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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 433-444 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, dilute solution characterization, and thermal analysis of seven polyaryloxyphosphazenes are described. Synthesis is accomplished by the ring-opening polymerization of hexachlorocyclotriphosphazene at 245°C, followed by reaction of polydichlorophosphazene with sodium aryloxide salts in solution at 115°C. Polymers prepared and characterized have the general structure [(ArO)2PN]n, with Ar = C6H5, m- and p-CH3C6H4, m- and p-ClC6H4, p-C2H5C6H4, or p-CH3OC6H4. Elemental and infrared analyses show these polymers are essentially free of reactive chlorine sites. All the polymers displayed high intrinsic viscosities [η] 〉 1 dl/g, in tetrahydrofuran or chloroform. Closer examination of the dilute solution properties of two polyaryloxyphosphazenes revealed high molecular weights (M̄w〉 6 × 105) and broad molecular weight distributions (M̄w/M̄n 〉 4.7). The experimental values for the Z-average radii of gyration, 〈S2〉z1/2, characterized at near theta conditions, are larger than the calculated values for a freely rotating chain, which suggests that these polymers are relatively linear and not highly branched. Thermal analysis revealed second-order glass transitions between -37 and +13°C and first-order endothermic transitions between 43 and 160°C for the different polymers. Although crystalline structure can persist above this first-order transition, this temperature can be regarded as a melting temperature or softening temperature at which films can be molded. Decomposition temperatures, measured in argon and oxygen, ranged from 250°C to 400°C.
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  • 2
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When cellulose triacetates and some hydrolyzed acetates are boiled in 2.5N hydrochloric acid there is no residue. Under the same conditions cellulose is hydrolyzed, and a residue is obtained with a limiting viscosity that is related to the average length of the cellulose crystallites. These findings are combined to develop a method for studying the progress of acetylation through the amorphous portion of cellulose and into the crystallites, and to investigate the relative reactivities of cellulose I and cellulose II. Acetates were made from cotton and wood cellulose by a “fibrous” (heterogeneous) esterification involving sulfoacetic acid or perchloric acid catalyst in acetic acid-acetic anhydride; the final acetyl contents (10-41%) were attained by stopping the reaction at various points short of the triester (rather than by hydrolyzing a triester). When these acetates were boiled in 2.5N HCI they did not disappear completely, and the residues were cellulose I, indicating that cellulose acetate had been removed. With increasing acetyl the yield of residue decreased, and beyond about 33% acetyl the viscosity and x-ray measurements showed that the length and width of the crystallites decreased. However, when a nonsolvent such as toluene was added to the acetylation medium, the limiting viscosity did not change over the same acetyl range (up to 40%). Samples of varying acetyl values were taken during a regular acetylation of cotton linters in a mixer with sulfuric acid catalyst. X-ray studies of the residues obtained by boiling the acetates in 2.5N HCI revealed the presence of unreacted cellulose I even after 40% acetyl had been reached. This explains why the manufacture of cellulose esters from cellulose I requires complete esterification before they are hydrolyzed to the desired acetyl level. It was shown that there is a distinct difference between the acetylation reactivity of cellulose I and cellulose II. This indicates the importance of avoiding cellulose II formation during the refinement of cellulose for the manufacture of cellulose acetate in a process involving activation with acetic acid.
    Additional Material: 22 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1067-1076 
    ISSN: 0887-6266
    Keywords: transmission electron microscopy ; block copolymer ; polyimide ; nanofoam ; porous films ; polymer foam ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transmission electron microscopy was performed on a polymeric nanofoam material, derived from a triblock copolymer composed of a fluorinated polyimide center block, 3F/PMDA (derived from pyromelletic dianhydride (PMDA) and 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (3F)) and polypropylene oxide (PO) end blocks. The cast and imidized polymer exhibits a microphase-separated morphology consisting of PO microdomains within a polyimide matrix. The final nanofoam material is obtained by decomposing PO microdomains into low molecular weight products, which diffuse out of the polyimide matrix leaving nanometer length scale voids. Ruthenium tetroxide staining prior to microscopy was used to enhance the contrast between the 3F/PMDA matrix and the PO microdomains or voids, which permitted a more detailed view of the microstructure of both the foamed and unfoamed materials. From the power spectra of the micrographs, spatial correlation between the PO microdomains in the unfoamed material and between the voids in the foam were found. An interdomain separation distance of ca. 37 nm was observed. Analysis of the image yielded an average area of 411 nm2 for the PO domains. The analysis indicated that the PO domains were oblong, having average major and minor dimensions of 35 and 12.5 nm, respectively. An autocorrelation of the image showed that the domain center of masses were positioned 41 nm apart, in close agreement with the domain spacing (ca. 37 nm) found as described above. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1067-1076, 1997
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 1429-1446 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Zirconium hydrocarbyl catalysts react with nylon and poly(ethylene terephthalate) (PET) fibers to produce a supported species which may be used to polymerize a sheath of polyethylene around the fiber. Very high catalyst activities have been achieved over very short reaction periods on PET spinning threadlines. It is also possible to use these reagents to produce strongly adhered oxide and sulfide surface coatings. Infrared evidence is given for a mechanism in the case of reaction between catalyst and PET.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3775-3779 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 6
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Liquid sulfur-olefinic reactions at 140°C forming crosslinked polysulfide polymers have been investigated. A systematic approach to the characterization and some structure-property studies on these new polymeric materials has been presented. The olefinic systems of interest are endo-and exo-dicyclopentadiene and an oligomeric alkenyl polysulfide. Equimolar S8-olefinic system copolymers are amorphous and they show no tendency for sulfur crystallization. A correlation has been drawn between chemical structure and glass transition temperature of the copolymers and terpolymers. Mechanical properties and, in particular, chemical stress relaxation of the crosslinked polysulfide polymers have been investigated.
