektroskopisch ermittelt. Die Copolymerisationsparameter (rDMA = 0,58, rIPM = 2,76) wurden nach Kelen-Tüdős berechnet.
    Notes: Copolymers of N,N-dimethyl acrylamide (DMA) and isopropylmethacrylate (IPM) were prepared in dimethyl formamide using azoisobutyronitrile as initiator. The composition of copolymers was determined by 1H-NMR analysis. Reactivity ratios (rDMA = 0.58, rIPM = 2.76) were calculated from these values by using the Kelen-Tüdős differential linear equation.
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  • 20
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    Angewandte Makromolekulare Chemie 192 (1991), S. 69-79 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird ein allgemeines numerisches Verfahren vorgestellt, um die Modifikation der Grundgleichung für hydrodynamische Schmierung, die von mit Polymeren versetzten Schmierölen mit scherabhängiger Viskosität erbracht wird, zu berechnen.Das Verfahren basiert auf dem verallgemeinerten Newtonschen Fileßmodell und erlaubt, alle Fileßregionen zwischen dem rein Newtonschen und dem Exponentialgesetzverhalten kontinuierlich zu behandeln. Die Ergebnisse zeigen, daß der Einfluß der scherspannungsabhängigen Viskosität durch eine dimensionslose Zahl vollkommen charakterisiert wird, nämlich U · τ*/h*, wobei U die relative Gleitgeschwindigkeit, h* die charakteristische Filmdicke und τ* die Relaxationszeit des Schmieröles darstellen.Als praktisches Beispiel wird die Anwendung des Verfahrens aufgezeigt, um den Einfluß des Molekulargewichts und der Konzentration der Polymerkomponente des Schmieröls auf die hydrodynamische Schmierung zu bestimmen. Dieser Einfluß ist durch die starke Beziehung zwischen Polymereigenschaften und τ* verursacht.
    Notes: A general numerical procedure is presented to calculate the modification of the basic equation for hydrodynamic lubrication brought about by the use of polymeric fluids with shear depending viscosity. The procedure is based on the generalized Newtonian fluid model and allows to treat continuously all the flow regions between the pure Newtonian and the power law behavior. The results show that the influence of the viscosity depending on shear stress is completely characterized by one dimensionless number, namely U.·τ*/h*, where U is the relative sliding velocity, h* is the characteristic film thickness, and τ* is a characteristic time of the lubricant. The procedure is exemplified by applying it for the determination of the influence of the molecular weight and concentration of the polymeric component of the lubricant on the hydrodynamic lubrication. This influence is brought about by the strong relation between the polymer properties and τ*.
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  • 21
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 192 (1991), S. 57-67 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Morphologien von spritzgegossenem und formgepreßtem Poly(1-buten) (PB-1) wurden im Polarisationsmikroskop und im Transmissionselektronenmikroskop untersucht. Eine dünne Oberflächenhaut und bis in den Kern der Probekörper reichende abgeplattet-sphärolithische Strukturen werden bei spritzgegossenem PB-1 beobachtet, während in formgepreßtem PB-1 typische Sphärolithe vorliegen. Das Bruchbild des spritzgegossenen PB-1 zeigt unter der Oberflächenhaut viele aufgereihte streifenartige Hohlräume, die senkrecht zur Spritzrichtung zur Mitte des Probekörpers wachsen. Aus diesen Beobachtungen kann geschlossen werden, daß eine beim Spritzgießen durch den Schmelzefluß induzierte Scherspannung nicht nur die Entstehung der Oberflächenhaut verursacht, sondern auch bis in die Mitte des Probekörpers hinein die Bildung abgeplatteter Sphärolithe bewirkt. Diese abgeplattet-sphärolithischen Strukturen sind für die beim Dehnen des spritzgegossenen PB-1 entstehenden, streifenartigen Hohlräume verantwortlich, während die Oberflächenhaut und die abgeplatteten Sphärolithe im Kern die Sprödigkeit und die im Vergleich zu formgepreßtem PB-1 geringere Bruchdehnung bewirken. Diese kann durch Tempern oberhalb des Schmelzpunktes erhöht werden.
    Notes: The injection-molded poly(1-butene) (PB-1) is found to be more brittle than the compression-molded PB-1. The morphologies of these specimens are examined by use of polarized optical microscopy and scanning electron microscopy (SEM). A skin layer and an oblate spherulitic structure extended to the core region are observed in the injection-molded PB-1, while typical spherulites exist in the compression-molded PB-1. Below the skin layer of the injection-molded PB-1, the fracture surface is found to consist of many aligned strip-like voids with ribbon edges propagating to the center of the specimen and perpendicular to the flow direction of injection-molding. Based on these observations, it can be inferred that shear stress induced by the melt flow during the injection-molding does not only cause the formation of skin layer, but also penetrates deeply into the central region of the injection-molded specimen causing the formation of oblate spherulites. The oblate spherulitic structure is responsible for the aligned voids during elongation of PB-1, while the existence of the skin layer and the oblate spherulites in core region is responsible for the brittleness of the injection-molded PB-1. The elongation of the injection-molded PB-1 is found to be lower than that of the compression-molded. This can be attributed not only to the presence of the skin layer but also to the oblate spherulites in the core region. The elongation can be improved by annealing at a temperature above the melting point of PB-1.
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  • 22
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 192 (1991), S. 103-111 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Kondensation von p-Xylol mit Chloracetylchloride, 1,2-Dichlorethan und Dichlormethan mit Aluminiumtrichlorid in Schwefelkohlenstoff wurden Polyketone hergestellt und IR-spektroskopisch sowie bezuglich des Molekulargewichtes charakterisiert. Die thermischen Eigenschaften wurden thermogravimetrisch und mittels DSC untersucht. Die Prüfung der Harze auf ihre biologische Aktivität gegen Pseudomonas fluorescens, Bacillus subtilis and Aspergillus niger ergab, daß deren Wachstum durch die Polyketonharze kontrolliert werden kann.
    Notes: Some polyketones were prepared from p-xylene, chloroacetylchloride, 1,2-dichloroethane and dichloromethane using anhydrous aluminiumtrichloride and carbon disulfide as solvent. The resins thus obtained have been characterized by IR spectra and number average molecular weight. The thermal properties have been studied by thermogravimetry and differential scanning calorimetry. All the resins were tested for their biological activity against Pseudomonas fluorescens, Bacillus subtilis and Aspergillus niger. The results show that the growth of the tested organisms can be controlled by the polyketone resins.
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  • 23
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    Angewandte Makromolekulare Chemie 192 (1991), S. 145-153 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In der Arbeit wurde die homogene Polyaddition von Pyromellitsäuredianhydrid und 4,4′-Diaminodiphenylmethan untersucht. Die Abhängigkeit des zahlenmittleren Molekulargewichts (M̄n) von der Zeit weist ein Maximum auf. Die Ursache der niedrigen Gleichgewichtswerte von M̄n beruht auf einer durch Wasserspuren im Lösungsmittel verursachten Dianhydridhydrolyse und damit einer gestörten Äquimolarität der funktionellen Gruppen. Im Laufe der Stabilisierung des M̄n-Gleichgewichtswertes entsteht auch die wahrscheinlichste Molmassenverteilung.
    Notes: The homogeneous polyaddition reaction of pyromellitic dianhydride with 4,4′-diaminodiphenylmethane was investigated. The dependence of the number average molecular weights on time has a maximum; low equilibrium values of M̄n are caused by a disturbed equimolarity of functional groups due to the hydrolysis of dianhydride with water present in the solvent. In the course of establishment of the equilibrium M̄n value, the molecular weight distribution changes to the most probable value.
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  • 24
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    Angewandte Makromolekulare Chemie 192 (1991), S. 133-144 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Phasen- und Mischbarkeitsverhalten der binären und ternären Polymermischungen von Polyarylat (PAR), Phenoxid und Poly(butylenterephthalat) (PBT) wurde untersucht. Die Mischungen wurden durch Ausfällen aus gemeinsamen Lösungen hergestellt, und die Mischbarkeit wurde durch DSC-Messungen und Transparenz der Schmelze beurteilt. Im Falle der binären Blends zeigten PAR/PBT und Phenoxid/PBT Mischbarkeit, während sich PAR/Phenoxid nicht mischen ließ. Die Mischbarkeitstendenz der unmischbaren PAR/Phenoxid-Mischungen konnte jedoch durch Zugabe von PBT erhöht werden; eine ausreichende Menge PBT machte die ternären Mischungen mischbar, so daß diese eine einzige Tg in der DSC-Kurve zeigten. Im ternären Phasendiagramm war das Maximum der Mischbarkeitsgrenze in Richtung auf die Phenoxidseite hin verschoben, was auf die bessere Mischbarkeit von PAR/PBT im Vergleich zu Phenoxid/PBT zurückgeführt wird.
    Notes: The phase and miscibility behavior of binary and ternary blends containing polyarylate (PAR), polyhydroxyether of bisphenol AIUPAC: poly[oxy(2-hydroxytrimethylene)oxy-1,4-phenylene-isopropylidene-1,4-phenylene]. (Phenoxy), and poly(butylene terephthalate) (PBT) were studied. The blends were prepared by solution-precipitation method and miscibility was examined by DSC and melt transparency. In binary blends, PAR/PBT and Phenoxy/PBT blends show miscibility, while PAR/Phenoxy appeared to be immiscible. However, the miscibility of incompatible PAR/Phenoxy blend was enhanced by addition of PBT. The addition of sufficient amount of PBT caused the ternary blend to have a single glass transition temperature. The shape of miscibility boundary of ternary blend was skewed to the apex of Phenoxy, which was attributed to the better miscibility of PAR/PBT than that of Phenoxy/PBT.
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  • 25
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Festphasen-Polykondensation von amorphen, unorientierten Poly(ethylenterephthalat)-Folien (PET) (Vorstufe der Du Pont Mylar® -Polyesterfilme), die mit einem speziellen Katalysator-und Monomer-System hergestellt wurden, war Gegenstand dieser Arbeit. Der Einfluß verschiedener Reaktionsparameter, wie Reaktionstemperatur und -zeit, auf die inhärente Viskosität (ηinh) und auf die Anzahl der Carboxy-und Hydroxy-Endgruppen wurde untersucht. Aus den Messungen von ηinh wurde eine empirische Gleichung erstellt, die die Berechnung von M̄n der PET-Folien nach der Festphasen-Polykondensation bei gegebener Zeit und Temperatur erlaubt. Das Schmelzverhalten verschiedener Festphasen-Polykondensate wurde ebenfalls untersucht.
    Notes: The solid-state polycondensation of poly(ethylene terephthalate) (PET) amorphous and unoriented films from Du Pont (precursor for their Mylar® Du Pont's registered trade mark for the polyester film. polyester film) prepared from a specified catalyst and monomer system has been studied. The effect of various reaction parameters such as reaction temperature and time on inherent viscosity (ηinh) and number of carboxy and hydroxy end-groups has been investigated. From ηinh measurements an empirical equation was taken which allows the calculation of (M̄n) of PET film after solid-state polycondensation at a certain temperature and time. The melting behaviour of the solid-state polycondensated samples was also studied.
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  • 26
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Sphärische makroporöse Partikel, die als Trägermaterialen für verschiedene Säulen-Operationen eingesetzt werden sollen, wurden mittels Suspensions- und Mikrosuspensionspolymerisation von Trimethylolpropan-trimethacrylat (TRIM) in Gegenwart verschiedener Mengen porogener Reagenzien (Toluol bzw. Mischungen von Toluol und Isooktan) hergestellt. Textur und Eigenschaften der Partikel variierten deutlich mit dem Anteil und der Zusammensetzung des porogenen Reagens und wurden zusätzlich durch die Wahl des Suspensionstabilisators beeinflußt. Die makroporösen Partikel wiesen ein Gesamtporenvolumen von 0,4 bis 3,6 cm3/g und eine spezifische Oberfläche von 7 bis 〉 450 m2/g auf. Alle Partikel enthielten Makroporen und, außer den Teilchen mit sehr niedriger spezifischer Oberfläche, einen gewissen Anteil an Mikroporen (Durchmesser 〈 60 Å). Durch Erniedrigung der Monomerkonzentration und Erhöhung des Isooktan-Gehaltes im porogenen Reagens auf 50 Gew.-% konnte das Auftreten von Mikroporen vollständig unterdrückt werden. Das Erhöhen des Isooktan-Gehaltes führte zu einem vergrößerten Gesamtporenvolumen und zu einem verringerten Quellvermögen der Polymermatrix in Toluol. Der Einfluß einer Hitzebehandlung bei 130°C und eines Aufpfropfens von Polymethylmethacrylat auf die Partikeleigenschaften wurde ebenfalls untersucht.Die Menge an nicht umgesetzten Doppelbindungen in den Partikeln konnte durch Variation der Polymerisationstemperatur verändert werden. Das Vorhandensein leicht zugänglicher Doppelbindungen ist wichtig, da sie zur Funktionalisierung der festen makroporösen Partikel verwendet werden können.
