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  • 101
    Electronic Resource
    Electronic Resource
    Analysis of the ultraviolet/visible spectrum of degraded poly(vinyl chloride) to determine polyene concentrations (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2115-2122 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120929
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  • 102
    Electronic Resource
    Electronic Resource
    Comments on a paper by Williams on latex particle morphology during polymerization and at saturation equilibrium (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2133-2135 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120931
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  • 103
    Electronic Resource
    Electronic Resource
    Bulk polymerization of methyl methacrylate in the presence of poly(methyl methacrylate). II. Effect of oxygen (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2145-2147 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120934
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  • 104
    Electronic Resource
    Electronic Resource
    Chemical modification of polymers. II. Reaction of poly(vinylbenzyl chloride) and phenols (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2141-2143 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120933
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  • 105
    Electronic Resource
    Electronic Resource
    Coordination polymers from polycondensates and metal oxides. II. Effect of water molecules on the reactions of polyesters with Mgo and ZnoPaper presented at the IUPAC Symposium on Macromolecules, Aberdeen, September 10-14, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2155-2163 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyester molecules containing free carboxyl end-groups react with MgO and ZnO as polydendate ligands to form donor-acceptor complexes, followed by the increase in molecular weight of the original polyester. The role of water in these coordination reactions was studied. It was demonstrated that the water can catalyze the reactions by promoting an ionization effect. In some case it can coordinate to the metal compound and effectively compete with the other ligands present.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121001
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  • 106
    Electronic Resource
    Electronic Resource
    Effect of neighboring groups in macromolecular reactions: Distribution of units (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2165-2185 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of the complete description of the sequence distribution of units in products of macromolecular reactions is discussed. The exact mathematical solution is proposed based on the muitiplet method and rate constants and including the distribution of reacted units as well as nonreacted units. Various approximate solutions of the same problem, i.e., Markovian approximations of the first, second, and third order and an approach based on the consideration of the kinetics of transformations of the sequences of reacted units (B approximation) are considered. To compare the efficiency of various methods of calculation some characteristics of the distribution of units are estimated following exact and approximate equations at various ratios of rate constants.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121002
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  • 107
    Electronic Resource
    Electronic Resource
    Preparation and photolysis of poly-p-methoxyacrylophenone and its copolymers with styrene and methyl methacrylate (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1913-1924 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-p-methoxyacrylophenone (PPMeOAP) and its copolymers with styrene (PMe-OAP-S) and with methyl methacrylate (PMeOAP-MMA) were prepared. The photolysis in solution with 313 and 366 nm radiation was followed viscometrically. In solvents such as chlorobenzene and ethyl benzoate, random main-chain scission from n-π* excited triplet state occurs. The lowest excited triplet state in formic acid and in ethylene chlorhydrin is of the character π-π*, from which no main-chain scission occurs. In solvents in which destruction occurs, the main-chain scission is retarded by triplet quenchers, such as naphthalene, 2,5-dimethyl-2,4-hexadiene, and biphenyl. Quenching experiments indicate that the lifetime for the excited triplet state of PPMeOAP is 25 times that for polyacrylophenone. In PMeOAP-MMA copolymers, quantum yields of main-chain scissions were lower and lifetimes of excited triplets were longer than in PPMeOAP, due to hindered intramolecular photoreaction.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120906
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  • 108
    Electronic Resource
    Electronic Resource
    Photosensitized dehydrochlorination of poly(vinyl chloride). III. Reaction of thermally degraded poly(vinyl chloride) with hydrogen chloride (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1933-1943 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Films prepared from thermally degraded poly(vinyl chloride) were photolyzed in the presence of hydrogen chloride. When the light was filtered through a Pyrex disk, the absorbance in the region between 270 nm and about 415 nm decreased and reached a minimum value but the absorbance increased at wavelengths shorter than 270 nm and longer than 415 nm. Maximum bleaching occurred at a wavelength which depended on that of the irradiating light. When the Pyrex filter was omitted, an additional slower photodehydrochlorination reaction was superimposed on the photobleaching reaction. Photolysis of hexane or ethanol solutions of 1,8-diphenyloctatetra-1,3,5,7-ene and hydrogen chloride showed a similar reaction involving bleaching of the absorption of the polyene structure. The problems of using absorbance as an indication of the extent of the photodegradation of poly(vinyl chloride) are discussed.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120908
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  • 109
    Electronic Resource
    Electronic Resource
    Aromatic polyethers, polysulfones, and polyketones as laminating resins. III (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1945-1952 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4,4′-Diphenoxydiphenylsulfone was polymerized with isophthaloyl chloride and terephthaloyl chloride in Friedel-Crafts polymerizations. These polymers had 5-cyanoisophthaloyl units in the backbone obtained either by using 1,3-bis(p-phenoxybenzoyl)-5-cyanobenzene or 5-cyanoisophthaloyl chloride as part of the acid chloride monomer. A terpolymer having 22 wt-% 5-cyanoisophthaloyl unit was also prepared from the Friedel-Crafts polymerization of 1,3-bis(p-phenoxybenzenesulfonyl)benzene and 5-cyanoisophthaloyl chloride. These terpolymers were crosslinked through heating to give insoluble products which proved to be thermally less stable than the uncrosslinked polymers.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120909
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  • 110
    Electronic Resource
    Electronic Resource
    Preparation of a polypentenamer having pendant ionic groups and its hydrogenated derivatives (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1965-1981 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polypentenamers having pendant carboxylate groups including esters, acids, and salts and their hydrogenated derivatives have been prepared and characterized, and some of their properties investigated. Reaction conditions were established to control the amount of pendant thioglycolate groups incorporated into the polypentenamer by the free-radical addition reactions of thioglycolic acid derivatives and subsequently to completely hydrogenate the polymers so formed, which contained thioglycolate contents ranging from less than 1 mole-% to about 16 mole-%, without backbone degradation and crosslinking reactions. The glass transition temperatures and the melting points of these polymers were observed to depend upon the pendant group content, as expected, but there appears to be little difference within these properties between polymers in which the pendant groups were in the salt form as compared to those of the corresponding carboxylic acid form. The thermal stabilities of the polymers having the pendant groups were somewhat lower than those of the parent polymers, apparently because of side reactions involving the thioglycolate groups. The calcium salt derivative showed a particularly low thermal stability compared to that of polymers with monovalent salts.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120911
