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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2105-2116 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In an effort to produce high-molecular-weight, linear ladder polymer by linking the nitrile groups within the molecule of polyacrylonitrile, polyacrylonitrile homopolymers were heat treated in N,N-dimethylformamide and N,N-dimethylacetamide solutions, in the presence of tertiary alkylamine catalysts. The products were soluble in formic acid, had relatively low molecular weight, and could be cast into brittle films. The infrared spectra indicated that the polymerization of the nitrile groups is initiated by a self-initiation mechanism based on the active methine groups in polyacrylonitrile, as proposed by Grassie and Hay, and that the reaction is complicated by molecular weight degradation via reverse Michael addition, as proposed by Hamada and Takahashi. The inherent viscosities of the products increase with increasing catalyst concentration, and further increases can be achieved by the addition of anionic chain coinitiators of phenolic nature. Density measurements indicated that the ladder structures undergo rearrangement into a more stereoregular form after formation, and that some aromatization occurs when the reaction is carried out in the presence of air.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic diamines react with pyromellitic dianhydride in solvents such as dimethyl-acetamide to form solutions of high molecular weight polyamic acids. These soluble polymers can be converted to insoluble aromatic polyimides. The aromatic poly imides exhibit zero strength temperatures above 700°C. and possess excellent thermal and oxidative stability. The stability characteristics of films and the relation of chemical structure to thermal and hydrolytic stability and to polymer properties such as crystallinity are described.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 1 (1963), S. 951-964 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study was made of the effect of polymerization temperature on the syndiotacticity of polyvinyl formate. Vinyl formate was polymerized with ultraviolet light initiation in the temperature range from -20 to +30°C. The value of (Ep  -  Et)/2 obtained, 4.5 kcal./mole, is characteristic of those values obtained by other workers for the free radical-initiated polymerization of vinyl acetate. A linear relationship was found to exist between the viscosities of the polyvinyl formates and those of the derived polyvinyl alcohols. The degree of polymerization of polyvinyl formate may be calculated from the equation: [η] = 4.42 × 10-3 DP0.63. The low temperature polymerization of vinyl for- mate results in more syndiotactic polymer, as shown by x-ray diffraction. Polyvinyl for-mate obtained at more elevated polymerization temperatures did not demonstrate the same degree of order. No difference was found between the infrared spectra of the polyvinyl formates. The polyvinyl alcohol derived from polyvinyl formate polymerized at low temperatures (0 to -35°C.) exhibits water resistance and forms a colored iodine complex similar to that obtained with the syndioactic polyvinyl alcohol derived from polyvinyl trifluoroacetate. Conventional polyvinyl alcohol and that derived from polyvinyl acetate polymerized at -30°C. do not exhibit the same properties. Minor differences in the 1,2-glycol content in the various polyvinyl alcohols do not account for the differences in the observations. The amount of head-to-head addition in various vinyl aliphatic esters seems to be related to the inductive strength of the acid portion of the ester. No difference was found between the crystallinities of the various polyvinyl alcohols, as measured by film density. Heat treatment increases the crystallinities about the same amount, but the water resistance of the stereoregular materials remains higher. From the good correlation between the observations made on polyvinyl formate and the derived polyvinyl alcohol, it is concluded that syndiotactic polyvinyl formate, and hence syndiotactic polyvinyl alcohol, is obtained by the low temperature free radical-initiated polymerization of vinyl formate. Increased syndiotacticity is more readily obtained in polyvinyl formate than in polyvinyl acetate, indicating the greater influence of inductive effect compared with the steric effect in controlling stereoregularity during free-radical propagation.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2607-2616 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermal conversion rates of the polyamic acid derived from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether are presented. Formation of the imide ring proceeds by fast and slow first-order processes. Tertiary amines give ring closures faster by a factor of 10 than the free acid. The enhancement is an activation entropy rather than an activation energy effect.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Aromatic diamines react with pyromellitic dianhydride in solvents such as dimethyl-acetamide to form solutions of high molecular weight polyamic acids. These soluble polymers can be converted to insoluble aromatic polyimides. The aromatic polyimides exhibit zero strength temperatures above 700°C. and possess excellent thermal and oxidative stability. The stability characteristics of films and the relation of chemical structure to thermal and hydrolytic stability and to polymer properties such as crystallinity are described.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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