    Notes: Spherical macroporous particles, intended for use as carrier particles in various types of column operations, were prepared by suspension and microsuspension polymerization of trimethylolpropane trimethacrylate (TRIM), in the presence of various amounts of porogenic agents (toluene or mixtures of toluene and isooctane). The texture and properties of the particles varied markedly with the amount and composition of the porogenic agent, and were also affected by the choice of suspension stabilizer. Macroporous particles were prepared, ranging in total pore volume from 0.4 to 3.6 cm3/g, and in specific surface area from 7 to 〉450 m2/g. All of the particles contained macropores, and except for those with very low specific surface area, contained a certain fraction of micropores (diameter 〈60 Å). The presence of micropores could be eliminated completely by decreasing the monomer concentration and increasing the isooctane content of the porogenic agent to 50 wt.-%. Increasing the isooctane content also resulted in an increase in the total pore volume and a decrease in the tendency of the polymer matrix to swell in toluene. The effect on properties of particles by heat treatment at 130°C and by grafting poly(methyl methacrylate) onto the particles was also studied.The amount of unreacted double bonds of the particles could be varied by varying the polymerization temperature. The presence of easily accessible double bonds is important as they can be utilized for functionalization of the rigid macroporous particles.
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  • 27
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    Angewandte Makromolekulare Chemie 191 (1991), S. 31-38 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine einfache Methode für die Bestimmung der Grenzflächenhaftung in kurzfaserverstärkten Polymeren, beruhend auf der Längenverteilung von aus der Bruchfläche herausgezogenen Faserteilen, wurde entwickelt. Die Messungen mit Faserverbundwerkstoffen von isotaktischem Polypropylen mit 32 Gew.-% Kurzglasfasern bestätigen die Brauchbarkeit dieser Methode für eine empfindliche Beurteilung von Unterschieden in der Grenzflächenhaftung. Die Einflüsse von Temperatur, Polymer- und Glasfasermodifizierung sowie Faserorientierung auf die Grenzflächenhaftung wurden untersucht.
    Notes: For the evaluation of the interfacial adhesion in short-fibre composites, a simple method based on fibre pull-out length distribution was proposed. The experiments with three composites of isotactic polypropylene with 32 wt.-% of short-glass fibres confirm the potentials of the method for a sensitive determination of differences in the interfacial adhesion. The effects of temperature, crystallinity and fibre orientation angle on the interfacial adhesion were investigated.
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  • 28
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: PE und EPDM-Kautschuk wurden durch Aufpfropfen von Dibutylmaleat (DBM) mit Dicumylperoxid (DCP) als Initiator in Substanz im Temperaturbereich von 140-220°C funktionalisiert. Der Pfropfungsgrad wurde IR-spektroskopisch und durch DSC-Messungen ermittelt. Die für die Pfropfung optimalen DBM- und DCP-Konzentrationen betragen 0,5 bzw. 0,2 Gew.-%. Die Kinetik der Pfropfreaktion ist für PE und EPDM vergleichbar; die Aktivierungsenergien betragen ca. 145 bzw. 130 kJ/mol. Die Pfropfungsgrade sind für PE höher als für EPDM; bei PE/EPDM-Blends steigt der Pfropfungsgrad mit zunehmendem PE-Anteil. Ein Pfropfungsmechanismus, der Nebenreaktionen berucksichtigt, wird vorgeschlagen.
    Notes: Functionalization of polyethylene (PE) and ethylene propylene diene terpolymer (EPDM) in the bulk through dicumyl peroxide (DCP) initiated grafting of dibutyl maleate (DBM) has been studied in the temperature range from 140 to 200°C. The degree of grafting has been determined by infrared spectrophotometry and DSC. The concentration of DBM and DCP has been optimized. 0.5 wt.-% and 0.2 wt.-% DCP for PE and EPDM, respectively, and 10% DBM for both have been found to be the optimum. The kinetics of the grafting reaction is comparable for PE and EPDM. The activation energy of grafting is ca. 145 kJ/mol for PE and ca. 130 kJ/mol for EPDM. The influence of structure of polyolefins on the degree of grafting has also been studied. A higher degree of grafting is obtained for PE than for EPDM. For PE/EPDM blends, the degree of grafting increases with increasing PE content in the blends. A through discussion and proposed mechanism for grafting and other competitive secondary reactions has been provided.
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  • 29
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    Angewandte Makromolekulare Chemie 191 (1991), S. 71-80 
    ISSN: 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 dynamisch-mechanischen Eigenschaften von gehärteten Epoxidharzen, gefüllt mit porösen Siliciumdioxid-Mikrokugeln mit unterschiedlichen spezifischen Oberflächen, Porenradien, Porenvolumina und adsorbierter Wassermenge, wurde untersucht. Die Glasubergangstemperaturten (Tg) der Composite sind 12-14°C niedriger als die des ungefullten Harzes, was auf die bevorzugte Adsorption von Härter an den porösen Mikrokugeln zurückgeführt wird. Mit zunehmender adsorbierter Wassermenge steigt die Tg der Composite an. Der Speichermodul ist mit der mit Quecksilber bestimmten spezifischen Oberfläche (Hg-Oberfläche) der Mikrokugeln, die der Summe der Oberfläche von Poren mit einem Durchmesser größer als 4 nm entspricht, korreliert.Das Verbältnis tan δc/tan δm nimmt mit zunehmender Hg-Oberfläche ab.
    Notes: Dynamic mechanical properties were studied for epoxy resin filled with porous silica microballoons with varying surface area, pore radius, pore volume and adsorbed water. The glass transition temperature (Tg) of the composites is 12-14°C lower than the Tg of the unfilled epoxy resin. This Tg depression is attributed to the preferential adsorption of curing agents on the porous silica microballoons. Tg of the composite increases with increase in the adsorbed water on fillers. The storage modulus has a distinct correlation with the Hg-surface area of silica microballoons, which corresponds to the sum of the surface area of pores with radii larger than about 4 nm.Tan δc tan δm decreases with increasing Hg-surface area.
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  • 30
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Membranen aus Blends von Nylon 6 mit Poly(acrylsäure) (PAA) mit PAA-Gehalten zwischen 25 und 45 Gew.-% wurden durch Filmgießen hergestellt und anschließend durch Eintauchen in eine Aluminiumsalzlösung ionisch vernetzt. Die Glasübergangstemperaturen (Tg) der Membranen wurden mit der DSC-Methode bestimmt. Alle Proben zeigen eine einzige Tg oberhalb der Tg der Homopolymeren, die sich mit zunehmender Scanzeit verschiebt; dies wird auf die Eliminierung von Wasser und die Bildung von Anhydriden im nicht vernetzten PAA-Anteil zurückgeführt.Die Morphologie wurde rasterelektronenmikroskopisch untersucht; die Membranen zeigen eine dichte, porenfreie Struktur ohne Phasenseparation, was auf eine völlige Mischbarkeit der beiden Homopolymeren im untersuchten Zusammensensetzungsbereich schließen läßt. Die Festigkeit der Membranen liegt je nach PAA-Gehalt zwischen 5 und 26 MPa; Membranen mit hohem PAA-Anteil zeigen trotz höherer Vernetzungsdichte eine geringere Zugfestigkeit, was mit der geringen Festigkeit von PAA und der mit größerem PAA-Anteil zunehmenden Quellung zusammenhängt. Letztere wurde durch Messen der Wasseraufnahme trockener Membranen bestimmt; sie steigt von 23,6 Gew.-% bei einem PAA-Gehalt von 25 auf 76,3 Gew.-% bei einem PAA-Gehalt von 45 Gew.-%.
    Notes: Ionically crosslinked blended membranes were prepared from blends of nylon 6 and poly(acrylic acid) (PAA) with the proportion of PAA ranging from 25 to 45 wt.-%. The technique consists of casting a film of the blend, followed by drying and immersion in an aluminum salt crosslinking solution for a predetermined time. The glass transition temperature (Tg) of the membranes was determined by differential scanning calorimetry (DSC). All the samples exhibited a single Tg, which is higher than that of either polymer. There is also a shift in the Tg with increasing scanning time. This phenomenon is attributed to the elimination of water molecules and the formation of anhydrides in the non-crosslinked PAA portion of the membrane. The membrane morphology was studied using scanning electron microscopy (SEM) and shows a dense structure without any pores. No phase separation is observed by scanning cross-sections of the samples, indicating that nylon 6 and PAA are completely miscible in the ranges studied. The membrane material strength lies in the range of 5 to 26 MPa and varies with the amount of PAA in the membrane. Samples with higher PAA content show lower tensile strength in spite of increased crosslinking density. This is due to the inherent low strength of PAA, coupled with increasing swelling of the membrane with increasing PAA content. The latter is confirmed by the measurement of water uptake into a dry membrane which increases from 23.6% to 76.3% with the membrane PAA content increasing from 25 to 45 wt.%.
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  • 31
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    Angewandte Makromolekulare Chemie 191 (1991), S. 81-107 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Practically no adhesion is observed at the interface poly(tetrafluoroethylene)/glass fiber. We have investigated methods to improve adhesion between these interfaces. We have also discussed the question of possible reinforcement, i.e. increase of tensile strength and a simultaneous decrease of elongation.In this first part we present some calculations demonstrating the prerequisites for reinforcement using existing theoretical models. We describe the influence of modification of the glass fiber surface by dispersion coating or by plasma polymerization.In a second part the influence of polymer surface modification and of additives will be dealt with.
    Notes: In Mehrphasensystemen aus Poly(tetrafluorethylen) (PTFE) und Glasfasern besteht praktisch keine Haftung zwischen Matrix und Füllstoff. Es wurde der Frage nachgegangen, ob es Wege zur Verbesserung der Grenzflächenhaftfestigkeit gibt und ob diese Verbesserungen ausreichen, eine Verstärkung, d. h. Anhebung der Reißfestigkeit bei gleichzeitigem Rückgang der Dehnung des Gesamtsystems zu erzielen.In diesem ersten Teil wird den theoretischen Voraussetzungen und der Modifizierung der Füllstoffoberflächen mittels Dispersionsbeschichtungen sowie Plasmaätzen und Plasmapolymerisation nachgegangen.In einem zweiten Teil werden Möglichkeiten zur Verbesserung der Grenzflächenhaftung durch Modifizierung der Polymer-Oberfläche und durch Additive untersucht.
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  • 32
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    Angewandte Makromolekulare Chemie 191 (1991), S. 109-126 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Practically no adhesion is observed at the interphase of poly(tetrafluoroethylene)/glass fiber. We have investigated methods to improve this adhesion and discuss the influence of this improved adhesion on the mechancial properties of the multiphase system.In this paper the influence of a modified polymer surface and of additives is described.
    Notes: In Mehrphasensystemen aus Poly(tetrafluorethylen) (PTFE) und Glasfasern besteht praktisch keine Haftung zwischen Matrix und Füllstoff.Es wurde die Frage untersucht, ob es Methoden gibt, diese Grenzflächenhaftung zu erhöhen und welchen Einfluß diese Erhöhung auf die Eigenschaften des Verbundsystems hat.In dem hier vorliegenden Teil 2 wird speziell auf den Einfluß der Modifizierung der Polymeroberfläche und des Zusatzes von Additiven eingegangen.
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  • 33
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    Angewandte Makromolekulare Chemie 191 (1991), S. 127-144 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Due to the very strong variation of the viscosity of the reaction mass with increasing monomer conversion, three stationary states for the tubes of a multitubular system with cooling vessel can be found. As a consequence, a maldistribution of the fluid arises, so that the reactor stability and the polymer quality are negatively influenced. The recycling of the reaction mass is a helpful method to increase the reactor stability. In this paper some fundamental aspects of the use of multitubular reactors for the polymerization of styrene are studied.
    Notes: Infolge der sich mit steigendem Monomerumsatz stark verändernden Viskosität der Reaktionsmasse existieren im Multirohrreaktor mit Kühlung mindestens drei stationaäre Punkte bezüglich des Einzelrohrmassenstromes gleichzeitig. Als Konsequenz ergibt sich eine Ungleichverteilung der Rohrbelastung, die sowohl die Reaktorstabilität als auch die Polymerqualität negativ beeinflußt. Das Betreiben einer Rückführung kann das Reaktorverhalten stabilisieren. In der vorgelegten Arbeit werden einige fundamentale Aspekte der Anwendung von Multirohrreaktoren für die Massepolymerisation von Styrol untersucht.
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  • 34
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    Angewandte Makromolekulare Chemie 191 (1991), S. 171-176 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die nucleophile Substitution von verschieden substituierten Phenoxygruppen in Polyphenylacrylaten durch Ethanolamin in Dioxan wurde bei 60, 80 und 100°C untersucht. Der Umsatz wurde IR- und 1H-NMR-spektroskopisch und elementaranalytisch bestimmt; er hängt sowohl von der Temperatur als auch von der Art der Substituenten am Phenylring ab.
    Notes: The nucleophilic substitution reaction of differently substituted phenoxy groups with ethanolamine in various poly(phenyl acrylate)s was investigated in dioxane at 60, 80, and 100°C. The conversion, as determined from IR- and 1H-NMR spectroscopy and elemental analysis, depends on the temperature and the kind of substituents at the phenyl ring.