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  • 111
    Electronic Resource
    Electronic Resource
    Kinetic analysis based on the excluded-volume effect for radical polymerization (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1991-2004 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When the potential of average force based on the excluded volume affects the relative motions of the polymer radicals, the specific rate for bimolecular reaction between them can be approximated as kt = const. (ns)-a, where a = 0.153(2b - 1), b being a constant in the Mark-Houwink equation, and n and s being degrees of polymerization. Introduction of such a rate into kinetic equation yields a relative molecular weight distribution: G(n) = (n/m)2-2a exp {ph(m1-a - n1-a)}, where m = (2/ph)1/(1-a) is a degree of polymerization for the maximum in G(n) and ph is a parameter denoting kinetic character. Further, the relationship between polymerization rate Rp, monomer concentration [M], and initiator concentration [ε] is found to be: \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{{R_p }}{{\left[ {\rm C} \right]^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \left[ {\rm M} \right]}}\left[ {\frac{{\eta \left[ {\rm M} \right]^2 + \sigma \eta \Theta R_p }}{{\eta \left[ {\rm M} \right]^2 - \sigma \eta \Theta R_p }}} \right]^{{{(1 - 2a)} \mathord{\left/ {\vphantom {{(1 - 2a)} {2(1 - a)}}} \right. \kern-\nulldelimiterspace} {2(1 - a)}}} = {\rm const}{\rm . }\left[ {\rm M} \right]^{{a \mathord{\left/ {\vphantom {a {(1 - a)}}} \right. \kern-\nulldelimiterspace} {(1 - a)}}} \left[ {\rm C} \right]^{{{ - a} \mathord{\left/ {\vphantom {{ - a} {2(1 - a)}}} \right. \kern-\nulldelimiterspace} {2(1 - a)}}} $\end{document} where σ is a parameter denoting primary radical termination and η and η⊖ are viscosities for an arbitrary solvent and ⊖-solvent, respectively. These relationships are sufficiently applicable to the data obtained in the polymerizations of styrene and methyl methacrylate.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120913
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  • 112
    Electronic Resource
    Electronic Resource
    Phenolic resins for solid-phase peptide synthesis: Copolymerization of styrene and p-acetoxystyrene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2017-2025 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Details are given of the synthesis and purification of p-acetoxystyrene and its solution and suspension copolymerization with styrene. Reactivity ratios, evaluated by the Tidwell-Mortimer method, were r1 (p-acetoxystyrene) = 1.18, and r2 (styrene) = 0.88 for (bulk) solution copolymerization. Corresponding values of the reactivity ratios for suspension copolymerization were, within experimental error, indistinguishable from unity. Thus the copolymer composition is governed simply by the monomer feed composition. Use of a specially designed reactor vessel permits convenient suspension copolymerization of styrene, p-acetoxystyrene, and divinylbenzene to give crosslinked resins having comparatively narrow particle size distributions. Acetoxy groups in the crosslinked resin are cleaved by hydrazine hydrate under very mild conditions to give crosslinked polystyrenes having phenolic groups which, in turn, provide a useful alternative to the more usual chloromethylated polystyrene resins for solid-phase peptide synthesis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120915
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  • 113
    Electronic Resource
    Electronic Resource
    Role of chain transfer in heterogeneous polymerization of ethylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2027-2033 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The role of chain transfer was studied for the radiation-induced polymerization of ethylene in precipitating media, namely n-butyl alcohol, tert-butyl alcohol and their mixtures. The affinities of those solvents for polyethylene are similar, but the chain-transfer coefficient of n-butyl alcohol is larger than that of tert-butyl alcohol. The polymerizations were carried out in a reactor of 100 ml under a pressure of 300 kg/cm2, at 60°C, dose rate of 3.07 × 104-1.75 × 105 rad/hr in the presence of 50 ml of solvents. The polymerization in tert-butyl alcohol shows the kinetic behavior characteristic of a heterogeneous polymerization, such as rate acceleration, high dose rate dependence of polymerization rate, and low dose rate dependence of polymer molecular weight, whereas the polymerization in n-butyl alcohol does not exhibit such behavior and gives polymer having a molecular weight much lower than that of polymer obtained in tert-butyl alcohol. The polymer formed in tert-butyl alcohol exhibits a bimodal molecular weight distribution measured by gel permeation chromatography. In mixed tert-butyl alcohol and n-butyl alcohol solvent, with increasing fraction of n-butyl alcohol, the two peaks not only shift to lower molecular weight but the higher molecular weight peak becomes relatively small. Eventually, the polymer formed in n-butyl alcohol exhibits a unimodal distribution. Those results are well explained on the basis of the proposed scheme for heterogeneous polymerization.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120916
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  • 114
    Electronic Resource
    Electronic Resource
    Influence of fine structure on the pyrolysis of cellulose. III. The influence of orientation (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2053-2063 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of orientation upon the pyrolysis of cellulose were investigated by using a series of rayon fibers which differed only in orientation. The initial weight loss seen in low-temperature vacuum pyrolysis is due to crosslinking in the less ordered regions and was shown to be a first-order reaction whose rate varies directly with the degree of orientation. The extent of this reaction decreases with increasing orientation and is directly related to the amount of char formed at higher temperatures. The bulk pyrolysis rate increases with increasing orientation. DSC, air pyrolysis rates, and levoglucosan formation were also studied.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120919
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  • 115
    Electronic Resource
    Electronic Resource
    Structure and reactivity in cationic polymerization of butadiene derivatives. III. 2-phenylbutadieneFor Part II of this series, see Masuda et al.1 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2065-2072 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic polymerization of 2-phenylbutadiene (2-PBD) has been investigated. Polymerization were performed by SnCl4·TCA, WCl6, and BF3·OEt2 as catalysts in methylene chloride. 2-PBD polymerized easily and gave low molecular weight polymers. The polymerization proceeded to give a polymer having 1,4-structure without 1,2- or 3,4-structure. The double bonds of the polymer were partially consumed, probably owing to cyclization and chain-transfer reactions. 2-PBD was 0.66 times as reactive as styrene and 1.2 times as reactive as isoprene in the copolymerization at -78°C by SnCl4·TCA in methylene chloride. Reactivities of ring-substituted 2-PBD obeyed the Hammett relation with ρ+ = -2.04. The 13C chemical shift of ring-substituted 2-PBD was measured. Chemical shift values for C1 and C3 were correlated with Hammett σ, but those for C2 and C4 were almost unaffected by the substituents. On the basis of experimental results, the transition state of the cationic polymerization of 2-PBD was depicted as a benzylic cation rather than a phenylallylic one.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120920
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  • 116
