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  • 1
    Electronic Resource
    Electronic Resource
    NMR of perfluoropolyether diols and their acetal copolymers (1995)
    s.l. : American Chemical Society
    Macromolecules 28 (1995), S. 7271-7275 
    Details
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ma00125a034
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  • 2
    Electronic Resource
    Electronic Resource
    End group chemistry of fluoro-oligomers: Highly selective syntheses of diepoxy, diallyl, and tetraol derivatives (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3263-3275 
    Details
    ISSN: 0887-624X
    Keywords: end group chemistry ; chemical modification ; fluoropolyether ; oligomer ; allyl ; epoxide ; polyol ; tetraol ; oxidation ; etherification ; NMR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Different synthetic methods for the preparation of polyfunctional fluorinated oligomers were explored and the results compared. Fluoropolyether macromonomers bearing epoxy, allyl, and polyhydroxy end groups were synthesized and spectroscopically characterized. For obtaining a polyol (namely tetraol) functionality, a highly selective route was the reaction of the fluoropolyether macrodiol ZDOL with allylic halides and subsequent oxidation reaction at the C=C double bond by means of peroxyacids. This approach made it possible to obtain a segmented structure RH-RF-RH in which the molecular body RF consisted of a perfluoropolyether block endcapped by two hydrogenated segments RH, where RH = - CH2OCH2CH(OH)CH2OH. Unlike other more conventional syntheses, which always produce byproducts and higher molecular weight species such as RH-(RF-RH)n-RF-RH or RH-RF-(RH)n-, the described method offers high yields and selectivity. The fluoropolyether polyfunctional derivatives offer the possibility to prepare a variety of highly crosslinked fluorinated materials and, owing to their well defined regularly segmented structures, they also constitute interesting models for the understanding of basic structure-property relations of fluoro-oligomers and their copolymers. © 1996 John Wiley & Sons, Inc.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Model structures of thermoplastic polyesters having regularly alternated aromatic and fluorinated segments (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 939-947 
    Details
    ISSN: 0887-624X
    Keywords: fluorine ; perfluoropolyether ; polyester ; segmented ; thermoplastic ; interfacial synthesis ; thermal transitions ; dynamic-mechanical properties ; chemical resistance ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear segmented polyesters containing soft perfluoropolyether (PFPE) and hard aromatic segments are obtained by an interfacial polycondensation reaction of an acyl chloride-ended fluorinated prepolymer with various aromatic diphenols in the presence of phase transfer catalysts (PTC) as accelerators. Experimental conditions for reaching high molecular weights are discussed. The calorimetric analysis (DSC) of all the polyesters synthesized shows a typical biphasic morphology, where a very low Tg (〈 -110°C) corresponding to the segregated PFPE moiety, is always accompanied by another Tg or a higher melting temperature, depending on the nature of the hard phase. Dynamic-mechanical analysis (DMA) has been carried out confirming the DSC results and suggesting diversified mechanical behaviors at the various temperatures in line with the amorphous or semicrystalline nature of the polymer. Chemical resistance was finally tested by dipping in several solvents and chemicals. The new polyesters show high contact angles, a moderate swelling in many organic solvents and excellent stability in aggressive hydrolytic environments. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 939-947, 1998
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Fractionation of reactive perfluoropolyoxyalkylene oligomers (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 55 (1995), S. 989-995 
    Details
    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: Fractional distillation, solubility fractionation, and column chromatographic separation have been applied in the study of fractionation of perfluoropoly(oxymethylene-co-oxy-ethylene) oligomers with —CH2OH end units, containing mono and bifunctional species. With a suitable choice of conditions, all three techniques proved to be useful for the preparation of fractions with narrow molecular weight distribution. Column chromatography allowed the separation of fractions having, in addition, sharp mono and bifunctionality. On the bsis of the experimental results, general indications for designing reactive oligomers fractionation procedures are discussed, prevalently centered on the copolymer end effect, which is typically present in this kind of compound. © 1995 John Wiley & Sons. Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1995.070550703