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  • 35
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    Angewandte Makromolekulare Chemie 214 (1994), S. 57-65 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Positive und negative Photostrukturen wurden in einem Polyimid (PI) aus 4,4′-Biphthalsäureanhydrid (BPA) und 4,4′-Diamino-3,3′-dimethyldiphenylmethan (DADMDPM), PI(BPA/DADMDPM) erzeugt, nachdem dieses mit Michlers Keton (MK) bzw. Benzophenon (BP) dotiert und einer ultravioletten Strahlung von 400 ± 50 nm ausgesetzt und naß entwickelt wurde. Das Prinzip der positiven Abbildung basiert auf dem Photokupplungseffekt von MK mit PI, der die Löslichkeit des Polyimids erhöht und so die Entwicklung eines Positivmusters ermöglicht. Die Erzeugung negativer Muster wird durch intermakromolekulare Wasserstoffbrücken zwischen der Carbonylgruppe des Imid-Rings und der Hydroxygruppe, die bei der photoinduzierten Kupplung von Benzophenon mit dem Polyimid gebildet wird, bewirkt. Die lithographische Auswertung zeigt, daß der mit MK dotierte, positive Polyimidfilm nicht in der Lage ist, brauchbare Muster zu erzeugen, da die UV-Wellenlängen von MK absorbiert werden, wodurch die Photokupplung in den tieferen Schichten des Films verhindert wird. Andererseits können in dem 0,6 μm dicken, mit Benzophenon dotierten Polyimidfilm sogar 2 μm schmale Linien aufgelöst werden.
    Notes: Positive and negative photostructures are formed after the polyimide (PI) of 4,4′-biphthalic anhydride (BPA) and 4,4′-diamino-3,3′-dimethyldiphenylmethane (DADMDPM), PI(BPA/DADMDPM) is doped with Michler′s ketone (MK) and benzophenone (BP), respectively, and is subjected to UV light (400 ± 50 nm) irradiation and solvent development. The principle of positive feature formation is based on the photocoupling of MK with PI, which increases PI solubility and thus enables a positive pattern to be developed. The phenomenon of negative photopatterning results from intermacromolecular H-bonding between the carbonyl group of the imide ring and the hydroxy group which is formed in the photoinduced coupling reaction between BP and PI. Lithographic evaluation shows that the MK-doped positive-acting PI film cannot form useful patterns because UV wavelengths are strongly absorbed by MK, which limits the depth of photocoupling in the film. On the other hand, 2-μm-wide lines can be resolved in the BP-doped negative-acting 0.6-μm-thick PI film.
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  • 36
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    Angewandte Makromolekulare Chemie 214 (1994), S. 101-113 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyhydrazid/Polyamid-Blends (PEHZ12/PA6) wurden durch Niedrigtemperatur-Polykondensation von 4,4′-Dichlorformyl-α,ω-diphenoxydodecan und Terephthaloyldihydrazid (TDH) zu Poly(etheraroylhydrazid) in Gegenwart von Polyamid 6 synthetisiert. Die DSC-Analysen lassen vermuten, daß die zwei Polymerkomponenten nicht wechselwirken. Bei der Extraktion des PA6-Anteils der Blends mit Ameisensäure zeigt die Charakterisierung des PEHZ12-Extraktionsrückstands aber, daß zumindest bei bestimmten Zusammensetzungen Wechselwirkungen zwischen den Komponenten auftreten. Modellreaktionen erlauben die Annahme, daß die PEHZ12-Polymerisation zwischen den Amino-Endgruppen des PA6 und den wachsenden PEHZ12-Polymerketten abläuft.
    Notes: Poly(etheraroylhydrazide) is synthesized in the presence of PA6 by means of low-temperature condensation polymerization of 4,4′-dichloroformyl-α,ω-diphenoxydodecane with terephthaloyl dihydrazide (TDH) in order to prepare polyhydrazide/poly-amide 6 (PEHZ12/PA6) blends. The thermal analysis of the blends by DSC seems to indicate that the two polymers are not interacting. Nevertheless, when the blends are subjected to an extraction process with formic acid in order to remove the PA6, the characterization of the residual PEHZ12 reveales that some interactions do occur between the constituent polymers, at least for selected compositions. Model experiments permit to hypothesize that the polymerization of PEHZ12 proceeds with a chemical interaction between amino end groups of PA6 and growing PEHZ12 chains.
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  • 37
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    Angewandte Makromolekulare Chemie 214 (1994), S. 179-196 
    ISSN: 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 crystallization behavior of PBT as well as PC is changed in the controlled-processed blend due to intermolecular interactions between the different macromolecules in molten state.If the kinetics of the crystallization process prevents a crystallization-induced separation, the partial miscibility of the amorphous phases, measured by the glass transition temperatures, will lead to a decrease of the crystallinity of PBT. The crystallinity, normalized to the concentration of PBT in the blend, is independent from the concentration of PC at low coolling rates.At high cooling rates, PBT is crystallizing stepwise in the blend PBT/PC 40/60 wt.-%. The crystallization temperature in the anisothermic crystallization process is increased at low contents of PC due to a changed nucleation mechanism. The half-time of crystallization is increasing in blends with an increasing PC-content in isothermic crystallization experiments.The normally amorphous PC crystallizes considerably fast in presence of PBT in PC-rich blends. The crystallization or change in the state of order of PC was measured in situ by X-ray diffraction. Calorimetric experiments confirm this result and allow a quantitative estimation of the PC-crystallinity, which amounts to some 20% in the blend PBT/PC 5/95 wt.-%.
    Notes: Das Kristallisationsverhalten sowohl von PBT als auch von PC ist im definiert verarbeiteten Blend infolge intermolekularer Wechselwirkungen zwischen den unterschiedlichen Molekülen in der Schmelze verändert.Die über die Glasübergangstemperaturen gemessene teilweise Mischbarkeit der amorphen Phasen führt bei PBT zu einer Erniedrigung des Kristallinitätsgrades, wenn die kinetischen Bedingungen des Kristallisationsprozesses keine kristallisationsbedingte Entmischung zulassen. Der auf den PBT-Anteil normierte Kristallinitätsgrad ist bei kleinen Abkühlgeschwindigkeiten vom PC-Anteil unabhängüg.In der Mischung PBT/PC 40/60 Gew.-% kommt es bei hohen Kühlraten zu einer fraktionierten Kristallisation. Die Kristallisationstemperatur bei anisothermer Kristallisation ist bei geringen PC-Gehalten durch Änderung des Keimbildungsmechanismus erhöht. Bei isothermer Kristallisation steigt mit zunehmendem PC-Anteil die Kristallisationshalbwertszeit des PBT an.Das normalerweise amorphe PC kann in Gegenwart von PBT in den PC-reichen Mischungen besonders schnell kristallisieren, wobei der Kristallisations- bzw. Ordnungsprozeß des PC in situ mittels der Röntgenbeugung gemessen wurde. Kalorimetrische Untersuchungen bestätigen dieses Ergebnis und erlauben eine quantitative Abschätzung des PC-Kristallinitätsgrades zu ca. 20% im Blend PBT/PC 5/95 Gew.-%.
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  • 38
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    Angewandte Makromolekulare Chemie 214 (1994), S. 197-210 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Elementaranalytische sowie NMR-, IR- und UV-spektroskopische Untersuchungen zeigen, daß die Photolyse von Halogenphenolnovolaken zur Substitution der Halogenatome durch Wasserstoff, der Bildung chinoider Gruppen und intermolekularen Vernetzung führt. Die Geschwindigkeit der Halogeneliminierung hängt von der Art des Halogens ab. Sie steigt in der Reihenfolge F 〈 Cl 〈 Br 〈 I. Die Chloreliminierung aus der 4-Position ist gegenüber der aus der 2- und 3-Position begünstigt. Außerdem verläuft die Abspaltung para-ständiger Chloratome aus Dimeren schneller als aus Trioder Tetrameren. ESR-Messungen bei 77 K sowie die Laserblitzphotolyse bei 296 K deuten auf die intermediäre Bildung von Phenoxyl- und Arylradikalen. Lithographische Tests belegen die hohe UV-Empfindlichkeit von Resisten auf der Basis von Halogenphenolnovolaken. Im Vergleich zu nichthalogenhaltigen Novolakresisten wird eine 6 - 10fache (System: 4-Chlorphenolnovolak/4,4′-Bisazidobiphenyl (5%)) bzw. eine ca. 25fache (System: 4-Chlorphenol-/m-Cresolnovolak/Hexamethoxymethylmelamin (5%)) Steigerung der Empfindlichkeit erreicht. Zur Interpretation wird ein Mechanismus postuliert, demzufolge die durch Halogenabspaltung hervorgerufene Sekundärradikalbildung zu einer zusätzlichen Vernetzung beiträgt. In den melaminhaltigen Resisten katalysiert der gebildete Halogenwasserstoff (Hal· + RH → H-Hal + R·) außerdem die Reaktion der Melaminverbindung mit der Novolakmatrix.
    Notes: The photolysis of halogenophenol novolacs is determined by the substitution of halogens by hydrogen and the formation of quinoid groups and intermolecular crosslinks. This is concluded from elemental analysis, NMR, IR and optical absorption measurements. The rate of halogen release depends on the chemical nature of the halogen. It increases in the order F 〈 Cl 〈 Br 〈 I. Chlorine elimination from 4-position is favored over that from 2- and 3-position. Moreover, dimers release chlorine from 4-position much more readily than trimers and tetramers. ESR measurements at 77 K and flash photolysis studies at 296 K yielded evidence for the intermediate existence of phenoxyl and aryl radicals. Lithographic tests demonstrated the high UV-sensitivity of resist formulations based on halogen-containing novolacs. The increase in sensitivity relative to that of formulations based on nonhalogenated novolacs is 6 to 10fold system: 4-chlorophenol novolac/4,4′-bisazidobiphenyl (5%) and ca. 25fold system: 4-chlorophenol/m-cresol novolac/hexamethoxymethylmelamine (5%). A postulated reactions mechanism concerning the sensitivity increase takes into account that halogen elimination results in the formation of additional radicals that accelerate the rate of crosslinking. Moreover, hydrogen halide generated by hydrogen abstraction of halogen radicals (Hal· + RH → H-Hal + R·) provides for the acid required to catalyze the reaction of the melamine compound with the novolac matrix.
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  • 39
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    Angewandte Makromolekulare Chemie 215 (1994), S. 11-24 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Calciumcarbonate unterschiedlicher Teilchenform (sphäarisch, kubisch und nadelfäormig) wurden mit Polypropylen (PP) in einer Zwei-Walzen-Mäuhle gemischt und anschließend zu Platten gepreßt. Der Einflußder Teilchenform auf das Kristallisationsverhalten der PP/CaCO3-Composite, d.h. Kristallisationspeaktemperatur (Tmax), Kristallisationsverlauf usw., wurde mittels Differentialkalorimetrie untersucht. Der Wert von Tmax häangt von der Größe der Gesamtoberfläache der CaCO3-Teilchen ab; Tmax ist bei nadelfäormigen Teilchen gräoßer als bei kubischen oder sphäarischen und hauangt in allen Fäallen der nicht-isothermen Kristallisation von der Abkäuhlgeschwindigkeit und der vorher erreichten maximalen Temperatur ab.
    Notes: Calcium carbonate of various particle shape (spheric, cubic, needle-shaped type) and polypropylene (PP) were mixed on a two roll mill and the mixture was pressed into plates. The effect of particle shape on the crystallization behavior of PP/CaCO3 composites, such as crystallization peak temperature (TMAX), crystallized pattern, etc., was investigated with differential scanning calorimetry measurements. The value of TMAX is explained by the total surface area of added CaCO3 particles; TMAX of needle-shaped series is larger than that of cubic or spheric ones. TMAX of various shaped CaCO3-filled PP totally depends on the cooling rate and maximum temperature in the non-isothermal crystallization, respectively.
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  • 40
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    Angewandte Makromolekulare Chemie 215 (1994), S. 107-119 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Polyaddition von Polyethylenglykol (PEG) Oligoglycidylethern (Mn (PEG): 396,587, 1437 und 3554) mit asymmetrischen Diaminen, wie N,N-Dimethylund N,N-Diethyl-1,3-diaminopropan, wurden wasserläosliche kationische Polymere erhalten. Die Eigenschaften der kationischen Polymeren sind vom urspräunglichen PEG-Molekulargewicht und der Diaminreaktivitäat abhäangig. PEG mit Mn = 396 zeigt das beste Verhalten. In verdäunnten wäassrigen Läosungen und in wäassrigen 2M NaCl-Läosungen der Polymeren wurde das Polyelektrolytverhalten veranschaulicht. Die Gegenwart der PEG Kette bestimmt das Polyelektrolytverhalten in den 2M NaCl Läosungen.
    Notes: Water-soluble cationic polymers were obtained by polyaddition of poly(ethylene glycol) (PEG) diglycidylethers (M̄n of PEG were 396, 587, 1437 and 3554, resp.) with asymmetrical diamines such as N,N-dimethyl-1,3-diaminopropane and N,N-diethyl-1,3-diaminopropane. The cationic polymer properties depend on the PEG initial molecular weight and on the diamine reactivity too. PEG with M̄n = 396 had the best behaviour in these reactions. The polyelectrolyte feature of cationic polymers was emphasized both in dilute aqueous solutions and in 2M aqueous NaCl solutions. The polyelectrolyte behaviour in 2M aqueous NaCl solution is determined by the PEG chain presence.