    Electronic Resource
    Electronic Resource
    Anionic polymerization of methacrylate esters initiated with esters of α-metallocarboxylic acids (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2091-2094 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120924
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  • 117
    Electronic Resource
    Electronic Resource
    Resolution of structural factors in gelatin films (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2095-2097 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120925
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  • 118
    Electronic Resource
    Electronic Resource
    On the morphology of occlusions in the discrete phase of high-impact polystyrene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2105-2109 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120927
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  • 119
    Electronic Resource
    Electronic Resource
    Effect of tacticity on some aspects of behavior of PVC in solution. I. Viscosity and huggins constant of fractionated samples (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2111-2114 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120928
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  • 120
    Electronic Resource
    Electronic Resource
    Radiation-induced ionic polymerization of isobutyl vinyl ether in bulk (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2457-2466 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced ionic polymerization of isobutyl vinyl ether was investigated under conditions where the monomer was dried with molecular sieves. The investigation covered the temperature range from -16°C to 90°C, and the dose-rate range from 1015 to 1020 eV/g-sec, using both γ-rays and electrons. A very high overall activation energy of 15.9 kcal/mole was found for the process below 30°C. Above 30°C, however, the value of the overall activation energy dropped to 4.9 kcal/mole, a phenomenon which is ascribed to the solvation of the propagating carbonium ion below 30°C. The dose-rate dependence of the rate of polymerization was found to be 0.58 over the entire dose-rate range investigated. The molecular weight of the polymer was found to be far less sensitive to trace amounts of water than the rate of polymerization. The molecular weight of the polymer depended strongly on the irradiation temperature, reaching a maximum value of about 120,000 at 35°C. It is shown that at temperatures above 20°C regenerative chain transfer processes play an important role in determining the molecular weight of the polymer.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121101
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  • 121
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    ESR and chemical study of p-polyphenylene formed by using an AlCl3-CuCl2 catalyst (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2477-2495 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free radicals in p-polyphenylene and the formation of free radicals in this polymer upon pyrolysis in vacuum have been studied by means of electron spin resonance. For an unpyrolyzed series of polymer samples, a linear relationship was observed between free radical concentration and increasing carbon content. The free radicals observed in the unpyrolyzed samples did not react with NO. When samples of polyphenylene were pyrolyzed, additional free radicals were produced which did react with NO. The growth of free radical concentration upon pyrolysis was observed to be closely related to the production of volatile products from the polymer. In the temperature range 250-600°C, HCl was the principal volatile species produced. Two mechanisms were involved in HCl production: a process with an activation energy of 7.1 kcal/mole which led to the production of stable free radicals; and a process involving 75 kcal/mole which was unconnected with the production of free radicals. From 600 to 700°C, H2 was the principal volatile degradation product. The rate at which H2 was evolved showed a second-order dependence on phenyl units bearing two or three substituents; this process had an activation energy of 79 kcal/mole. Electron spin resonance spectra indicated that this process led to the production of free radicals, and infrared spectra showed that a highly crosslinked product resulted.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121103
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  • 122
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    Inorganic coordination polymers. XVI. Zinc(II) phosphinate polymers containing polyphenylene and poly(phenylene oxide) side groups (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2525-2534 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of a series of new phosphinic acids and the zinc polymers prepared from them are reported. These compositions are characterized by the presence of short polyphenylene and poly(phenylene oxide) chains as side groups. Some of the zinc derivatives were found to be tractable polymers with good thermal stability.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121106
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  • 123
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    Electronic Resource
    Sorption of gaseous ammonia on sulfonated macroreticular ion exchangers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2535-2543 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amount of gaseous ammonia sorbed on dry sulfonated macroreticular ion exchangers with different contents of divinylbenzene was found to be greater than the number of sulfonic acid groups. The excess ammonia could be removed by washing with water. With ion exchangers containing more than 20% of divinylbenzene a certain amount of chemically bonded ammonia could not be removed, even by elution with strong acid. Sorption of ammonia occurred also on dry ion exchangers fully neutralized with sodium ion, and in that case also, ammonia could only partially be removed by water from higher crosslinked samples. On desorption into a gaseous phase the amount of desorbed ammonia was proportional to the surface area of the ion exchanger, since desorption occurred only from surface layers. The results obtained indicate that ammonia migrates among acid groups located within the mass of the ion exchanger.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121107
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  • 124
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    Electronic Resource
    Photopolymerizations initiated by oxime derivatives (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2553-2566 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of ester, urethane, and carbonate derivatives of biacetyl monooxime, dimethylglyoxime, and ketone oxime, were synthesized and their photolyses studied by means of ultraviolet spectroscopy. Most of the oxime derivatives photolyzed easily upon UV irradiation. Among them, however, only the free radicals formed by photolysis from the ester and carbonate of biacetyl monooxime could effectively initiate the polymerization of a vinyl monomer such as methyl methacrylate. Based on the results obtained from the monomeric reactions, syntheses of grafting polymers were made. Graft polymers were obtained by using a copolymer of methyl methacrylate and methacrylic acid-biacetyl monooxime ester (copolymer I) and that of methyl methacrylate and vinyl benzioc acid-biacetyl monooxime ester (copolymer II) in good yield and without the formation of homopolymer. It was also found that when copolymer I was employed as a grafting polymer, a considerable amount of main-chain scission was seen, but no chain degradation was noted in the case of copolymer II. Photocrosslinking was attempted by using these copolymers in the presence of divinyl benzene. It was confirmed that copolymer II was photocrosslinkable, whereas copolymer I underwent photodegradation.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121109