    Additional Material: 12 Ill.
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  • 7
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthetic route to polyetherimides by displacement of nitro-groups from disubstituted bis-imides by the dianion of bisphenols are described. The prepration of bis-imides and bisphenol dianions, their polymerization, and some of the properties of the polymers are presented in detail. The 13C-NMR spectra of intermediates and products were used to establish compositions and determine molecular weights.
    Additional Material: 8 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 23 (1985), S. 525-533 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sulfonated polystyrene (S-PS), which is of considerable scientific and technological interest, has been traditionally prepared by the sulfonation of preformed polystyrene. This report describes the preparation and properties of S-PS prepared by emulsion copolymerization of styrene and sodium styrene sulfonate. S-PS prepared by copolymerization gave solubility, solution behavior and thermal characteristics that are consistent with an ionomeric structure. The solubility characteristics indicated some chain-to-chain sulfonate heterogeneity. Thermal analysis studies indicated that the glass transition does not increase with increasing sulfonate content. This is contrary to what has been observed for S-PS prepared by sulfonation and suggests that the S-PS prepared by copolymerization is fundamentally different in structure than S-PS prepared by sulfonation of polystyrene.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 23 (1985), S. 549-568 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As part of a continuing study of ion-containing polymers, a comparison has been made on styrene-based sulfonate ionomers obtained by two different processes. Copolymers of styrene with sodium styrene sulfonate (SSS) have been compared with corresponding polymers obtained by the sulfonation/neutralization of preformed polystyrene (S-PS). The former system covered a range of sulfonate level from 1 to 30 mol %, while the latter ranged from about 1 to 7 mol %. The characterization of these materials has been conducted using solubility behavior, dilute solution viscometry, thermal mechanical analysis, density measurements, and water adsorption studies. At low (ca. 1%) levels the solubility behavior of the SSS copolymers and the sulfonated polystyrenes were similar. However, at higher sulfonate levels the solubility behavior in different solvents and the dilute solution viscometry were significantly different for the two systems. Similarly, thermal analysis studies (DSC) showed that the glass transition of the sulfonated polystyrene increased linearly with sulfonate level, while the Tg for the SSS copolymer increased modestly, up to about 7 mol % sulfonate content, and then remained constant. Significant differences in the softening behavior and water absorption characteristics were also observed for these two classes of ionomers. Although molecular weights and molecular weight distributions are not now available for these ionomers, the differences in their behavior does not appear to be due simply to differences in molecular weight. It is postulated that the differences in the copolymer and the S-PS ionomers may originate with differences in sulfonate distribution. It is suggested that the SSS monomer units are incorporated as blocks in the copolymer as opposed to a more random distribution in the S-PS ionomer. Indirect evidence in support of his argument is found, for example, in the case of the copolymer in the solubility behavior, the relative independence of Tg on sulfonate concentration and the apparent existence of a second, high temperature transition tentatively attributable to an ion-rich phase. Additional studies are required to confirm this hypothesis.
    Additional Material: 14 Ill.
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  • 10
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The technique for determining branching in polymers by using a combination of GPC and intrinsic viscosity data has been extended beyond current methods. Equations used in these analyses are presented. The derivations are based upon the assumption that branching is present only when there is a measurable reduction in the intrinsic viscosity. Techniques for calculating the functionality of the star branch point in starbranched polymers are given. Three random-branching parameters are calculated from a knowledge of the average branching density, \documentclass{article}\pagestyle{empty}\begin{document}$ \bar \lambda $\end{document}: (a) the lowest molecular weight branched polymer that can be measured, M̄*; (b) the average molecular weight between branch points, M̄bp; (c) the weight percentage of polymer that is branched. The applicability of this technique is demonstrated by using an analysis of published data on characterized fractions of a randomly branched polystyrene.
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