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  • 1
    Electronic Resource
    Electronic Resource
    Polymerization of styrene by poly(bisphenol a 4,4′-azobis-4-cyanopentanoate) (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2909-2926 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A free radical initiator, poly(bisphenol A 4,4′-azobis-4-cyanopentanoate) (BPA), containing more than one azo group per molecule, was used to polymerize styrene in N,N-dimethylformamide (DMF) at 60°C. Polymerization rates were measured gravimetrically or dilatometrically, and the molecular weights of the isolated polystyrenes were determined viscometrically, both before and after hydrolysis. BPA has a relatively low initiator efficiency of 0.28. The activation energy and velocity constant at 60°C for decomposition of BPA per azo group in DMF were found spectroscopically to be 105.9 kJ/mole and 2.08 × 10-5 sec-1, respectively. The molecular weights of unhydrolysed polystyrenes increased with increasing conversion and a theory is developed to explain these results.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.170111112
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  • 2
    Electronic Resource
    Electronic Resource
    Free-radical polymerization of vinylferrocene. I. Kinetics (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1049-1070 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of vinylferrocene in benzene at 60°C in the presence of 2,2′-azobisisobutyronitrile has been studied. Densities and apparent densities were determined and rates of polymerization measured dilatometrically. The results show that vinylferrocene does not obey normal vinyl polymerization kinetics. Thus the rate of polymerization is proportional to the mean monomer and mean initiator concentrations both raised to a power of 1.1, and the degree of polymerization is independent of the initiator concentration. The polymerization reaction also has a high overall activation energy of 139 kJ/mole. The unusual kinetics are due to a monomolecular termination of the polyvinylferrocene chain radical which is also intermolecular with respect to the chain radical. Termination occurs by an intramolecular electron transfer reaction from a ferrocene nucleus to the growing chain radical which deactivates the chain radical and produces a polymer molecule containing a high spin Fe (III) complex. The presence of this species has been confirmed by Möussbauer and ESR spectroscopy. The rate constant for termination is between 3 and 60 sec-1. Intramolecular electron transfer has not been previously observed in vinyl polymerizations. The term “intralectran” is suggested to describe this new type of termination. Vinylferrocene readily undergoes transfer to monomer (with a transfer constant equal to about 8 × 10-3) and to polymer, but not to benzene.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130503
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  • 3
    Electronic Resource
    Electronic Resource
    Synthesis of vinyl graft copolymers of poly(hexamethylene adipamide) and poly(m-phenylene isophthalamide) (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 533-537 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nylon 66 [poly(hexamethylene adipamide)] and Nomex [poly(m-phenylene isophthalamide)] were metalated by using solutions of sodium in liquid ammonia. Metalation of the Nomex polymer was also carried out by using sodium naphthalene in tetrahydrofuran. The metalated polymers were then reacted with acrylonitrile monomer to yield the corresponding anionic graft copolymers. The heterogeneous nature of these reactions is discussed in relation to the structure of the graft copolymers.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160301
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  • 4
    Electronic Resource
    Electronic Resource
    Anionic synthesis of poly[ethylene methylene bis(4-phenyl-carbamate)-g-acrylonitrile] (1981)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 57-64 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A relatively high-molecular-weight polyurethane based on MDI and ethylene glycol was prepared and characterized. This polymer was metalated with sodium hydride in N,N-dimethylformamide (DMF) at about 0°C. Metalation was confirmed principally by spectroscopic identification of the N-methyl derivative obtained by coupling the metalated polymer with methyl iodide. Under appropriate reaction conditions the metalated polyurethane was used for the anionic graft polymerization of the reactive monomers acrylonitrile and ethylene and propylene sulfides. Attempted anionic graft polymerizations with other monomers, including styrene and ethylene and propylene oxides, were unsuccessful. The polyurethane grafted with acrylonitrile was separated by fractionation from accompanying small amounts of polyacrylonitrile, a low-molecular-weight homopolymer. One sample of polyurethane grafted with acrylonitrile was identified by microanalysis, IR, NMR, and increase in weight and was also characterized by differential thermal analysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1981.170190107
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  • 5
    Electronic Resource
    Electronic Resource
    Free-radical synthesis of poly(urethane-g-N-vinyl pyrrolidone) (1982)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 2879-2885 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relatively high-molecular-weight segmented polyurethanes based on methylene bis(4-phenyl-iso-cyanate), poly(propylene glycol), butane-1,4 diol, and cis-2-butene-1,4 diol have been synthesized and characterized. These unsaturated polyurethanes were successfully grafted using N-vinyl pyrrolidone as monomer and 2,2′-azobisisobutyronitrile as free-radical initiator. However, grafting experiments involving benzoyl peroxide as initiator were unsuccessful. The graft copolymers were isolated from the ungrafted polyurethane and poly(N-vinyl pyrrolidone) by selective solvent extraction. Elemental microanalysis, IR, NMR, thermogravimetric analysis, and equilibrium water sorption measurements were used to characterize the graft copolymers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1982.170201013