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    Aspects of the synthesis and the properties of linear poly-2,5-dimethylbenzylenes (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2567-2579 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polydimethylbenzylenes, \documentclass{article}\pagestyle{empty}\begin{document}$\rlap{--} [C_6 H_2 (CH_3 )_2 CH_2 \rlap{--} ]_n$\end{document}, have been obtained by polycondensation of the monochloromethyl, acetoxymethyl, and methoxymethyl derivatives of p-xylene, via an acid-catalyzed reaction in anhydrous acetic acid and in 1-nitropropane. In the highly ionizing solvent acetic acid, because of ionic depolymerization, chain growth takes the form of an equilibrating polycondensation, of a maximum number-average molecular weight of 2200. In the noninteracting solvent 1-nitropropane, the molecular weight distribution is more random, and soluble polymers of number-average molecular weight up to 3900 are formed. The polycondensation reaction in 1-nitropropane is also initiated by perchlorate salts, in support of the suggestion of a “hot carbonium ion” propagation mechanism. The results are explained by a cataionic polycondensation reaction, yielding crystalline “living polymers” of high structural purity.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121110
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  • 126
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    Luminescence from thermally oxidized model amides in relation to nylon 66 degradation (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2623-2629 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluorescence and phosphorescence are observed following the mild thermal oxidation of two model compounds for nylon 66. Both emissions are remarkably similar in structure and in wavelength location to the corresponding emissions normally observed from the commercial polymer. Although the fluorescence could not be characterized, the phosphorescence exhibits several features which are clearly consistent with that of a nπ* carbonyl emission. The role of carbonyl groups in the thermal and photochemical oxidation of nylon 66 is discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121115
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  • 127
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    Block polymers from isocyanate-terminated intermediates. II. Preparation of butadiene-∊-caprolactam and styrene-∊-caprolactam block polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2613-2622 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polystyrene-nylon 6 and polybutadiene-nylon 6 block copolymers have been prepared from isocyanate-terminated prepolymers. From extraction and fractionation data the products obtained were found to be mixtures of both homopolymers and pure block copolymer. The polybutadiene-nylon 6 copolymers are extremely pliable at ambient temperatures even at high ∊-caprolactam contents (70-80 wt-%). This is true even though these copolymers show a crystalline melting point at 213°C similar to poly-∊-caprolactam. Presumably this unusual behavior occurs because of the nature of the synthesis which renders the butadiene portion of these copolymers the continuous phase. Plasticity measurements indicate that pliability is dependent on the molecular weight of the block poly-∊-caprolactam.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121114
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  • 128
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    Swelling measurement of some ethylene copolymers crosslinked by dicumyl peroxide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2631-2638 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Swelling equilibrium of crosslinked ethylene copolymers prepared by the curing of ethylene-vinyl acetate (EVA), ethylene-ethyl acrylate (EEA), and ethylene-acrylic acid (EAA) with dicumyl peroxide (DCP), has been measured in toluene at 23°C. The stress-strain behavior of the swollen EVA and EEA networks was in accord with that predicted from the statistical rubber elasticity theory, while that of the swollen EAA network was divergent. The concentration dependence of the polymer-solvent interaction parameter for the EAA network-toluene system was observed to be highest, while that for the EVA network-toluene system remained nearly zero. The order of the reactivity of pendant groups in the copolymers by radicals from DCP was estimated to be carboxyl 〉 acetyloxy 〉 ethoxycarbonyl group.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121116
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  • 129
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    Effect of photochemical oxidation on polypropylene phosphorescence (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2647-2650 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphorescence from polyolefins was studied from the aspects of excitation and emission wavelength and lifetime. Effects of photochemical oxidation on polypropylene phosphorescence are discussed in contrast to the effects of thermal oxidation.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121118
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  • 130
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    Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolytes. I. Potentiometric titrations of PLL in water and aqueous-organic mixtures (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2659-2670 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The potentiometric and viscosity behavior of salt-free solutions of the polycondensate between L-lysine and 1,3-benzenedisulfonyl chloride (PLL) and related polyelectrolytes, have been investigated in water and in aqueous-organic mixtures (acetone-water). The effects of counterions and solvent on the pH-induced conformational transition is related to hydrophobic interactions. The transition from a compact state to a more extended one shifts towards high values of neutralization with increasing length of N-tetraalkylammonium counterions. Moreover, the above transition gradually disappears as the percentage of acetone in the mixture is increased, which is interpreted as reflecting the breakdown of the compact structure due to hydrophobic interactions stabilized by bulky counterions. A linear decrease in the free energy variation ΔGt° is observed with increasing percentage of acetone up to about 40% of acetone, and a value of 1200 cal/unit is obtained for PLL in water, which is a reasonable value compared to other data for hydrophobic polyelectrolytes.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121120
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  • 131
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    Effect of nonelectrostatic interactions on the macromolecular behavior of polyelectrolyes. II. Influence of urea and dyes on the viscometric and optical behavior of PLL (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2671-2682 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of urea and of dyes on the viscometric behavior of aqueous solutions of PLL has been investigated. The compact structure, which is characteristic of PLL in pure water, is found to disappear progressively as the amount of urea is increased. This is interpreted as due to the destruction in such media of nonelectrostatic interactions responsible for the stabilization of the compact structure of PLL in pure water. In 8M urea, the macromolecular behavior of PLL during the ionization is dependent only on the repulsive interactions between the charged groups. The extension of PLL is then practically independent of the nature of counterions, contrary to what was observed in pure water. In the presence of dye (acridine orange), the compact form of PLL is stabilized, and the dye is found to bind for the two structures of PLL. The analogy between the behavior of Bu4N+ and that of dye is in agreement with the fact the Bu4N+ leads to a stabilization of the compact structure by way of specific interactions between N-tetraalkylammonium counterions and the PLL chain through the structure of water. The hydrodynamic behavior of PLL is in good agreement with data obtained from potentiometric and optical activity measurements.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121121
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  • 132
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    Photolysis of poly(ethyl acrylate) and poly(n-butylacrylate) in oxygen (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2697-2698 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121124