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  • 41
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    Angewandte Makromolekulare Chemie 215 (1994), S. 139-145 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Reaktion von o-Kresol mit Formaldehyd wurde unter Verwendung verschiedener tertiäarer Amine als Katalysatoren untersucht. Der Einfluß der Reaktionsparameter Basizitäat, Temperatur, Reaktionszeit und Formaldehydkonzentration wird diskutiert. Für die bevorzugte Bildung von 2,4-Bis(hydroxymethyl)-6-methylphenol wurden optimierte Synthesebedingungen erarbeitet. Die Bildung von Zwei-bzw. Mehrkernprodukten konnte nicht ausgeschlossen werden.
    Notes: The reaction between o-cresol and formaldehyde was investigated using various tertiary amines as catalysts. The influence of the reaction parameters basicity, temperature, reaction time and concentration of formaldehyde was discussed. To yield preferentially 2,4-bis(hydroxymethyl)-6-methylphenol the conditions of synthesis were optimized. The formation of bi- and polynuclear products cannot be avoided.
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  • 42
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    Angewandte Makromolekulare Chemie 215 (1994), S. 189-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Scherviskositäat fläussigkristalliner Ethylcellulose, die mit Cellulosepulver unterschiedlicher Partikelgräoße gefäullt war, wurde bei konstantem Schergefäalle mit einem Kegel-Platte-Viskosimeter bestimmt. Der Einfluß des Cellulosepulvergehalts, des Läange/Breite-Verhäaltnisses der Pulverteilchen und der Temperatur auf das viskose Verhalten und die Phasenäubergäange wird diskutiert. Der Zusatz von Cellulosepulver erhäoht die Viskositäat und verringert die Aktivierungsenergie des Fließens(Ea), ohne jedoch die Phasenäubergäange zu beeinflussen. Die Viskositäat und die Aktivierungsenergie sind abhäangig vom Läange/Breite-Verhäaltnis der Pulverteilchen; mit zunehmender Gräoße dieses Verhäaltnisses wird die Viskositäatszunahme beschleunigt und die Aktivierungsenergie des Fließens erhäoht, wäahrend die Aktivierungsenergie mit steigendem Pulvergehalt abnimmt. Die Phasenumwandlungen sind unabhäangig von der Partikelform. Der Einfluß des Pulvergehalts auf Viskositäat und Aktivierungsenergie ist abhäangig von der Art der fläussigen Phase; in der anisotropen Phase ist der Einfluß geringer als in der isotropen Phase. Dies scheint von der Ausrichtung der Pulverteilchen und der stäabchenfäormigen Molekäule herzuräuhren.
    Notes: Steady-state shear viscosity for the liquid crystalline ethyl cellulose solution filled with cellulose powders was determined using a cone-plate-type viscometer and the effects of cellulose powder content, powder aspect ratio and temperature on the viscometric behavior and phase transformation were discussed. The addition of powder increased the viscosity and decreased the activation energy (Ea) for flow, but did not affect the phase transformation. The viscosity and Ea depended on the aspect ratio; with greater aspect ratio, the viscosity enhancement was accelerated and Ea as well as the decrease in Ea with powder content increased. The phase transformation did not depend on the aspect ratio, the dependences of viscosity and of Ea on powder content depended on the solution phase; the dependences for the anisotropic phase were smaller than those for the isotropic one. The findings appeared to originate from the alignments of powders and rod-like molecules.
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  • 43
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UV-degradation of an unstabilized and two HALS stabilized polyethylene (PE) films is described. The degradations are characterized by measuring the oxygen uptake, the formation of CO and CO2, the FT-IR spectra, the mechanical properties, the stabilizer concentration and the oxygen content of the film.The oxygen uptake of the unstabilized PE film led to the expected changes in the IR spectra and embrittlement of the film, while the oxygen uptake by the HALS stabilized films caused only minor changes. The differences between the results for the unstabilized and the HALS stabilized polymers are explained assuming that the initiation of the photodegradation of PE is due to charge transfer complexes.
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  • 44
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Principal chemical pathways characteristic of active participation of radical scavenging polymer stabilizers (phenols, aromatic, hydroaromatic and hindered aliphatic amines) are outlined. Pathways resulting in a partial depletion or distortion of activity of stabilizers, in formation of polymer discolouring products, or in interactions in bifunctional stabilizers are involved.
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  • 45
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Irradiations (λ≥300 nm) of poly(butyleneterphtalate) films were carried out in both vacum and air. Photoproducts were investigated by FTIR spectroscopy, chemical derivatization reactions and physical treatments. The repartition of photoproducts in the polymer was shown to be heterogeneous. A scheme accounting for the main routes of PBT photolysis was found on the basis of photoproducts identification. Most of oxidation products were analogous to vacum photolysis species; the mechanism of photooxidation proposed implied both pure photolytical processes and a photo-induced oxidation route.
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  • 46
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of polymer density, processing conditions (quenching of annealing), degree of crystallinity, size of crystallite and mobility of polymer chains on the photo-and radiation-induced degradation and the polymer stability have been studied by UV, FTIR spectroscopic, viscosity and mechanical property measurements. Four kinds of annealed or quenched polyethylene (PE) films varying densities were used to the studies. Polystyrene (PSt) films were used to investigate the effect of chain mobility on polymer degradation. The following results were obtained. 1.In linear low density (LLD) PE, greater amounts of crosslinking (irradiated in vacuum) and chain scission (irradiated in air) were noticed than in mediun density (MD) PE and high density (HD) PE samples.2.Polyene formation is favored in the case of the irradiation in vacuum for LLDPE.3.Polymer stability evaluated by mechanical property such as elongation at break (%) is superior in LLDPE to MDPE and HDPE for annealed and quenched samples.4.Segmental motion of polymer chain also affects the polymer stability
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  • 47
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    Angewandte Makromolekulare Chemie 217 (1994), S. 43-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The study is on two component blends of high density polyethylenes, having normal and ultra-high molecular weight. The polyethylenes were homogenized by two routes: in powder state or by rolling in melt, then pressed at temperatures in the range from 140°C to 220°C. Comparative studies showed that the way of homogenizing of the components does practically not affect the main mechanical properties of the blends when pressed at temperatures ≥ 160°C. Of special interest are the characteristics of those systems where ultra-high molecular weight polyethylene is the matrix component.
    Notes: Untersucht wurden binäre Mischungen von Polyethylenen hoher Dichte rnit normaler und ultrahochmolekularer Molmasse, die auf zweierlei Weise - in Pulverform oder durch Walzen im Schmelzezustand - homogenisiert und bei Temperaturen zwischen 140 und 220°C gepreßt waren.Es wurde festgestellt, daß die Art der Homogenisierung der Komponenten praktisch keinen Einfluß auf die Eigenschaften bei Preßtemperaturen ≥ 160°C hat. Von besonderem Interesse sind die Eigenschaften der Systeme, in welchen das ultrahochmolekulare Polyethylen die Rolle der Matrixkomponente spielt.
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  • 48
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    Angewandte Makromolekulare Chemie 218 (1994), S. 81-109 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Verhalten eines neuartigen photoinitiierenden Systems, das die Polymerisation von pigmenthaltigen Schichten großer Dicke in einem Reaktionsschritt gestattet, wird dargestellt. Die verschiedenen Wechselwirkungen, die in einem pigmenthaltigen System auftreten, werden qualitativ beschrieben, und der Anteil der von einem Photoinitiator absorbierten Lichtintensität wird berechnet. Neben dem Absorptions- und Reflexionsverhalten von verschiedenen Pigmentklassen werden die optischen Eigenschaften verschiedener Strahlungsquellen untersucht, um die Strahlungsbereiche zu finden, die am besten mit den optischen Parametern der Pigmente korrespondieren. Weiterhin wird die Beschleunigung von Polymerisationen durch die photokatalytische Wirkung einiger Pigmente behandelt.
    Notes: Ce travail sur le rôe des pigments définit le comportement d'un nouveau systeme photosensible qui permet de polymériser des milieux épais et pigmentés selon un procédé en une seule étape. Les différentes interactions présentes en milieu pigmenté sont décrites de façon qualitative, et la part de l'intensité lumineuse absorbée par un photo-amorceur dans un systéme pigmenté est evaluée. Les propriétés optiques telles que l'absorption et la réflectance des différentes familles chimiques de pigments sont déterminées, et, en paralléle, les propriétés optiques des différentes sources d'irradiation sont étudiées de manière à répondre au mieux aux fenêtres de transmission des pigments. L'effet photocatalytique de certains pigments est mentionné, ceci afin d'amkliorer la réaction de polymérisation.
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  • 49
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    Angewandte Makromolekulare Chemie 218 (1994), S. 153-162 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Herstellung von cis-1,4-Polybutadien erfolgte mittels Polymerisation von 1,3-Butadien mit einem Katalysatorsystem, das in einer zweistufigen Reaktion gebildet wird: (1) BF3 · O(C2H5)2 und Al(C2H5)3, (2) Ni(OOC8H15)2 und Al(C2H5)3, genannt in-situ-Katalysatorsystem.Die Molmassenverteilungen (MMD) der erhaltenen Polymeren sind mit der Größenausschlußchromatographie (SEC) untersucht worden. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Veränderte Katalysatorformierungs- und Polymerisationsbedingungen beeinflussen die Parameter der SFF. Veränderte Peakflächen und Molmassenmittelwerte der Einzelpeaks zeigen, daß die Polymerisation über mehrere Arten aktiver Zentren verläuft.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system formed by a two-step formation, Namely (1) BF3 . O(C2H5)2 and Al(C2H5)3, (2) Ni(OOC8H15)2 and Al(C2H5)3 named in-situ-catalyst.The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Changed catalyst formation and polymerization conditions influenced the parameters of the SFF. Changed areas and changed molar mass averages indicate a polymerization with more than one peak maximum and kind of active species and lead to a better understanding of the polymerization.
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  • 50
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    Angewandte Makromolekulare Chemie 219 (1994), S. 1-10 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Durch Umsetzung von Chromacrylat mit Bisphenol A und einem Überschuß Epichlorhydrin wurden neuartige Epoxid-Harze hergestellt. Epoxy-Äquivalentgewicht, Gehalt an Hydroxygruppen und hydrolysierbarem Chlor sowie die Viskosität wurden bestimmt, und die Harze wurden mittels IR- und 1H-NMR-Spektroskopie charakterisiert. Die thermischen Eigenschaften der bei 30°C für 24 h mit Ciba Geigy HY 850 (aliphatisches Amin) gehärteten Harze wurden gemessen. Die Harze besitzen eine gute thermische und chemische Stabilität und eine gute elektrische Leitfähigkeit. Die Reaktion verläuft nach erster Ordnung; die Aktivierungsenergie beträgt 47 kJ mol-1 bzw. 34 kJ mol-1 mit bzw. ohne Chromacrylat. Aus spektroskopischen Untersuchungen wird geschlossen, daß das Chrom mit Bisphenol A einen Komplex bildet, der die Epoxidierung beschleunigt.
    Notes: Novel epoxy resins containing chromium acrylate have been synthesized by reacting chromium acrylate with bisphenol-A and excess epichlorohydrin. The quantities such as epoxy equivalent weight, hydroxy content, hydrolyzable chlorine content and viscosity have been determined. The resins have been characterized by IR and 1H NMR spectroscopy. The cured resins were evaluated for thermal properties. The curing of resins was carried out with Ciba Geigy HY 850 (aliphatic amine adduct) at 30°C for 24 h. The cured resins have excellent thermal and chemical resistance, in addition to an excellent electrical conductivity. The reaction follows first order kinetics with an activation energy of 47 kJ mol-1 and 34 kJ mol-1 in the presence and absence of chromium acrylate, respectively. The chromium forms a complex with bisphenol-A, as indicated by spectroscopic studies, which increases epoxidation.
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  • 51
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    Angewandte Makromolekulare Chemie 219 (1994), S. 67-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Interpenetrierende Polymernetzwerke (IPNs) aus Polystyrol und Polyurethan auf der Basis von hydroxyterminiertem Naturkautschuk mit unterschiedlichen NCO/OH-Verhältnissen wurden unter verschiedenen Reaktionsbedingungen hergestellt und zu widerstandsfähigen Filmen verarbeitet. Die IPNs wurden durch ihre physikalischen, mechanischen und morphologischen Eigenschaften wie Dichte, Shore-A-Härte, Vernetzungsdichte, Zugfestigkeit und Reißdehnung charakterisiert. Mit steigendem Polystyrolgehalt erhöhen sich auch Dichte, Shore-A-Härte und Zugfestigkeit, während die Reißdehnung abnimmt. Die Untersuchungen der Vernetzungsdichte lassen eine Phasenumkehr vermuten.
    Notes: Interpenetrating polymer networks (IPNs) of polyurethane based on hydroxyterminated natural rubber with varying NCO/OH ratios and polystyrene were synthesized under different experimental conditions. These IPNs were found to make tough films. The IPNs were characterized by their physical, mechanical and morphological properties like density, Shore-A hardness, crosslink density, tensile strength and elongation at break. The IPNs exhibited an increasing trend in density, Shore-A hardness and tensile strength with increasing polystyrene content, while elongation at break decreased with similar variation in polystyrene content. The crosslink density measurements indicated a possible phase inversion process.
