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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 26 (1993), S. 4984-4985 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Statistische Copolymere aus Styrol und Methacrylsäure mit unterschiedlicher Zusammensetzung wurden hergestellt und ihre Konformationen in verschiedenen Lösungsmitteln durch potentiometrische Methoden untersucht. In Abhängigkeit vom Ionisationsgrad (α) tritt eine Konformationsumwandlung ein. Die Änderung der freien Enthalpie (ΔG0) für die Umwandlung der beiden ungeladenen Konformationen wurde bestimmt. Die Abhängigkeit von ΔG0 vom Styrolgehalt sowie von der Zusammensetzung der Lösungsmittelmischung und der Temperatur zeigt, daß die ungeladenen Polyelektrolytketten eine kompakte (kugelförmige) Konformation einnehmen, die durch hydrophobe Wechselwirkungen maximaler Stärke stabilisiert wird. Grobe Abschätzungen der freien elektrostatischen Energie des Makroions zeigen, daß die Dimensionen der kompakten Form zwischen α=0 und dem Umwandlungspunkt ansteigen, so daß eine von Lösungsmittel freie “Kugel” nicht an der Konformationsumwandlung beteiligt sein kann. Es wird vorgeschlagen, daß letztere in einem eindimensionalen System erfolgt, abhängig von der Wechselwirkung benachbarter Gruppen.
    Notes: Random copolymers of styrene and methacrylic acid were prepared in a wide composition range, and their conformational properties were investigated by potentiometric methods in different solvent media. A conformational transition occurs as a function of the degree of ionization (α). The Gibbs free energy change of the transition between uncharged conformers (ΔG0) was determined. The dependence of ΔG0 on styrene content as well as on the composition of the solvent mixture and the temperature, shows that the uncharged polyelectrolyte chains assume a compact conformation (globule) stabilized by hydrophobic interactions of maximum strength.Rough considerations on the electrostatic free energy of the macroion indicate that the dimensions of the compact form increase between α=0 and the transition point, so that the “globule” does not participate in the conformational change. It is suggested that this latter occurs in a one-dimensional system, depending on the interaction of neighboring groups.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The activated anionic polymerization of ε-caprolactam in presence of LiCl (up to 10 wt.-%) is studied under quasi-adiabatic conditions. The temperature increase of the system, after proper corrections for the heat exchange with the surroundings, allows to evaluate the enthalpies of polymerization δHp and to correlate their variations with the specific interactions of LiCl with monomer and polymer. The sharp decrease of -δHp as function of LiCl content is attributed to the stabilizing effect of the ion-dipole interactions, which is higher for the monomer-salt pair than for the polymer-salt mixture. The initial rates of polymerization are enhanced by a few percents of added LiCl, with a maximum at about 3 wt.-%. The relative influence of various physical factors on the polymerization kinetics and thermodynamics is discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 182 (1981), S. 1399-1405 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study on the anionic polymerization of 2-pyrrolidone in bulk and suspension under isothermal conditions is described. After a discussion about the disadvantages of the bulk process carried out by using N-potassium-2-pyrrolidone as initiator and N-acetyl-ε-caprolactam as activator, a possible alternative way is proposed on the basis of the suspension polymerization initiated by N-potassium-2-pyrrolidone and activated by silicon tetrachloride. The ultraviolet absorption spectra of the polymer samples obtained by the above methods reveal that undesiderable side reactions leading to degradation of the keto amide groups, are almost negligible under the aforementioned conditions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The activated anionic polymerization of ∊-caprolactam is strongly affected by LiCl addition to the polymerizing medium. Large variations in the yield of the polymerization products are induced by increasing salt content: both high polymer and cyclic dimer yields sharply decrease as functions of the salt concentration, whereas monomer and (in part) higher oligomers show a relevant increase. Also the production of low molecular weight side products is influenced by LiCl: higher salt concentrations induce the formation of larger amounts of side compounds. Monomer equilibrium data reveal that the salt negatively affects the thermodynamics of polymerization. ΔG0p variation as a function of LiCl content shows an increasingly relevant influence of the entropic contribution to the standard free energy change. The effects of LiCl on ring-ring equilibria are qualitatively interpreted on the basis of both the strong ion-ion interactions between Li+ ions and carbonyl groups and the interchain densification process.