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  • 133
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    Kinetic approach to radiation-induced grafting in the polyethylene-styrene system (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2729-2739 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To investigate the mechanism of radiation-induced grafting in this system, the increase of monomer concentration in the polyethylene film in styrene vapor was evaluated by measuring the weight increase and formulated to be V([M∞] - [M]). The decay of radical concentration was also measured by ESR and the rate constant of the decay was determined. The alkyl type radical was affected only a little by styrene, while the allyl type radical was much affected by styrene. A new computer investigation method was proposed to clarify the reaction mechanism. The data obtained were substituted into differential equations and used to calculate the pattern of increase of the degree of grafting for the preirradiation method with reaction in the vapor phase. Results of these calculations suggest that only allyl type radicals induce grafting reactions and that the grafting reaction seldom occurs in the region of grafted polystyrene.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121203
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  • 134
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    Melting behavior of highly stretched isotactic polypropylene film (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2721-2728 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotactic polypropylene film was stretched in poly(ethylene glycol) at 140°C and its melting behavior was investigated by using a differential scanning calorimeter (DSC-1B). The shape of the melting curve depends largely on the stretching ratio, v. A sample stretched to moderate extension (1 〈 v 〈 3.5-4) has only a single melting peak (163°C) in the thermogram. When the sample is stretched beyond v = 3.5-4, the thermogram becomes more and more complex with increase of v, and some peaks appear when stretched to 10 〈 v 〈 13. The lowest peak which is considered to be the melting peak of the intermolecular crystals produced by the unfolding of chain molecules in the lamellae develops gradually with increase of v. In the thermogram for v = 18 the lowest temperature peak is most pronounced, in contrast to the highest temperature peak which decreases markedly in intensity. The phenomenon shows that large amounts of lamellar crystals are converted to intermolecular crystals in this region. On further stretching (v 〉 20) a very sharp high temperature peak appears, whose half-width is about 1°C. Qualitatively similar results were obtained for the samples stretched in poly(ethylene glycol) at 150°C and in air at 140 and 150°C.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121202
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  • 135
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    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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  • 136
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    NMR study of poly-p-isopropyl-α-methylstyrene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2391-2401 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 220 MHz NMR spectra of sample of poly-p-isopropyl-α-methylstyrene prepared through anionic (A) and cationic (B) polymerizations are studied. Peaks at τ values of 9.07, 9.41, and 9.71 are assigned to isotactic (i), heterotactic (h), and syndiotactic (s) α-methyl triads, respectively. From the α-methyl triads and the β-proton tetrads it is found that polymer A deviates little from Bernoullian statistics and that first-order Markov configurational statistics applies to polymer B. Isopropyl methine and methyl proton resonances are also analyzed in terms of the configurational statistics of the polymer. Resonances of the phenyl protons are assigned with increasing field to s, h, i meta and ortho protons.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121021
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  • 137
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    Radiation-induced emulsion polymerization of ethylene. VI. Continuous flow system (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2403-2417 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The radiation-induced emulsion polymerization of ethylene in a continuous flow system was carried out at 100°C by using FC-143 and potassium myristate. The polymer concentration in the latex during the course of the polymerization oscillated several times and then approached a steady-state value in a few hours in the case of short residence time. The rate of polymerization was almost constant within the residence time range of 0.2-0.9 hr. This is explained by the kinetics assuming the same mechanism previously proposed in the batch system, that is, the number of polymer particles in this range is considered to be constant. Gel formation was observed at longer reaction times in spite of the continuous supply of myristate micelles, possibly because large polymer particles are produced in this stage. The concentration of carbonyl group in the polymer produced by chain transfer to absorbed myristate ion changes in the same way as the polymer concentration with reaction time. The methyl group in the polymer is produced mainly by chain transfer to the polymer, and the concentration is nearly constant during the polymerization except in the initial stage. The rate constants for the continuous polymerization were very different from the batch polymerization previously studied, despite their similarities in nature. The mass transfer rate of the emulsifier from the micelles to the polymer particles requires future study.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121022
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    1-methacryloylimidazole as methacrylating agent (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2453-2455 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121026
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  • 139
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    Solid-state polymerization of a cyclic diacetylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2467-2475 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Large polymeric single crystals of a unique ring-bridged polymer have been produced by the solid-state polymerization of a cyclic diacetylene (o,o′-diacetylenyldiphenyl glutarate). These crystals are of high thermal stability, metallic in appearance with an asbestos-like texture, infusible, and insoluble. Single-crystal x-ray diffraction investigation indicates that the polymer is monoclinic (probable space group C2/c or Cc) with a unit cell containing four monomer units of dimensions α = 20.8 Å, b = 8.0 Å, c = 9.7 Å, and β = 106°. Infrared spectra eliminate the previously suggested possibility that the solid-state reactivity of the above monomer corresponds to either reaction of the carbonyl function with the acetylenic bond or the cleavage of the ester linkage. Diffraction, dichroism, and Raman spectral studies indicate instead that the reaction proceeds by 1,4-addition polymerization at the diacetylene group to produce a trans-trans polymer of structure where the curved lines represent the di-(o-phenyl)-glutarate linkages which are on opposite sides of the chain for adjacent monomer units.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121102
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  • 140