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  • 5
    Electronic Resource
    Electronic Resource
    Thermovolumetric properties versus glass transition temperature of diolic perfluoropoly(oxyethylene-ran-oxymethylene) oligomersIn honour of Professor Mario Farina (1995)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 196 (1995), S. 2855-2871 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The specific volume v from - 20 to 60°C and the glass transition temperature Tg was measured of a homologous series of linear diolic oligomer fractions constituted by a random perfluoro-poly(oxyethylene-ran-oxymethylene) chain of fairly uniform composition and two —CH2OH end units, with a degree of polymerization x̄n from 5,4 to 165,9 (M̄n from 400 to 14900). An empirical parabolic v = v(T, wE) equation of state is found as satisfactory, wE being the end copolymeric composition expressed as weight fraction of end units, inversely proportional to M̄n. A predictive bridge is then established between thermovolumetric parameters and Tg, through a highly reliable linear relation vg - Tg between experimental Tg and calculated specific volume at Tg, which leads with measurable parameters to a Tg - wE relation, in very good agreement with experimental results. For the range of M̄n above 1500-2000, simpler relations can also be used to a good approximation, which are discussed in their physical meaning and validity.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1995.021960911
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  • 6
    Electronic Resource
    Electronic Resource
    Molecular characterization and chain flexibility of linear polyacetals containing poly-perfluoro(oxymethylene-ran-oxyethylene) macromers (1997)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 198 (1997), S. 3215-3228 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proper samples of polyacetals containing poly-perfluoro(oxymethylene-ran-oxye-thylene) macromers were synthesized by polycondensation of a fluorinated macrodiol (Fomblin ®ZDOL) and formaldehyde and fractionated by solvent/non-solvent separation. Of eight selected fractions, whose compositional homogeneity was checked by 19F and 13C NMR spectroscopy, the following measurements were performed: Mw by static light scattering; retention volume Vr at GPC; [η] by conventional capillary viscometry; glass transition temperature by DSC. 1,1,2-Trichlorotrifluoroethane was used for solution measurements, from which the second virial coefficient A2, the linear Mw-Vr equation of GPC calibration, and the [η]-Mw Mark-Houwink-Sakurada constants K and a were determined. From [η] and Mw data, the Kθ value (unperturbed state) was estimated by the Stock-mayer-Fixman-Burchard extrapolation procedure, and the characteristic ratio C∞ of polyacetals containing poly-perfluoro(oxyethylene-ran-oxymethylene) macromers was calculated through the Fox-Flory equation. Factors related to chain flexibility were finally discussed and compared with those of corresponding fully perfluorinated copolyethers.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1997.021981019
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  • 7
    Electronic Resource
    Electronic Resource
    Fundamental properties of fluoropolyether-based resins and related coatings (1996)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 236 (1996), S. 111-127 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Neuartige Fluoropolyether-Polyol-Harze, die mit konventionellen Härtern wie Polyisocyanaten oder Melaminen aushärtbar sind, wurden hergestellt. Zunächst wurden oligomere NCO-terminierte Prepolymere durch Addition von Fluorpolyether-Makrodiolen unterschiedlicher Molekulargewichte an Isophorondiisocyanate erhalten. Durch die Reaktion dieser Prepolymeren mit Trimethylolpropan wurden endständige Hydroxygruppen eingeführt. Die Viskosität von Lösungen dieser Harze wurde bei unterschiedlichen Konzentrationen (Massenbruch 0,4-0,8) und Temperaturen (25°C-65°C) gemessen. Die erhaltenen Werte wurden auf der Basis der Erickson-Gleichung (Konzentrationsabhängigkeit von η) und unter Berücksichtigung des WLF-und des Arrhenius-Modells (Temperaturabhängigkeit von η) diskutiert. Das thermische Verhalten der Harze und von ausgehärteten Filmen wurde mit DSC bestimmt. Dabei wurden zwei Glasübergange beobachtet, die den separierten fluorhaltigen und nicht-fluorhaltigen Phasen zugeordnet werden können. Die Analyse des Zugverhaltens der Filme zeigte besonders bei den mit Isocyanat gehärteten Proben ein ausgeprägtes hart-plastisches Verhalten. Diese Werkstoffe erscheinen für die Anwendung als hoch-wertige, dauerfeste und klare Beschichtungen geeignet.