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  • 52
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    Angewandte Makromolekulare Chemie 219 (1994), S. 117-124 
    ISSN: 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 Plasmabehandlung von Ultrafiltrationsmembranen aus Polyethylen auf die Fouling- und Reinigungseigenschaften bei der Filtration von Rinderserumalbumin werden diskutiert. Bei 2,45 GHz erzeugtes Luft-Plasma steigert die Hydrophilie der Membranoberfläche von 0 auf 60%. Der Durchfluß bleibt bei 90 bis 99%. Mit Plasma behandelte Membranen sind leichter zu reinigen als unbehandelte; dennoch sind sie anfälliger für die Ablagerung von Rinderserumalbumin.
    Notes: The effect of plasma treatment of polyethylene ultrafiltration membranes on fouling and cleaning phenomena during filtration of bovine serum albumin solutions is discussed. Air-plasma of 2.45 GHz raises the membrane surface hydrophilicity from 0 up to 60%. The flux is maintained at 90-99%. Plasma-treated membranes are easier to clean than untreated polyethylene membranes. Despite that, the plasma-modified membranes are susceptible to more intensive deposition of albumin.
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  • 53
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    Angewandte Makromolekulare Chemie 219 (1994), S. 101-115 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Immobilisierung von Glucose-Oxidase in einer Poly(vinylalkohol) (PVAL)-Membran in Gegenwart von UV-Photoinitiatoren wurde untersucht. Enzym-Membranen wurden aus PVAL-Diazoharz- und PVAL-Photoinitiator-Systemen durch Vernetzung mit UV-Licht hergestellt. Mit diesen immobilisierten Glucose-Oxidase-Membranen wurde eine wirkungsvolle Enzymelektrode entwickelt, deren Eigenschaften untersucht wurden. Der Einfluß der Photoinitiatorkonzentration in Poly(vinylalkohol) und der UV-Bestrahlungsdauer auf den Grad der Unlöslichkeit sowie die Aktivitätsausbeute der Membran wurden mit Glucose als Substrat untersucht. Temperatur- und pH-Abhängigkeit der relativen Aktivität, Stabilität bei mehrmaligem Gebrauch, Lagerstabilität und Kalibrierungsdiagramme der Enzym-Membranen wurden ermittelt. Eine beim Erstgebrauch auftretende Instabilitätserscheinung der Membranen wurde ebenfalls untersucht.
    Notes: A study of the immobilization of glucose oxidase on a poly(vinyl alcohol) (PVAL) membrane in the presence of UV sensitizers was carried out. Enzyme membranes were prepared from PVAL-diazoresin and PVAL-sensitizer systems, crosslinked by means of UV irradiation. An effective enzyme electrode was developed by using the immobilized glucose oxidase membrane, and its characteristics were investigated. The effects of the concentration of sensitizers in poly(vinyl alcohol) and UV irradiation time on the degree of insolubility as well as the activity yield of the membrane were examined for the immobilized glucose oxidase using glucose as a substrate. Temperature and pH dependences of the relative activity, stability in repeated use, storage stability and calibration plots of the enzyme membranes were evaluated. The unstability phenomenon, found in the initial use of the immobilized glucose oxidase membrane, which was prepared from PVAL-sensitizer system, was also investigated.
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  • 54
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    Angewandte Makromolekulare Chemie 219 (1994), S. 11-26 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Biopol, Biocellat and Mater-Bi, three biologically decomposable plastics have been tested for their use in medical industries. Biopol did not loose its stress and stiffness under sterilisation, and was also resistant against temperature and alcohol. Mater-Bi and Biocellat, the two other materials, did not satisfy the test applications. Water vapor sterilisation, temperature up to 60°C, at higher temperatures this material will embrittle.
    Notes: Für den Einsatz biologisch abbaubarer Kunststoffe in der pharmazeutischen Industrie und Medizintechnik wurden Produkte verschiedener Hersteller, wie Biopol, Biocellat und Mater-Bi untersucht. Dabei zeigte vor allem Biopol das notwendige Anforderungsprofil, d.h. die Anwendbarkeit aller Sterilisationsverfahren ohne Festigkeitsbzw. Steifigkeitsverluste sowie Temperatur- und Alkoholbeständigkeit. Dagegen wiesen die Werkstoffe Mater-Bi und Biocellat einige Schwachstellen auf. Bei Mater-Bi lagen diese bei der Wasserdampfsterilisation sowie bei der geringen thermischen und Medienbeständigkeit. Biocellat versprödet dagegen durch die erhöhte Temperatur bei der Dampfsterilisation, d.h. daß ein Einsatz über 60°C nicht möglich wäre.
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  • 55
    ISSN: 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 Alkylierung von Poly(5-vinyltetrazol) mit Dimethylsulfat und tert-Butylalkohol sowie Alkylhalogeniden RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9 und t-C4H9) und die Kinetik dieser Reaktion wurden untersucht, um eine neue Herstellungsmethode für tetrazolhaltige Polymere mit wertvollen Eigenschaften zu entwickeln. Die vergleichenden Untersuchungen über die isomere Zusammensetzung und die spektroskopischen Daten von Poly(N-alkyl-5-vinyltetrazol)en, die durch die Alkylierung von Poly(5-vinyltetrazol) sowie durch die Copolymerisation der entsprechenden Monomeren hergestellt wurden, wurden mit IR-, 1H-NMR- und 13C-NMR-Spektroskopie durchgeführt. Der Alkylierungsumsatz beträgt bis zu 99,8%; dadurch können polymere Produkte erhalten werden, deren Zusammensetzung, Struktur und Eigenschaften denen der Homo- und Copolymeren sehr ähnlich sind.
    Notes: Alkylation of poly(5-vinyl tetrazole) with dimethyl sulfate and tert-butyl alcohol as well as with alkyl halides RHal (R=CH3, C2H5, CH2—CH=CH2, n-C4H9, t-C4H9) has been studied under various conditions in order to develop a new method of synthesis of tetrazole-containing polymers having a complex of valuable properties. The kinetic study of the process and comparison of isomeric compositions and spectroscopic characteristics (IR, 1H NMR and 13C NMR) of poly(N-alkyl-5-vinyl tetrazole)s synthesized by alkylation of poly(5-vinyl tetrazole) and of those prepared by (co)polymerization of the corresponding vinyl tetrazoles have been carried out. The alkylation is found to proceed to high conversion extents (up to 99.8%) and enables to obtain a wide variety of polymeric products having the composition, structure and properties very similar to those of homo- and copolymers.
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  • 56
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Farbstoffe mit nichtlinearen optischen Eigenschaften wurden in einer zweistufigen Synthese aus 2-Hydroxyethylmethacrylat (HEMA), 4-Carboxybenzaldehyd und verschiedenen Anilinderivaten hergestellt. Die Farbstoffe (aromatische Iminester von HEMA) wurden mit Styrol copolymerisiert, die erhaltenen Copolymere wurden mit DSC sowie IR-, 1H NMR- und UV-VIS-Spektroskopie charakterisiert, und ihre nichtlinearen Eigenschaften wurden untersucht. Es zeigte sich, daß die nichtlinearen Koeffizienten d31 und d33 vom Farbstoffgehalt der Copolymeren und der Art der elektronenspendenden Gruppen abhängig sind.
    Notes: Dyes for nonlinear optics have been synthesized in two steps from 2-hydroxyethyl methacrylate (HEMA), 4-carboxybenzaldehyde and various substituted anilines. The obtained dyes (aromatic imine esters of HEMA) have been copolymerized with styrene, the copolymers characterized by DSC as well as IR, 1H NMR and UV-VIS spectroscopy, and studied for their nonlinear properties. The d31 and d33 nonlinear coefficients proved to be dependent on the dye content of the copolymers and on the nature of electrondonating groups.
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  • 57
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    Angewandte Makromolekulare Chemie 220 (1994), S. 123-132 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß von Ca2+-bzw. Al3+-Ionen auf das Viskositätsverhalten (Salzverträglichkeit) wäßriger Lösungen von Natriumcarboxymethylcellulose (CMC) sowohl mit unterschiedlichem Polymerisationsgrad (DP) als auch mit unterschiedlichem Substitutionsgrad (DS) und verschiedenartiger Substitutentenverteilung wurde untersucht. Aus Viskositätsmessungen mit einem Rotationsviskosimeter bei einer Scherrate von 500 s-1 geht hervor, daß die relative Abnahme der Viskosität im Ergebnis des Zusatzes der mehrwertigen Metallkationen unabhängig vom DP (im Bereich von 160 bis 900) der CMC ist. Homogen hergestellte CMC-Proben 2 mit einem größeren Gehalt an 2,3,6-Tri-O-carboxymethylglucose-Einheiten in der Polymerkette weisen im Vergleich zu heterogen hergestellten CMCs 1 bei gleichem Gesamt-DS eine höhere Salzverträglichkeit auf.
    Notes: The influence of Ca2+-and Al3+-ions, respectively, upon the viscosity behaviour (so-called salt tolerance) of aqueous solutions of sodium carboxymethyl cellulose (CMC) with different degree of polymerization (DP) and, on the other hand, with both different degree of substitution (DS) and distribution of substituents, was investigated. Viscosimetry by means of a rotational rheometer at a shear rate of 500 s-1 shows that the relative drop in viscosity as a result of addition of the multivalent metal cations is independent of DP (ranging from 160 to 900) of the CMC samples. Homogeneously synthesized CMCs (2) with a higher content of 2,3,6-tri-O-carboxymethyl glucose units in the polymer chain possess a significantly higher salt tolerance than those (1) prepared under heterogeneous reaction conditions at comparable total DS values.
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  • 58
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    Angewandte Makromolekulare Chemie 222 (1994), S. 61-87 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Melamin-Formaldehyd-Harz-Formmassen (MF) wurden durch mechanisches Mischen mit Ethylen-Vinylacetat-Copolymeren (EVA) und teilverseiftem EVA modifiziert, wobei Etherbindungen zwischen dem hydrolysierten EVA und dem MF-Harz nachgewiesen werden konnten, die die mechanischen Eigenschaften von spritzgepreßten Formteilen im Vergleich zur Modifizierung mit EVA verbessern. Der Zusatz solcher Modifikatoren erhöht die Duktilität und verringert im Falle von EVA die Nachschwindung der überaus steifen MF-Matrix, solange der Modifikatoranteil gering bleibt. Dagegen werden die Steifigkeit und die Wärmeformbeständigkeit verschlechtert. Die durch solche unvernetzten Polymeren erreichbare Steigerung der Schlagzähigkeit bleibt allerdings unzureichend.
    Notes: Melamine-formaldehyde moulding compounds (MF) were modified by mechanical mixing with ethylene/vinyl acetate copolymers (EVA) and with partially hydrolysed EVA. Ether linkages between the hydrolysed material and the MF resin improve the mechanical properties of the transfer moulded parts containing the hydrolysed material compared to those made with EVA. The use of both modifying polymers improves the ductility and, in case of the partially hydrolysed material, the postshrinkage of the extremely rigid MF matrix, as long as the modification polymer content is kept low. On the contrary, Young's modulus and the heat deflection temperature are deteriorated. The improvement in impact strength by use of those uncrosslinked polymers is still insufficient.
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  • 59
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    Angewandte Makromolekulare Chemie 222 (1994), S. 111-123 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe von Copolyesteramiden mit Molekulargewichten zwischen 1000 und 7000 (GPC, NMR) wurden aus Adipinsäure/1,6-Hexandiamin/∊-Caprolacton bzw. Nylon 6,6-Salz/∊-Caprolacton hergestellt. Die thermischen Eigenschaften der synthetisierten Polymeren (Glasübergangs-, Schmelz-, und Zersetzungstemperaturen, Schmelzenthalpien) wurden durch DSC- und TGA-Messungen bestimmt und in Bezug auf das Comonomerverhältnis in der Ausgangsmischung diskutiert. Die Übereinstimmung der Copolymerzusammensetzung mit dem Ausgangscomonomerverhältnis wurde mit FT-IR- und NMR-Spektroskopie untersucht. Die Bioabbaubarkeit der Copolyesteramide wurde durch enzymatische Hydrolyse geprüft.
    Notes: A series of copolyesteramides based on adipic acid/1,6-hexane diamine/∊-caprolactone and Nylon 6,6 salt/∊-caprolactone were synthesized. Their molecular weights, determined by gel permeation chromatography and NMR spectroscopy, were found to lie within the range from 1000 up to 7000. Their thermal properties (glass transitions, melting points and heats of melting, and decomposition temperatures) were recorded with diferential scanning calorimetry and thermogravimetry, respectively, and correlated to the comonomer feed composition. The FT-IR and NMR spectra were also recorded in order to confirm the composition of the copolyesteramides and to compare them with that of the comonomer feed. The biodegradability of the synthesized copolymers was tested by enzymatic hydrolysis.
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  • 60
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    Angewandte Makromolekulare Chemie 222 (1994), S. 165-174 
    ISSN: 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 sulfonsäurekatalysierte Umsetzung von Abietinsäure und Paraformaldehyd bei hohen Temperaturen wurden neuartige Kondensationsprodukte erhalten. Als Nebenprodukte der Polykondensation werden eine Ketoverbindung sowie Wasser und Kohlendioxid gebildet. Die Carboxygruppen der Abietinsäure sind an der Kondensationsreaktion beteiligt. In Abwesenheit von Paraformaldehyd wurde das Abietinsäure/Sulfonsäurekatalysator-System untersucht, um zusätzliche Informationen über die Reaktion zu erhalten. Der Reaktionsverlauf hängt von der Temperatur und der chemischen Struktur des Katalysators ab. Ein möglicher Reaktionsmechanismus der Kondensation wird diskutiert.