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    Modification of PVC. XXVI. Syntheses and photocrosslinking of polysulfide pendant poly(vinyl chloride) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2497-2509 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(vinyl chloride) pendant with polysulfide (PS-PVC) having various degrees of substitution, various S substituents, and various numbers of atoms in the sulfur chain has been synthesized by the reaction of poly(vinyl chloride) with a thiol, sulfur, and triethylamine in dimethylformamide at 30°C for 0.4-5 hr. The photocrosslinking reaction has been investigated under ultraviolet irradiation at 250-450 mμ. The photocrosslinking reaction of PS-PVC is influenced by the degree of substitution, the nature of the S substituent, and the number of atoms in the sulfur chain. The degree of photocrosslinking r increased in the order, n-C4H9— 〈 n-C8H17— 〈 C6H5CH2— 〈 i-C3H7— 〈 t-C4H9—. On the photocrosslinking of PS-PVC having two different S substituents, r increases in the similar order for aliphatic substituents and in the order NO2C6H4— 〈 ClC6H4— 〈 C6H5CH2— 〈 CH3C6H4— 〈 t-C4H9C6H4— 〈 C6H5— for the aromatic substituents. Further, r increases markedly with the increase of sulfur chain number for all PS-PVC. The chemical structure of the crosslinks and the crosslinking mechanism are discussed on the basis of the results.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121104
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  • 141
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    Photochromic behavior of copolymers of indolinospirobenzopyrane methacrylic derivatives (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2511-2523 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three photochromic 3,3-dimethyl-6′-nitroindolinospirobenzopyran methacrylic derivatives have been synthesized, namely, 1-methyl 8′-methacryloxymethyl (A), 1-(β-methacrylamidoethyl) (B), and 1-(β-methacryloxyethyl) (C). They have been copolymerized with methyl, isobutyl, and n-propyl methacrylates. The photochromic behavior of these copolymers in the solid state has been compared to that of the homologous isobutyric compounds dissolved in corresponding polymeric matrices. The kinetics of decoloration were resolved in three simultaneous first-order reactions with rate constants k1, k2, and k3. The influence of the polarity of the polymeric matrix and of the photochrome incorporation has been examined. The rates of decoloration of the copolymers with isobutyl and n-propyl methacrylate are very sensitive to the glass transition temperature Tg; the activation energy of decoloration increases markedly above Tg, from 19.8 to 36.5 kcal; below Tg the entropy of activation is strongly negative (around -20 e.u.), above Tg strongly positive. These effects are interpreted on the basis of an increasing chain segment mobility above Tg.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121105
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  • 142
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    Isotopic exchange of gaseous ammonia 14NH3 and 15NH3 in sulfonated macroreticular ion exchangers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2545-2551 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Adsorption and 15NH3 isotopic exchange was performed on dry macroreticular polystyrene ion exchanges crosslinked with varying amounts of divinylbenzene and partially neutralized by 14NH3. Data on pressure changes and mass spectrometric analyses of isotopic composition of the gaseous phase were used to calculate equilibrium distribution of 14NH3 and 15NH3 under various dislocation conditions. It was established that along with the exchange of 14NH3 to a gaseous phase, 15NH3 penetrates to the mass of ion exchanger. This is evidently due to the migration of ammonia among functional groups. It was found that by thermal desorption under reduced pressure ammonia is released only from functional groups located on the surface of ion exchanger.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121108
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  • 143
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    Relationship between radical polymerization rate and initiator concentration in various solvents (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2581-2593 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl methacrylate and styrene were polymerized by using 2,2′-azobis(2,4-dimethyl valeronitrile) as initiator in various solvents. When a poor solvent is used, the dependence of polymerization rate Rp on initiator concentration [C] is small and can be treated by equations for the analysis of the polymerization with primary radical termination. With a good solvent, the dependence of Rp on [C] is so large that such equations are not applicable. Thus, the [C] dependence in a good solvent is explained qualitatively through the molecular weight dependence of rate for termination between polymer radicals, based on the excluded volume effect.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121111
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  • 144
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    Low-angle x-ray estimation of macromolecular parameters of the scattering particles in Agave sisalana (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2595-2602 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various macromolecular parameters of Agave sisalana (sisal) fiber were investigated by the low-angle x-ray scattering method. The well known Kratky camera of the latest design was utilized for the experimental measurements. The sample studied was a densely packed colloidal system belonging to a general micelle system, and the theories of Kratky and Kratky and Porod were utilized to estimate the parameters. Pore analysis of the substance yields a value for the specific inner surface of the dispersed phase of 0.406 × 10-1 m2/cm3; the transversal length is the same as the length of inhomogeneity, 107.31 Å, and the length of coherence is 342.21 Å. The air fraction of the scattering particles was found to be 0.01%.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121112
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  • 145
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    Further studies on the ultraviolet graft copolymerization of maleimide by vapor-phase method (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2603-2612 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graft copolymerization of maleimide onto polyethylene and ethyl cellulose films by using its sublimation vapor was carried out under ultraviolet irradiation in the presence or absence of air; the effect of air or additives on the grafting reaction and on the nature of the grafted films was investigated. The extent of grafting gradually approached a fixed value, in spite of the continuous ultraviolet irradiation. Air retarded the grafting reaction but did not suppress the reaction nor alter the final extent of grafting. Benzoquinone showed no inhibiting effect on the grafting. The grafted polymaleimide was found to be amorphous, even though ultraviolet irradiation produces a highly crystalline homopolymer in the solid phase as well as in the liquid phase. The results were discussed in comparison with those of the vapor-phase grafting under γ-ray irradiation; the reaction is attributed to the vapor-crystal equilibrium of monomer and to the formation of short-chain crosslinks.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121113
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  • 146
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    Influence of the low molecular weight amides on the dynamic behavior of polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2639-2645 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dependence of the dynamic shear modulus G′ and mechanical damping tan δ was measured for mixtures of low molecular amides with VC/VAc copolymer and polystyrene, respectively. A new secondary relaxation was found, which in some cases depends on content of moisture. The effect of molecular structure and concentration of amide is shown.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121117
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  • 147
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    Conductivity of carbon black-loaded styrene-butadiene rubber (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2651-2657 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene-butadiene rubber (SBR) charged with 50 phr of HAF carbon black has been found to show a positive temperature coefficient of resistivity close to 0.07/°C at 27°C. Beyond a point (75°C) of minimum conductivity, however, it behaves as a normal noncrystalline semiconductor with a resistivity which decreases with rise of temperature with an activation energy of 0.56 eV. Blending the composition with poly(vinyl chloride) (PVC) shifts the minimum towards lower temperatures. The descending branch of the conductivity versus reciprocal absolute temperature characteristic is probably associated with thermal expansion of tunnelling paths separating the conducting carbon particles.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121119