    Notes: New fluoropolyether polyolic resins are presented suitable to be cured with conventional hardeners as polyisocyanates or melamines. These resins are prepared by addition of fluoropolyether macrodiols (Fomblin® ZDOLTX) of various molecular weights to isophorone diisocyanate (IPDI) to give oligomeric NCO-terminated prepolymers. The final hydroxy functionality is obtained by the reaction of those prepolymers with trimethylolpropane (TMP). The viscosity of the resins is measured at various concentrations (weight fraction 0.8 - 0.4) and temperatures (T = 25-65°C). The results are discussed in terms of the Erickson equation (η vs. concentration) and using the WLF and Arrhenius models (η vs. T). The thermal behavior is studied by DSC for both the resins and cured films indicating the presence of two Tgs, corresponding to the segregated fluorinated and hydrogenated phases, the former particularly evident with the highest molecular weights of the fluorinated macromer. Tensile curves of selfsupported films are then analyzed showing an evident tough-plastic behavior especially for the isocyanate-cured films. The application of such materials as high-durability clear coats is finally proposed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1996.052360109
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  • 8
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of low-viscosity fluoropolyether-based segmented oligomers (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 231 (1995), S. 47-60 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden sechs oligomere Polyole synthetisiert und charakterisiert. Die Oligomeren waren aus strukturell gleichen Perfluorpolyether-Ketten, aber mit unterschiedlichen Endgruppen aus Hydroxygruppen enthaltenden hydrogenierten Segmenten aufgebaut. Zur Synthese der Polyole wurde der Fluorpolyetherdiol-Precursor (ZDOL) mit Epoxiden oder Dibromalkanen verethert. Die Reaktion mit Epoxiden führte direkt zu den Polyolen, während mit Dibromalkanen zunächst die fluorierten Dibromderivate erhalten wurden, die mit Malonat und durch anschließende Reduktion in die Polyole umagewandelt wurden. Die Viskosität der Oligomeren wurde bestimmt, und der Einfluß von Temperatur, Lösungsmittelkonzentration sowie Gehalt an Hydroxyendgruppen auf die Viskosität wurde ermittelt. Die außergewöhnlich niedrige Glastemperatur und Viskosität sowie die gute Mischbarkeit mit gängigen Lösungsmitteln machen diese Polyole als Harze für hochfeste Beschichtungen interessant.
    Notes: Six oligomeric polyols having a common perfluoropolyether chain end-capped by different hydrogenated segments containing hydroxylic groups were synthesized and their properties described. The general scheme for the synthesis of these polyols involved the etherification of the fluoropolyether diol precursor (ZDOL) with epoxides or dibromoalkanes. The former reaction gave directly the polyolic derivatives, while the latter yielded the fluorinated dibromoderivative which could be converted to polyols through the reaction with malonate and final reduction.The viscosity of these oligomers was measured and its dependence on temperature, solvent concentration and hydroxylic end-groups content was established. The exceptionally low Tg and viscosity together with the good miscibility with common solvents make these polyols very interesting as “resins” suitable for high-solid coatings.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052310105
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  • 9
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    NMR of perfluoropolyether diols and their acetal copolymers (1995)
    American Chemical Society
    Details
    Publication Date: 1995-10-01
    Print ISSN: 0024-9297
    Electronic ISSN: 1520-5835
    Topics: Chemistry and Pharmacology , Physics
    Published by American Chemical Society
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  • 10
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    Hydrophilic–oleophobic behaviour in thin films from fluoromodified nanoclays and polystyrene (2009)
    Springer
    Details
    Publication Date: 2009-04-18
    Print ISSN: 0170-0839
    Electronic ISSN: 1436-2449
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Published by Springer
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