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 10 (1985), S. 11-23 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The comonomer system based on vinylidene fluoride (VDF) and hexafluoropropene (HFP) has been polymerized in soapless emulsion, at various pressures of the gaseous feed and different concentrations of the free-radical initiator. The particle size and number, evaluated as a function of conversion, suggest a rather long nucleation period. In Smith-Ewart's Interval II the limiting particle number decreases with increasing monomer fugacity (which is proportional to the monomer concentration in water), and increases with increasing initiator concentration. The kinetic data cannot be fully accounted for by changes of particle number. On the contrary, there is evidence that the average number of free radicals per particle is affected by experimental conditions and follows a trend very similar to that predicted by Stockmayer's model.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Physical and mechanical properties of poly(ε-caprolactam) synthesized in presence of various amounts of lithium chloride are measured on compression moulded films and correlated to the molecular organization, both in the amorphous and in the crystalline regions. By increasing the amount of LiCl present in the system it can be observed a heigtening of Tg and density of the amorphous phase as well as an increase of tensile modulus and yield strength. A transition from ductile to brittle failure occurs for both semicrystalline and amorphous samples in dry conditions, when the salt content in the amorphous phase is about 6 wt.-%. These phenomena and the capability of the salt to reduce the crystallinity of the polymer are interpreted in the frame of the already accepted model of ion-dipole interactions between lithium ion and the carbonyl groups of the polyamide. Effects due to moisture uptake are also discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 1213-1222 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and yields of N-trifluoracetylation of polyamides, polyesteramides, polyurethanes were studied by direct titration of trifluoracetic acid formed during the conversion. For polycaprolactam a limiting yield, corresponding to a complete substitution, was always achieved, independently of polymer molecular mass. The functionalization was equally effective on ultra high molecular masses or “gels”, as well as on low molecular mass compounds (monomer and higher oligomers), making possible their fast detection in any polycaprolactam sample. As the reaction starts and proceeds for most of its time in the heterogeneous phase, the substitution rate was found to be strongly dependent on the size of polymer particles. Extension of the above reaction to polyurethanes revealed that they react much slower than aliphatic polyamides, showing relevant differences in the behaviour of aromatic and aliphatic moieties.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 3297-3303 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two carbamoyl-type activators of ε-caprolactam (CL) anionic polymerization have been used in quasi-adiabatic conditions with sodium caprolactamate as initiator, at different concentrations and relative ratios. The reaction products have been characterized in terms of high-polymer content and extent of crosslinking. Correlations between the various polymerization parameters on one side, and amount of crosslinked fraction and resultant polymer properties on the other side, have been found. Potential implications on a fine control of PCL properties, exerted by the experimental conditions chosen for the anionic synthesis, are envisaged.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(∊-caprolactam) (PCL) with improved flame-retardant (FR) properties can be easily obtained by activated anionic polymerization of the monomer, ∊-caprolactam (C), in the presence of adequate amounts of red phosphorus (red P). Analogous results with reduced P content can be achieved by coupling red P with a synergistic compound such as a chlorinated hydrocarbon or magnesium oxide (MgO). A peculiar advantage of this method is the possibility of obtaining a very fine and homogeneous dispersion of the FR additive in the polymer matrix, meanwhile avoiding the typical compounding techniques, which are expensive, often unsafe, and require melt mixing of the ingredients. Molecular, thermal, and mechanical characterization, as well as morphology of the resultant products, have been determined: No significant properties change have been found when FR agents are present, apart from the relevant improvement of the flame-resistance. Thus, by this novel procedure it is possible to prepare FR poly-(∊-caprolactam) without any appreciable deterioration of its typical properties.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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