    Notes: New condensation products have been synthesized by heating abietic acid and formaldehyde at high temperatures in the presence of sulfonic-type acid catalysts. The main polycondensation reaction is associated with a secondary one which leads to a ketonic compound, carbon dioxide and water. The carboxylic groups of abietic acid participate in this condensation reaction. The behaviour of the abietic acid-sulfonic acid catalyst system was studied in absence of formaldehyde to acquire additional information about the reaction. The process is defined by the reaction temperature and chemical nature of the catalyst. A possible mechanism of the condensation reaction is discussed on the basis of the obtained results.
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  • 61
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    Angewandte Makromolekulare Chemie 223 (1994), S. 1-11 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: After a general classification of the cationic ring-opening polymerizations (CROP's) according to their polymerization mechanism, a number of examples of tailored polymers based on CROP are presented. The monomers used for the synthesis of these tailored structures are tetrahydrofuran (THF), N-tert-butyl aziridine (TBA), 2-methyl-1,3-oxazoline (MeOX) and 1,3-dioxolane (DXL).The polymer structures include different block and graft copolymers, macromonomers, star-shaped polymers, polymer networks and interpenetrating polymer networks (IPNs).
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  • 62
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In diesem Beitrag wird ein überblick über neuere Entwicklungen auf dem Gebiet der Synthese von Telechelen, Makromonomeren, Block- und Pfropfcopolymeren gegeben. Synthesestrategien aus den Bereichen der Polykondensation, der radikalischen, anionischen und kationischen Polymerisation, der Kettenspaltung sowie der Criss-Cross-Cycloaddition werden diskutiert.
    Notes: New developments in the synthesis of telechelics, macromonomers, block- and graftcopolymers are presented. Synthetic strategies for them are demonstrated with examples from different fields such as polycondensation, radical, anionic, and cationic polymerization, chain cleavage and criss-cross-cycloaddition.
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  • 63
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    Angewandte Makromolekulare Chemie 223 (1994), S. 69-79 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Alkanes with highly substituted carbon-carbon bonds can be cleaved in free radicals by homolytic dissociation under the influence of thermal energy. The energy of dissociation is mainly determined by the type and size of the respective substituents. For tetraarylbutane dinitriles the temperatures of decomposition are in the range of other technically used initiators. But nevertheless, these compounds are up to now rather seldom used to initiate free radical polymerizations. This is connected with the special mechanism of initiation: the formed highly substituted alkyl radicals are relatively stable and show only a rather low reactivity against the usually used monomers. Therefore, in the beginning of the polymerization the radical concentration is rather high which leads not only to addition to monomers but also to a pronounced primary radical termination. In some cases this termination process is reversible which results in an unusual polymerization kinetics. Depending on the type of monomer and the degree of reversibility of the primary radical termination, either a period of “dead-end” polymerization follows or the cleavage of the oligomers at the chain end results in a re-initiation process with a “normal” polymerization with increased rate. The reaction mechanism, kinetics and some possible applications of such initiating alkanes are reported.
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    Angewandte Makromolekulare Chemie 223 (1994), S. 121-133 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Untersuchungen wesentlicher Aspekte der Polymerisation und der Eigenschaftsmodifikation auf Metallocen-Katalyse basierender Cycloolefin-Copolymere (COC) zeigen, daß mit dieser Monomer-Katalysator-Kombination eine neue Klasse transparenter Thermoplasten zugänglich gemacht wird. COC können mit Metallocenen in beliebiger zusammensetzung und mit kontrollierter Mikrostruktur hergestellt werden. Die somit erreichte und durch zusätzliche Modifikationen noch erweiterbare Breite des Eigenschaftsspektrums ermöglicht vielfältige Anwendungen dieser neuen Polymerklasse. Die wichtigsten Schlüsselfaktoren im rohstofflich-technologischen Bereich, die diese Struktur- und Eigenschaftsvielfalt ergeben, werden beispielhaft beschrieben.
    Notes: Investigation of the polymerization process and property modification of metallocene-based cycloolefin copolymers (COC) shows that this monomer-catalyst combination enables synthesis of a new class of transparent thermoplastic polymers. Metallocene catalysis offers much opportunity to vary the composition and microstructure of the copolymers. The breadth of the polymer spectrum which can be further widened by polymer modification enables many applications for this new class of thermoplastics. The key parameters that control structure and properties in the COC family are discussed in this paper.
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  • 65
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    Angewandte Makromolekulare Chemie 223 (1994), S. 165-175 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The present paper deals with the synthesis and modification of functionalized polymers characterized by a special molecular architecture. The reactivity of a functionalized polymer with comb-like structure can be controlled in a significant manner by the crystalline order of the side chains. In contrast, photocrosslinking of comblike polymers containing cinnamic components in the side chains influences the crystallization process. The air drying process of a modified polybutadiene system with comb-like structure was shown to depend sensitively on the side chain order. Enzymatic synthesis of new monomers and polymers is briefly reviewed. The complexing capability of cyclodextrines were used to synthesize polyrotaxanes. Finally, the synthesis of a chiral polymerizable dendrimer containing eight estergroups in the monomer unit is presented.
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  • 66
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    Angewandte Makromolekulare Chemie 223 (1994), S. 203-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Intramolecularly crosslinked poly(organosiloxane) particles are prepared by means of emulsion polycondensation or emulsion polymerization of alkoxysilanes or cyclic organic siloxanes. Starting from these intramolecularly crosslinked poly(organosiloxane) particles, graft copolymers are obtained by free-radical emulsion polymerization of unsaturated olefinic monomers (e.g. acrylates, styrene) in the presence of (functionalized) organosiloxanes. Intramolecularly crosslinked poly(siloxane) particles and their graft copolymers are characterized by means of light scattering (in dispersion), electron microscopy and thermal analyses (DSC, DMTA).
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  • 67
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    Angewandte Makromolekulare Chemie 214 (1994), S. 153-167 
    ISSN: 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 Zusammenhang zwischen der Mischbarkeit und den physikalischen Eigenschaften von Polymerblends aus Poly(2,6-dimethyl-1,4-phenylenoxid) (PPO), die in unterschiedlichen Zusammensetzungen in einem Doppelschneckenextruder mit Polystyrol, schlagzähem Polystyrol oder Styrol-Butadien-Copolymeren hergestellt wurden, wird diskutiert. Die Verträglichkeit der Komponenten wurde mittels DSC und DMA, die Morphologie der Blends mittels SEM untersucht. Mit abnehmendem Polystyrolanteil wurde eine schlechtere Mischbarkeit bei den Blends beobachtet, deren Kerbschlagempfindlichkeit sich erhöhte. Die Untersuchungsergebnisse werden mit dem Micellmodell interpretiert.
    Notes: The relationship between the miscibility and the physical properties of polymer blends of poly(2,6-dimethyl-1,4-phenylene oxide) and polystyrene (PS), high-impact polystyrene (IPS) and poly(styrene-block-butadiene-block-styrene) (SBS), which are blended in different compositions by a twin-screw extruder is discussed. The three types of SBS that were used are SBS1, SBS2 and SBS3 having different styrene/butadiene ratios. Dynamic mechanical analysis and differential scanning calorimetry were used to study the miscibility. The morphology was examined by SEM. The miscibility of the blends decreases with decreasing PS content. The notch sensitivity is improved by blending. Finally, the micelle model was used to explain the testing phenomena.
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  • 68
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aliphatische Polyamide mit Poly(ethylenoxid)-Kettensegmenten unterschiedlicher Länge wurden durch Grenzflächenpolymerisation aus Succinylchlorid und Jeffamine ED-900 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 800) bzw. Jeffamine ED-2001 (O,O'-Bis(2-aminopropyl)poly(ethylenglykol) 1900) zur Verwendung als Trägersubstanzen für Medikamente synthetisiert. Copolyamide mit kurzkettigen Diamin- und Jeffamine-Segmenten sowie Polyamide aus Cystin und Diamineinheiten wurden auf die gleiche Weise hergestellt. Die Polymerisationen wurden im zweiphasigen System Dichlormethan/Wasser bei Temperaturen um 0°C durchgeführt. Die Polymerprodukte wurden durch stufenweise Dialyse in wäßriger Phase bis zu einem Molekulargewicht von 25000 fraktioniert, nach Gefriertrocknung als wasserlösliche Harze oder Feststoffe erhalten und durch Mikroanalyse sowie 1H NMR-Spektroskopie charakterisiert. Die inhärenten Viskositäten liegen im Bereich von 10-20 ml/g. Die Eignung eines repräsentativen Zielmoleküls zur Bindung von Medikamenten wurde durch eine kovalente Verankerung einer als Medikamentmodell fungierenden Ferrocen-Verbindung untersucht. Dabei wurde ein wasserlösliches Polymer-Ferrocen-Konjugat erhalten.
    Notes: Aliphatic polyamides comprising poly(ethylene oxide) chain segments of various lengths, designed for use as drug carriers, are synthesized by interfacial polymerization of succinyl chloride with the two Jeffamine types ED-900 and ED-2001, formally described by the supplier as O,O'-bis(2-aminopropyl)poly(ethylene glycol) 800 and O,O'-bis(2-aminopropyl)poly(ethylene glycol) 1900. Copolyamides comprising both short-chain diamine and Jeffamine segments are similarly prepared, as are polyamides made up of cystine and diamine segments. The polymerizations are performed in a two-phase methylene chloride-water system at temperatures near or below 0°C. The product polymers, crudely fractionated by staged aqueous-phase dialysis at an ultimate molecular-mass cut-off of 25000, are collected after freeze-drying as water-soluble resins or solids and are characterized microanalytically and by 1H NMR spectroscopy. Inherent viscosities are in the range of 10-20 ml g-1. The drug-binding potential of a representative target polymer is probed by the covalent anchoring of a ferrocene compound used as a drug model, giving a water-soluble polymer-ferrocene conjugate.
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  • 69
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    Angewandte Makromolekulare Chemie 214 (1994), S. 211-216 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Über die Anwendung von Vinylesterharzen aus dem Diglycidylether von Bisphenol A sowie dessen Urethanderivat als Beschichtungsmaterial wird berichtet. Die mit den Harzen beschichteten Flußstahlplatten wurden auf Oberflächenglanz, Kratzfestigkeit und Chemikalienbeständigkeit untersucht. Harze mit Styrolanteil zeigen deutlich verbesserte Beschichtungseigenschaften.
    Notes: The present paper is concerned with the coating applications of a vinyl ester resin derived from diglycidyl ether of bisphenol-A and its urethane derivative. The mild steel panels coated with the synthesized resins were evaluated for their gloss on the surface, scratch hardness and chemical resistance. The incorporation of styrene in the resin systems improves the properties of coatings remarkably.
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  • 70
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Katalysatorsystem Zirkonocendichlorid/Methylalumoxan wurde auf Siliciumdioxid aufgebracht, um Katalysatoren fur die Suspensions- order Gasphasenpolymerisation von Ethylen herzustellen. Die häochste Aktivitäat wurde für eine sandwichartige, dreilagige Verankerung von Zirkonzentren auf der Träageroberfläache gefunden. Dieneuen Katalysatorsysteme besitzen eine im Vergleich zu den entsprechenden homogenen Katalysatoren geringere Aktivitäat. Die Immobilisierung der aktiven Katalysatorzentren führt zu einer deutlichen Erhäohung der Polymermolmassen. Dabei bleibt die enge Molekulargewichtsverteilung der Polymerprodukte nahezu erhalten. Solche auf Träager aufgebrachte Metallocen-Katalysatoren käonnten für die Herstellung von Polyethylenen mit kontrollierter Rheologie Anwendung finden.
    Notes: The system zirconocene dichloride/methylalumoxane was supported on silica in order to provide ethylene polymerization catalysts for suspension or gas phase processes. Highest activity was found for a sandwich-like, three layer anchoring of the zirconium centers on the support surface. The new catalyst systems show a decrease of activity compared to polymerization experiments in homogeneous phase. However, the molecular weights are increased and the weight distributions remain narrow by immobilization of the active catalyst sites. Those supported metallocene catalysts could find application for the synthesis of polyethylene materials with controlled rheology.
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  • 71
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    Angewandte Makromolekulare Chemie 215 (1994), S. 129-138 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Vernetzte Copolmere aus Butylacrylat (BA) und Ethylenglycol-dimethacrylat (EGDMA) wurden auf ihre Eignung als stationäare Phase für die Chromatographie untersucht. Es wurde festgestellt, daß gering vernetzte Copolymere (〈 30 Gew.-% EGDMA) nicht poräos sind, wäahrend Matrices mit mehr als 40 Gew.-% EGDMA eine konstante Porositäat aufweisen. Eine Erhäohung des Vernetzergehaltes beeinflußt hauptsäachlich die Hydrophobie der Oberfläache. Zwei Meßmethoden für diese Eigenschaft werden diskutiert: Die Absorption von Alkylalkoholen und von Aminosäauren. Für letztere wurde aus der Steigung der Beziehung zwischen der Sälenkapazitäat und dem Hydrophobie-Parameter der Aminosäauren ein Matrix-Hydrophobie-Index berechnet und dieser mit den bekannten Energien der Wechselwirkung von Alkylalkohol—CH2 Gruppen mit der Polymermatrix verglichen. Die Vorteile der Verwendung des Hydrophobie-Indexes bei der Bewertung von polymeren Sorbentien werden aufgezeigt.