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  • 148
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    Effects of additives on the radiation-induced emulsion copolymerization of tetrafluoroethylene with propylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2693-2696 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121123
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  • 149
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    Cationic starch-polyacrylonitrile graft copolymer latexesPresented at the 8th Great Lakes Regional Meeting, American Chemical Society, West Lafayette, Indiana, June 3-5, 1974. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2683-2692 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylonitrile (AN) was graft-polymerized onto gelatinized cationic starch (CS) possessing diethylaminoethyl ether groups by cerium (IV) initiation to give stable latexlike copolymer dispersions. Dispersions of the latex copolymers, having up to 50% grafted polyacrylonitrile (PAN), air- and heat-dry on glass to clear, adhesive films. Sonification of up to 8% dispersions at 20 Khz reduced their viscosities from 1500-3000 cP to 15-40 cP. Scanning electron microscopy revealed that both nonsonified and sonified dispersions consist of ball-like particles measuring about 0.05-0.15 μ in diameter when dry. The films are formed by coalescence of these particles. The degree to which AN grafts onto CS at ambient temperature is related to the nitrogen content of CS, gelatinization time of CS at 95°C, sequence of AN and cerium(IV) addition, concentration of cerium (IV), concentration of AN, and severity of reaction agitation. Number-average molecular weight values of PAN were about 106 when grafting was conducted under stirring and about 5 × 105 when conducted under shaking action.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121122
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  • 150
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    Polymerization of coordinated monomers. VI. Molecular complex formation of methyl methacrylate coordinated to stannic chloride with styrene or toluene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2701-2719 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium constants for the complex formation between stannic chloride and methyl methacrylate were determined in n-hexane-toluene solution at 0, -20, and -30°C by using the absorption band at 350 nm. Continuous variation plots at -20°C in n-hexane based on the 1H-chemical shifts definitely show a 1:1 interaction between the coordinated methyl methacrylate and styrene or toluene. The magnitudes of the shifts for the four groups of protons in methyl methacrylate are found to be in a specific ratio in common with the 1:2 complex-styrene or -toluene system. The equilibrium constants for the ternary molecular complex formation between the 1:2 complex and styrene or toluene were determined in n-hexane in the temperature range -50 to +20°C by use of the chemical shifts. The concentrations of the complex species in the alternating copolymerization solutions were estimated by use of the equilibrium constants. There is a linear relationship between the enthalpy and the entropy changes for the ternary molecular complex formation, which is governed by the enthalpy factor. The specificity of the interactions indicates a specific time-averaged orientation of benzene ring to the coordinated methyl methacrylate. The effects of the coordination of methyl methacrylate to stannic chloride were discussed on the basis of results of 13C-NMR spectroscopy.
    Additional Material: 10 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170121201
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  • 151
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    Salt-catalyzed addition reaction of monoepoxides with philosamia cynthia ricini and bombyx mori silk fibroins (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2741-2754 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heterogeneous addition reaction of various monoepoxides with silk fibroins of Philosamia cynthia ricini and Bombyx mori was investigated at 45-75°C by use of aqueous solutions of various salts as padding catalysts. The effects of salt on the epoxide-silk fibroin reactions were attributed mainly to the nucleophilicity of the anions and also to the acidity or the electronegativity of the cations. The effect of the substituent of the epoxide on the add-ons was elucidated by the modified Taft equation, (log W - log W0)/σ* = ρp + ρsEs/σ*, where W0 and W are the add-ons for the reaction of a given compound and of its substituted derivatives, σ* and Es are the polar and the steric substituent constants, ρp and ρs are the polar and the steric reaction constants, respectively. Histidine, lysine, arginine, tyrosine, serine, and acidic amino acids were found to react. The reactivity difference between Philosamia cynthia ricini and Bombyx mori fibroins towards the epoxide was discussed in the light of the observed phenomena.
    Additional Material: 8 Ill.
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  • 152
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    Crystallization-induced reactions of copolymers. IV. Ester-interchange reorganization of poly(ethylene terephthalate-co-2-methylsuccinate) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1-10 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The application of ester-interchange reactions to the crystallization-induced reorganization of random to block copolymers, which was demonstrated in the previous paper of this series, was followed quantitatively in this investigation. Structural changes based upon dyad compositions in copolyesters of terephthalic acid and 2-methylsuccinic acid with ethylene glycol were determined by high-resolution NMR. Sequence length distributions so calculated were related to the effects of copolymer composition, catalyst concentration, and reaction temperature on the rate of the ordering process and to the effect of structure on crystalline properties.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120101
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  • 153
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    Simultaneous polymerization and formation of polyacetylene film on the surface of concentrated soluble Ziegler-type catalyst solution (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 11-20 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A direct method of simultaneously polymerizing and forming acetylene monomer to produce uniformly thin films of polyacetylene was investigated in terms of catalyst system, catalyst concentration, and polymerization temperature. The best catalyst was a Ti(OC4H9)4-Al(C2H5)3 system (Al/Ti = 3-4) and the critical concentration was 3 mmole/l. of Ti(OC4H9)4. Below the critical concentration, only a solid or a powder was obtained. The configuration of the polymers obtained depends strongly upon the polymerization temperature. Thus an all-cis polymer was obtained at temperatures lower than -78°C, whereas an all-trans polymer resulted at temperatures higher than 150°C. Observations either in an electron microscope by direct transmission or in a scanning electron microscope showed that the film is composed of an accumulation of fibrils about 200-300 Å in width and of indefinite length.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120102
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  • 154
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    Diffusion into and adsorption of polyethylenimine on porous silica gel (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 29-43 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polyethyleneimine (PEI)-water-silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI-cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.