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  • 6
    Electronic Resource
    Electronic Resource
    Fire- and heat-resistant polymer based on maleimido-substituted 2,2-bis(anilino)-4,4,6,6-tetrakis-(4-aminophenoxy)-cyclotriphosphazene (1984)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 1141-1151 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fire- and heat-resistant polymer was obtained by the thermal polymerization of bismaleimido-substituted 2,2-bis(anilino)-4,4,6,6-tetrakis-(4-Aminophenoxy)-cyclotriphosphazene. The thermal stabilities of the polymer were evaluated in nitrogen and in air by thermogravimetric analysis. This polymer was stable to 345°C and had char yields of 78% at 800°C in nitrogen and of 71% at 700°C in air. The structures of cyclotriphosphazene precursors and the polymer were characterized using Fourier-transform infrared and proton nuclear magnetic resonance spectroscopy.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1984.170220514
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  • 7
    Electronic Resource
    Electronic Resource
    Effect of oxygen on the polymerization of vinyl chloride. II. Polymer properties (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2779-2788 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bulk and suspension polymerizations of vinyl chloride have been carried out in the presence of small known amounts of added oxygen at 54°C in the presence of peroxide initiators. The concentrations of oxygen were in the range 0-1240 ppm for 1-gal bulk polymerization systems and 0-400 ppm for 15-gal suspension polymerization systems. The thermal stabilities of the polymers prepared in the presence of oxygen were lower than those prepared under corresponding oxygen-free conditions. The average molecular weights of bulk polymers isolated at relatively low conversions were reduced in the presence of oxygen, and the infrared spectra of the polymers were altered. The significance of the decreased thermal stabilities of the polymers prepared in the presence of oxygen is discussed briefly in relation to the possible sites of initiation of dehydrochlorination.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121207
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  • 8
    Electronic Resource
    Electronic Resource
    Thermal polymerization of styrene in the presence of some ferrocene derivatives. I. Evidence of ferrocene-styrene interaction (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2005-2017 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene has been polymerized thermally at 60.5°C, without added initiator, in the presence of ferrocene. An increase in the rate of polymerization was observed, but the degree of polymerization remained constant. Evidence of ferrocene-styrene interaction is presented, and a kinetic scheme involving propagation with styrene in such an interaction state is proposed to account for these findings. Various kinetic parameters defined by this scheme have been evaluated.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130905
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetics of the homopolymerization of vinylferrocene in dioxane in the presence of 2,2′-azobisisobutyronitrile (1975)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 2133-2141 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the AIBN-initiated homopolymerization of vinylferrocene in dioxane has been investigated at 60°C. The rate of polymerization was found to be dependent on the monomer concentration to a power 0.97 and on the initiator concentration to a power 0.42. The overall activation energy for polymerization over the range 50-80°C was 84 kJ/mole. Analysis of polymer molecular weight data gave the chain transfer constant to monomer Cm as 1.2 × 10-2 and analysis of both rate and molecular weight data gave kp/(kt)0.5 as 2.36 × 10-2 dm1.5/mole0.5-sec0.5. Mössbauer and ESR spectra indicated the absence of Fe(III)-containing paramagnetic species in the polyvinylferrocene formed under these conditions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1975.170130917
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  • 10
    Electronic Resource
    Electronic Resource
    Free-radical polymerization of vinylferrocene. II. Spectroscopic and physical properties (1976)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 475-488 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spectroscopic and physical properties of poly(vinylferrocene) prepared by free-radical polymerization in benzene are discussed. The results obtained in these studies are in accord with the kinetic analysis of the polymerization reactions in benzene. ESR spectroscopy shows that the polymer is paramagnetic and contains a species which is identified by Mössbauer spectroscopy as an ionically bound complex of Fe(III) in a high spin (3d5) configuration. The concentration of this species is shown to be dependent upon kinetic parameters. Magnetic susceptibility measurements show that the polymer does not contain any oxidized ferromagnetic impurities. Infrared spectroscopy indicates that the polymer contains vinylidene groups. The presence of these groups is explained by chain transfer to monomer followed by reinitiation. Ultraviolet spectroscopy also suggests the presence of unsaturation in the polymer. Gel-permeation chromatography indicates that poly(vinylferrocene) is branched even at low conversions. The effect of transfer reactions and the intramolecular electron transfer termination of the chain radical on the structure of poly(vinylferrocene) is discussed. The glass transition temperature and thermal stability of the polymer are also examined.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1976.170140218
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