    Notes: Copolymers of butyl acrylate (BA) crosslinked with ethylene glycol dimethacrylate (EGDMA) were evaluated as potential chromatographic packings. It was found that slightly crosslinked copolymers (up to 30 wt.-% EGDMA) did not provide porous material, while for matrices which exceeded 40 wt.-% of EGDMA the porous structure remained unchangeable. The increase of crosslinker content mostly affected the surface hydrophobicity. Two methods of measurement of this property were discussed: Sorption of alkyl alcohols and amino acids. Taking the latter for testing, a polymer matrix hydrophobicity index was calculated as the slope of dependence of column capacity vs. amino acid hydrophobicity parameter. The indices were verified against well-established interaction energies of —CH2— groups of alkyl alcohols and polymer surfaces. Some benefits of the use of the hydrophobicity index in evaluation of polymer sorbents were demonstrated.
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  • 72
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kondensation von 3-Glycidyloxypropyltrimethoxysilan I mit Diphenylsilandiol II wurde untersucht. Abhängig von Lösungsmittel, Temperatur und Katalysator werden unterschiedliche Primärprodukte erhalten. Die Reaktion in Masse bei 120°C mit Titan(IV)-isopropylat als Katalysator liefert ein transparentes Harz A. Das eduktfreie Produkt wurde IR-, 1H- und 13C-NMR-spektroskopisch charakterisiert und chromatographisch mit GPC und HPLC untersucht. Die trimeren und tetrameren Siloxane bestehen aus Diphenylsilan- und 3-Glycidyloxypropylmethoxysilaneinheiten. Das Verhältnis von cyclischen zu linearen Molekülen beträgt 2:1. Höhermolekulare Verbindungen entstehen nur in geringen Mengen. Das Epoxysiloxangemisch löst sich in unterschiedlichen organischen Lösungsmitteln und ist mit kommerziell verfügbaren Epoxiden mischbar. Die Zeitabhs̈ngigkeit von Viskosität und Epoxidwert bei der Lagerung unter Normalbedingungen wurden gemessen und mit HPLC verfolgt . Die Lagerstabilität wurde durch eine zusätzliche thermische Behandlung verbessert.
    Notes: Condensation of 3-glycidyloxypropyltrimethoxysilane I with diphenylsilanediol II was investigated. Depending on solvent, temperature and catalyst, different products were obtained. Bulk reaction at 120°C using titanium(IV)-isopropylate as a catalyst provided the transparent resin A. A was characterised by IR, 1H- and 13C-NMR spectroscopy and contained no reactants. GPC and HPLC studies revealed that A consists of trimer and tetramer siloxanes of pertinent diphenylsilane and 3-glycidyloxypropylmethoxysilane moieties. The proportion of cyclic to linear molecules was evaluated 2:1. Only small amounts of high-molecular-weight compounds were observed. The epoxysiloxane product proved to be miscible with various organic solvents and with commercial epoxy resins. Time dependence of viscosity and epoxy content were recorded during ambient storage and monitored by HPLC. Pot-life was improved by a subsequent thermal procedure.
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  • 73
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    Angewandte Makromolekulare Chemie 218 (1994), S. 163-170 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Cis-1,4-Polybutadien wurde durch Polymerisation von 1,3-Butadien mit Katalysatorsystemen hergestellt, die Ni(OOC8H15)2 und Al(C2H5)3 sowie die Lewissäuren BF3 · O(C2H5)2 oder TiCl4 enthalten. Die Molmassenverteilungen (MMD) der erhaltenen Polybutadiene wurden mit der Größenausschlußchromatographie (SEC) untersucht. Sie lassen sich mit Summen aus Schulz-Flory-Funktionen (SFF) beschreiben. Da eine Art aktiver Zentren eine SFF ergibt, die durch Molmassenmittelwerte definiert ist, lassen sich verschiedene Molmassenverteilungen nach Bandentrennung auf gleiche und verschiedene Arten aktiver Zentren untersuchen. In den untersuchten Systemen lassen sich zwei vergleichbare und eine unterscheidbare Art aktiver Zentren zuordnen. Auf diese Weise wurde das Kettenwachstum in Abhängigkeit von den Komponenten und Katalysatorformierungsbedingungen untersucht.
    Notes: Cis-1,4-polybutadiene was produced by polymerization of 1,3-butadiene using a catalyst system containing Ni(OOC8H15)2 and Al(C2H5)3 and the Lewis acids BF3 · O(C2H5)2 or TiCl4. The molar mass distributions (MMD) of the polybutadienes are investigated by means of size exclusion chromatography (SEC). The MMD's were fitted by a sum of Schulz-Flory-Functions (SFF). Taking into account that one kind of active species gives one SFF defined by molar mass averages, one comparable active species in both systems and one different were found. This way it was tried to find a relationship between the grown up of the active species depending on components and reactions conditions.
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  • 74
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-L-proline in the molecular weight range 50,000-90,000 has been synthesized from L-proline-N-carboxyanhydride. The molecular weight obtained is dependent on the initiator concentration. The rate constants for the polymerization have been determined by measuring the CO2 evolution. By observation of rotation during the polymerization, it is possible to deduce the conformation of the polymer in the polymerization solution. It is concluded that the immediate product of the polymerization is neither pure form I nor pure form II. The differences between form I and form II of poly-L-proline have been further characterized by measurements of their ultraviolet rotatory dispersion and their ultraviolet spectra.
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  • 75
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The base-catalyzed hydrolysis rate of the cationic esters obtained by quaternization of N,N,N′,N′-tetramethylethylenediamine with phenylbromoacetate was studied in buffers and in solutions of partially neutralized polymeric acids. The polyanions were found to be powerful inhibitors of the reaction. This effect was interpreted as due to the association of the ester with the polyanion, from which the catalytically active hydroxyl groups are repelled. It is shown that kinetic data may be interpreted by a procedure similar to the Lineweaver-Burk plot to yield the reactivity of the bound ester and the dissociation constant of the polymer-ester complex.
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  • 76
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of high molecular weight copolypeptides of L-proline and sarcosine have been synthesized. Experimental evidence is presented which indicates that the products are true copolymers rather than mixtures of homopolymers. In contrast to poly-L-proline I, a copolymer of L-proline-sarcosine I containing approximately 50% sarcosine is soluble in water. Two molecular conformations of the copolymers, similar to those found for polyproline, have been characterized by means of infrared spectroscopy and optical rotatory dispersion. The residue rotation of L-proline has been obtained from the copolymers and is -250°.
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  • 77
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    Biopolymers 21 (1982), S. 17-24 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Computer simulation shows that the time required to attain near sedimentation equilbrium is dramatically reduced by a two-step initial loading in which a macromolecular solution at low or zero concentration is layered above one at a higher concentration. To achieve the minimum time requires a good estimate of the molecular weight, but at least a 50% reduction in time can be achieved if the molecular weight of the macromolecule is known only within a factor of 2. Numerical solutions to the differential equation of the ultracentrifuge are calculated using the finite element method. An efficient Gaussian elimination algorithm can be used to minimize calculation time and computer storage requirements.
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    Biopolymers 21 (1982), S. 79-88 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The aldehydes present in acid-soluble type I collagen react with pyrenebutyrylhydrazine to form various types of complexes under different reaction conditions. These complexes exhibit one or more of three different pyrene fluorescence bands: monomer, excimer, and aggregate fluorescence. Collagen, whose aldehydes have been reduced with NaBH4, does not react with this fluorescent hydrazine, confirming that the hydrazine reacts specifically with aldehyde groups to form hydrazones. The absence of a reaction with pepsin-treated collagen also shows that the fluorescent labels are primarily in the nonhelical terminal telopeptides. Upon dialysis, the pyrene label bound to a saturated aldehyde in an α-chain is lost; whereas that bound to an unsaturated aldehyde remains on the protein. The pyrene monomer fluorescence in the β-chain of old collagen is stronger than that of young collagen. The formation of the pyrene excimer fluorescence implies the proximity of two pyrene molecules, probably attached to two adjacent aldehydes. Upon changing from acidic to neutral pH, both excimer and aggregate fluorescence bands disappear within a few seconds, revealing a very rapid alteration at the telopeptides.
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    Biopolymers 21 (1982), S. 147-157 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We describe conditions which lead to complete helix formation of poly(I) in the presence of NH4+. Binding of NH4+ is shown to be specific in the presence of Li+, which does not by itself support helix formation under these conditions. The NH4+-poly(I) complex is characterized by uv, CD, and ir spectroscopy. The CD spectrum is strikingly different from those of the Na+ or K+ complexes, the first extremum being changed from negative for the metal ions to positive for NH4+. A stereospecific model is proposed for the NH4+-poly(I) helix in which the N of NH4+ is located on the axis of the four-stranded helix, midway between planar tetramers formed by the bases. The model is consistent with the tetrahedral symmetry of NH4+, the requirement for four acceptable hydrogen bonds, the observed stability of the helix, and the accepted geometry of the backbone.
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    Biopolymers 21 (1982), S. 159-167 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has recently been proven that the counterion condensate around an isolated line charge in an electrolyte, as characterized by nonlinear Poisson-Boltzmann theory, is an encapsulating δ-function. Here the identical result is shown to hold in the framework of the polyelectrolyte theory of Fuoss, Katchalsky, and Lifson. The proof fully exploits analytic solutions to the differential equation which are not available for the nonlinear, cylindrical Poisson-Boltzmann equation.
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  • 81
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    Biopolymers 21 (1982), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The extent and modes of binding of the divalent metal ions Mn2+ and Co2+ to DNA and the effects of salt on the binding have been studied by measurements of the effects of these paramagnetic metal ions on the longitudinal and transverse relaxation rates of the protons of the solvent water molecules, a technique that is sensitive to overall binding. The number of water molecules coordinated to the DNA-bound Mn2+ and Co2+ is found to be between five and six, and the electron spin relaxation times and the electron-nuclear hyperfine constants associated with Mn2+ and Co2+ are little or not affected by the binding. These observations indicate little disturbance of the hydration sphere of Mn2+ and Co2+ upon binding to DNA. An average 2-3-fold reduction in the exchange rate of the water of hydration of the bound metal ions and an order-of-magnitude increase in their rotational correlation time are attributed to hydrogen-bond formation with the DNA. The binding constants of Mn2+ to DNA, at metal concentrations approaching zero, are found to be inversely proportional to the second power of the salt concentration, in agreement with the predictions of Manning's polyelectrolyte theory. A remarkable quantitative agreement with the polyelectrolyte theory is also obtained for the anticooperativity in the binding of Mn2+ to DNA, although the experimental results can be well accounted for by another simple electrostatic model. The various modes of binding of divalent metal ions to DNA are discussed.
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    Biopolymers 21 (1982), S. 265-275 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dc electrical conductivity of films of the polyelectrolyte complexes of glycol chitosan (GlChi) with the sodium salts of dextran sulfate (DS), carboxymethyl cellulose (CMC), polygalacturonic acid (GalUA)n, and alginic acid (AlgA) was measured at temperatures above and below room temperature. The maximum field strength in the thinnest film used amounted to 3 × 104 V/cm. A plot of normalized current against the reciprocal of the absolute temperature revealed two regions with different slopes, and activation energies in these two regions have been obtained for all the complexes. The activation energies in the high-temperature region vary from 0.85 to 1.18 eV and in the low-temperature region from 0 to 0.22 eV. Reasons are given to show that the conductivity is probably ionic. Near room temperature, the current-voltage relation is almost linear in the GlChi-DS complex, while in the other three complexes the current varies as a power n of the voltage with the value of n ranging from 1.7 to 2.5. A rise in temperatures causes an increase in the slope of the log I vs log V plot in GlChi-DS and GlChi-CMC complexes. The nonlinear current-voltage relation is ascribed to a space-charge-limited conductivity.
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  • 83
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    Biopolymers 21 (1982), S. 301-319 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Five different glucomannan samples were recrystallized from dilute solution. Depending on the experimental conditions, the crystals obtained could be identified as corresponding to the mannan I (anhydrous precipitate of more or less regular lozenge-shaped crystals) or mannan II (hydrated gel-forming pseudo-fibrillar precipitate). High-molecular-weight material, low temperature of crystallization, or a polar crystallization medium favored the mannan II polymorph, whereas a low-molecular weight, a high temperature of crystallization, and a crystallization medium of low polarity yielded the mannan I polymorph. Since the base-plane unit-cell dimensions are fairly constant with respect to variation of glucose, it is likely that isomorphous replacement of mannose by glucose occurs in glucomannan crystallization; the data also indicate that perfection of the glucomannan crystals was reduced in specimens having a high glucose:mannose ratio. The oriented crystallization of glucomannan on cellulose microfibrils was also studied under conditions where the mannan I polymorph was obtained. This gave shish-kebab structures that were characterized.
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  • 84
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The primary hydration process of native biopolymers is analyzed in a brief review of the literature, pertaining to various aspects of biopolymer-water systems. Based on this analysis, a hydration model is proposed that implies that the solution conformation of native biopolymers is stable at and above a critical degree of hydration (hp′ = 0.06-0.1 g H2O/g polymer). This water content corresponds to the fraction of strongly bound water, and amounts to ∼20% of the primary hydration sphere. In order to test this model, detailed sorption-desorption scanning experiments were performed on a globular protein (α-chymotrypsin). The results obtained are consistent with the proposed hydration model. They show that under certain experimental conditions, sorption isotherms can be obtained that do not exhibit hysteresis. These data represent equilibrium conditions and are thus accessible to thermodynamic treatment. Valid thermodynamic functions, pertinent to the interaction of water with biopolymers in their solution state, can be obtained from these sorption experiments.
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  • 85
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    Biopolymers 21 (1982), S. 451-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The light scattering of bovine serum albumin (BSA) has been measured at protein concentration up to 90 g/L and at pH values between 4.4 and 7.6. The dependence of scattering on both protein concentration and pH may be quantitatively accounted for by a simple extension of the hard-sphere model for protein solutions [Ross, P. D. & Minton, A. P. (1977) J. Mol. Biol. 112, 437-452] allowing for electrostatic repulsions between molecules. According to the extended model, the radius of the effective hard spherical particle representing BSA varies with the net electrical charge of the BSA molecule in a manner which may be calculated from electrostatic theory.
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  • 86
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    Biopolymers 21 (1982), S. 475-497 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A complete analysis of all possible conformations with correct hydrogen bonds of the collagen II type was performed on the basis of developed simultaneous equations. Using a unimodal search (by varying Ψ3), the energetically favorable structure was obtained. No other energetically satisfactory structural solutions are possible. The next aim was to obtain a precise model of the molecule. The program used includes a subroutine for continual deformation of the pyrrolidine rings. The set of parameters determining the structure consists of 14 independent variables (8 dihedral and 6 bond angles). As starting points for the energy optimization, conformations produced by scanning and some structures from previous work were used. The final structures (practically the same for both polymers) have helix parameters h = 0.285 nm and t = 52°, which are in excellent agreement with the 7/2 symmetry of diffraction data. The conformations of the pyrrolidine rings are of the B type, i.e., C2-Cβ-exo-Cγ-endo. For both polypeptides, the conformations of imino acids in position 3 of the triplet are the same; in position 2, however, they are slightly different. The difference in diffraction patterns for the 7/2 and 10/3 helices is discussed.
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  • 87
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    Biopolymers 21 (1982), S. 547-563 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The CD spectrum of the enzyme adenylate kinase has been investigated. Theoretical calculations, based on the x-ray crystal structure, have been carried out by means of an origin independent matrix formalism. The entire molecule was included in the calculations in the sense that essentially all electronic transitions that occur at wavelengths longer than 185 nm were included in the basis set. A linear dielectric function was utilized to evaluate the intertransition coupling potentials. The results of the theoretical calculations were in reasonable agreement with experimental CD spectra of the molecule.
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  • 88
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    Biopolymers 21 (1982), S. 633-652 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mode of action of many antitumor agents entails the inhibition of nucleic acid synthesis. Because many of the drugs can intercalate, it is assumed that intercalation is an important step in the mechanism of biological activity. As intercalants contain a planar chromophore as an ingredient essential for intercalation, chromophores that should fit into DNA are desired. This is the main theme of this investigation. Binding to DNA of fundamental moieties, protonated pyridine, aniline, phenol, quinone, and 4H-thiopyran-4-one, is studied to determine their optimum placement in DNA. The optimum orientations for each moiety are superimposed to form polyaromatic systems that can intercalate in a manner in which functional groups on these chromophores are oriented as in the moieties themselves. Ideal intercalants proposed contain three and four fused ring system, have protonated ring nitrogen atoms located to maximize the electrostatic interactions with DNA, hydroxy and amino groups that can hydrogen bond to the OII and O5′ phosphate backbone atoms, and carbonyl and sulfur groups in the central position of the ring system to provide variations in the chromophore and to interact with the relatively positive region in the intercalation site. The optimum orientation occurs when the chromophore and the base pairs overlap to the maximum extent. The ideal intercalants are fundamentally of the type:
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  • 89
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    Biopolymers 21 (1982), S. 665-677 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: DNA reassociation kinetics using the phenol emulsion reassociation technique (PERT) [Kohne, D. E., Levison, S. A. & Byers, M. J. (1977) Biochemistry 16, 5329-5341] has been investigated at high DNA concentrations using an endonuclease S1 assay of reaction progress. Apparent second-order rate constants fall on two intersecting straight lines when presented as a function of DNA concentrations on a log-log plot. In the low DNA concentration range, the rate constants drop about 10-fold when concentration increases 1000-fold. In the high DNA concentration range, the rate constants drop more than 10-fold when concentration increases 10-fold. The slopes of these lines are the same in different solvents and at different temperatures. The intersection between the lines occurs when the available catalytic surface is saturated. At high DNA concentrations, high-complexity heterologous denatured DNA apparently competes 2-4 times better for the surface than homologous DNA because it does not participate in a reassociation reaction. Native and partially native DNA molecules cannot compete with single-stranded DNA for a saturated surface. At high DNA concentrations, reactions using PERT become dependent on the single-strand DNA length. Increasing length lowers reassociation rates.
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  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Biopolymers 21 (1982), S. 859-872 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Classical potential functions (CPF) calculations on 3′-mononucleotides, the building blocks of nucleic acids, predict a correlation between the sugar ring pucker and the torsion angle Φ′ around the C3′—O3′ bond. In ribonucleotides, the value of Φ′ depends on the sugar pucker, viz. the C2′-endo sugar pucker is associated with Φ′ = 210° and 270°, while the C3′-endo sugar pucker favors only Φ′ = 210°. On the other hand, in deoxyribonucleotides, both sugar puckers show a preference for Φ′ = 180°. These theoretical predictions are fully corroborated by the results obtained from x-ray and nmr studies on mono-, di-, and polynucleotides.
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of several surfactants on the secondary structure of bovine β-lactoglobulin B was determined from the circular dichroism spectra. The spectra were measured at several concentrations of surfactant ranging from 1 mg/mL to the critical micelle concentration. The surfactants studied were sodium dodecyl, decyl, and octyl sulfate, sodium dodecyl sarcosinate, dodecyltrimethylammonium bromide. The data were analyzed using the method of Chen et al. [Biochemistry (1974) 13, 3350-3359] to determine the percentage of α-helix, β-sheet, and unordered form at each surfactant concentration. In every case, an increase in structured form and a 20-25% decrease in the amount of unordered form was noted when the surfactant concentration reached the critical micelle concentration. However, the relative amounts of the two structured forms present depend on the surfactant used. The profile of the secondary structure of the protein also varied from surfactant to surfactant as the protein was titrated, probably reflecting the delicate balance between ionic and nonionic forces that governs the secondary structure of β-lactoglobulin and most other globular proteins in aqueous solution.
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  • 93
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Amino acids are known to differ in their individual preferences for each of the four positions of the β-turn conformation formed by tetrapeptide segments. Proline and glycine show relatively high preferences for positions 2 and 3, respectively, of the β-turn. Using tripeptides of the type N-acetyl-Pro-Gly-X-OH, where X = Gly, Ala, Leu, Ile, and Phe, we have sought to study the influence of the 4th residue X on the stability of the β-turn conformation in these tripeptides. Our nmr and CD results show that the β-turn stability is quite significantly governed by the nature of the amino acid residue at this position in the following order: Leu 〉 Ala 〉 Ile, Gly 〉 Phe.
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  • 94
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    Biopolymers 21 (1982), S. 1153-1166 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermodynamic studies of the binding of adamantanecarboxylate to cyclodextrins have been made as a function of temperature and added organic cosolvent (methanol) using flow microcalorimetry. The negative heat capacity change associated with the adamantanecar-boxylate/β-cyclodextrin interaction and the fact that the interaction is weakened by the addition of methanol implicate the binding process as being a hydrophobically driven one. The negative enthalpy change (ΔH0 = -5.5 kcal/mol) and near-zero entropy change (ΔS0 = 1.5 cal/mol deg) are quite different from the values normally expected for a hydrophobic bond, indicating that other bonding forces are important in addition to the hydrophobic effect. The relative contribution of the hydrophobic effect and other bonding forces (most likely van der Waals forces) to the overall binding was judged from an analysis of the dependence of the thermodynamics of the association process on the surface tension of the water-methanol mixtures following a model for “solvophobic” bonding described by Sinanoglu [Molecular Associations in Biology (1968) Academic Press, New York, pp. 427-445]. From this analysis, adamantane-carboxylate/cyclodextrin complex formation is found to be driven to the extent of -1.9 kcal/mol by the hydrophobic effect. Furthermore, the hydrophobic driving force is found to be characterized by a positive ΔS0 of 10 cal/mol deg. The remaining free energy of binding (and the ΔH0 of binding of ∼-6 kcal/mol) is then due to the intrinsic (surface-tension-independent) van der Waals interaction between the ligand and cyclodextrin cavity.
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  • 95
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    Biopolymers 21 (1982) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 96
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pivaloyl-L-Pro-Aib-N-methylamide has been shown to possess one intramolecular hydrogen bond in (CD3)2SO solution, by 1H-nmr methods, suggesting the existence of β-turns, with Pro-Aib as the corner residues. Theoretical conformational analysis suggests that Type II β-turn conformations are about 2 kcal mol-1 more stable than Type III structures. A crystallographic study has established the Type II β-turn in the solid state. The molecule crystallizes in the space group P21 with a = 5.865 Å, b = 11.421 Å, c = 12.966 Å, β = 97.55°, and Z = 2. The structure has been refined to a final R value of 0.061. The Type II β-turn conformation is stabilized by an intramolecular 4 → 1 hydrogen bond between the methylamide NH and the pivaloyl CO group. The conformational angles are φPro = -57.8°, ψPro = 139.3°, φAib = 61.4°, and ψAib = 25.1°. The Type II β-turn conformation for Pro-Aib in this peptide is compared with the Type III structures observed for the same segment in larger peptides.
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  • 97
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    Biopolymers 21 (1982), S. 1333-1363 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The folding-unfolding process of reduced bovine pancreatic trypsin inhibitor was investigated with an idealized model employing approximate free energies. The protein is regarded to consist of only Cα and Cβ atoms. The backbone dihedral angles are the only conformational variables and are permitted to take discrete values at every 10°. Intraresidue energies consist of two terms: an empirical part taken from the observed frequency distributions of (φ,ψ) and an additional favorable energy assigned to the native conformation of each residue. Interresidue interactions are simplified by assuming that there is an attractive energy operative only between residue pairs in close contact in the native structure. A total of 230,000 molecular conformations, with no atomic overlaps, ranging from the native state to the denatured state, are randomly generated by changing the sampling bias. Each conformation is classified according to its conformational energy, F; a conformational entropy, S(F) is estimated for each value of F from the number of samples. The dependence of S(F) on energy reveals that the folding-unfolding transition for this idealized model is an “all-or-none” type; this is attributable to the specific long-range interactions. Interresidue contact probabilities, averaged over samples representing various stages of folding, serve to characterize folding intermediates. Most probable equilibrium pathways for the folding-unfolding transition are constructed by connecting conformationally similar intermediates. The specific details obtained for bovine pancreatic trypsin inhibitor are as follows: (1) Folding begins with the appearance of nativelike medium-range contacts at a β-turn and at the α-helix. (2) These grow to include the native pair of interacting β-strands. This state includes intact regular secondary conformations, as well as the interstrand sheet contacts, and corresponds to an activated state with the highest free energy on the pathway. (3) Additional native long-range contacts are completely formed either toward the amino terminus or toward the carboxyl terminus. (4) In a final step, the missing contacts appear. Although these folding pathways for this model are not consistent with experimental reports, it does indicate multiple folding pathways. The method is general and can be applied to any set of calculated conformational energies and furthermore permits investigation of gross folding features.
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  • 98
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peptide NH chemical shifts and their temperature dependences have been monitored as a function of concentration for the decapeptide, Boc-Aib-Pro-Val-Aib-Val-Ala-Aib-Ala-Aib-Aib-OMe in CDCl3 (0.001-0.06M) and (CD3)2SO (0.001-0.03M). The chemical shifts and temperature coefficients for all nine NH groups show no significant concentration dependence in (CD3)2SO. Seven NH groups yield low values of temperature coefficients over the entire range, while one yields an intermediate value. In CDCl3, the Aib(1) NH group shows a large concentration dependence of both chemical shift and temperature coefficient, in contrast to the other eight NH groups. The data suggest that in (CD3)2SO, the peptide adopts a 310 helical conformation and is monomeric over the entire concentration range. In CDCl3, the 310 helical peptide associates at a concentration of 0.01M, with the Aib(1) NH involved in an intermolecular hydrogen bond. Association does not disrupt the intramolecular hydrogen-bonding pattern in the decapeptide.
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  • 99
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    Biopolymers 21 (1982), S. 1469-1472 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 21 (1982), S. 1479-1487 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A formalism for extracting the conformations of a proline ring based on the bistable jump model of R. E. London [(1978) J. Am. Chem. Soc. 100, 2678-2685] from 13C spin-lattice relaxation times (T1) is given. The method is such that the relaxation data are only partially used to generate the conformations; these conformations are constrained to satisfy the rest of the relaxation data and to yield acceptable ring geometry. An alternate equation for T1 of 13C nuclei to that of London is given. The formalism is illustrated through an example.
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