    Additional Material: 7 Ill.
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  • 155
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    Radiation-induced emulsion polymerization of ethylene. I. Effect of reaction conditions on the polymerization (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 83-92 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of reaction conditions on the rate of radiation-induced emulsion polymerization of ethylene was studied by use of a 500-ml autoclave. Among various kinds of emulsifiers, a series of potassium salts of fatty acids gave high rates of the polymerization. The polymerization was inhibited by the presence of oxygen, but the rate of polymerization followed by the induction period was not influenced by the initial presence of oxygen. Stirring rate and the monomer: water ratio did not affect the rate of polymerization. The rate of polymerization was maximum at about 80°C, and number-average molecular weight was influenced by the temperature in a similar manner as the rate of polymerization. This suggests that the change of mobility of propagating radical in the polymer particle changes the rate of termination reaction. The rate of polymerization was proportional to the 1.7 power of the reaction pressure.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120108
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  • 156
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    Decay of catalytic activity during the cationic polymerization of capryllactam (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 21-28 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At lower concentrations of initiator and temperatures above 200°C, the polymerization of capryllactam initiated by hydrogen chloride is characterized by two kinetically different stages: the initial rapid growth becomes considerably slower due to the fast transformation of the original growth centers into amidines. The steep decrease in molecular weight during hydrazinolysis indicates that the amidine groups are also present inside polymer molecules. The formation of these structures may be explained by condensation of the amino endgroups with the amide or acyllactam groups.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120103
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  • 157
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    Photoreactions of N-vinylcarbazole induced by metal salts. II. Further studies on the photocationic polymerization sensitized by sodium chloroaurate(III) in nitrobenzenePart I: Tazuke, Asai, and Okamura.2 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 45-56 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Further investigations of the photopolymerization of N-vinylcarbazole(VCZ) sensitized by sodium chloroaurate(III) in nitrobenzene were undertaken under irradiation of near-ultraviolet light at 30°C. Copolymerization with isobutyl vinyl ether and the kinetic behavior of polymerization were studied. These propagation and chain-breaking features were discussed in comparison with those obtained in the thermal polymerization. Electron spin resonance spectroscopy was conducted at 77°K in various systems.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120105
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  • 158
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    Stereochemistry of alternating methacryloyl-L-valine methyl ester-maleic anhydride copolymer (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 57-65 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereochemical composition of an alternating methacryloyl-L-valine methyl estermaleic anhydride (L-MAVM/MAn) copolymer which was prepared by the photocopolymerization of L-MAVM and MAn in dioxane at 25°C without initiator was investigated by proton magnetic resonance spectroscopy. The resonance of the ester methyl protons of the L-MAVM unit appeared as three split peaks at 3.65, 3.76, and 3.82 ppm, which could be assigned to those of the coisotactic (di-threo-tri-isotactic), coheterotactic and cosyndiotactic triads, respectively. The triad cotacticity determined according to these assignments indicated that the copolymer was composed predominantly of di-threo-tri-isotactic triad. Similarly PMR spectroscopic investigation of the acryloyl-L-valine methyl ester-maleic anhydride (L-AVM/MAn) copolymer with a 1:1 molar ratio of the monomers showed that the main tactic fraction of the copolymer was also di-threo-tri-isotactic one. Nevertheless, the circular dichroic investigation of the L-AVM/MAn copolymer before and after hydrolysis denied asymmetric induction into the polymer main chain. These results suggest that the propagation step in the photocopolymerization of L-MAVM or L-AVM with MAn proceeds by the trans-trans opening of the complexmer composed of a 1:1 molar ratio of L-MAVM or L-AVM and MAn.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120106
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  • 159
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    An application of spin trapping to radical polymerizationsContribution No. 313 from this department. A part of this study was briefly described previously.1 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 67-81 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical polymerizations and copolymerizations were carried out in the presence of phenyl tert-butyl nitrone(PBN) and tert-nitrosobutane (t-BuNO), and the structure of the spin adduct formed was investigated by ESR spectroscopy. PBN adducts gave the same ESR pattern, and the variation of the splitting constant was not large enough to warrant its use for the structure assignment. Therefore, the subsequent trapping experiments were performed with t-BuNO. The polymerization mixture of representative monomers showed esr patterns that are indicative of the propagating radical being trapped. These trapped radicals were not necessarily very stable and, in most cases, disappeared after long reaction periods. In the case of α-methyl substituted monomers, additional nine-line spectra were observed which were attributed to trapping of the radical species formed by hydrogen abstraction from the α-methyl group. The tert-butyl radical which was formed by decomposition of t-BuNo was probably responsible for the hydrogen abstraction. In the case of styrene, methyl acrylate, and methyl methacrylate, characteristic ESR patterns of the propagating radicals were observed with polymers which were prepared in the presence of t-BuNO and purified by reprecipitation. Simultaneous trapping of different propagating radicals was attempted in several copolymerization systems. However, this was generally unsuccessful, because of the large difference in reactivities of the propagating radical with t-BuNo.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120107
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  • 160
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    Radiation-induced emulsion polymerization of ethylene. II. Effect of potassium myristate concentration and dose rate on the rate of polymerization in connection with polymer properties, kinetics, and mechanism (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 93-103 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced emulsion polymerization of ethylene with potassium myristate as an emulsifier was studied in connection with the kinetics and the mechanism. The molecular weight of polymer was relatively low, of the order of 103, when a sufficient amount of emulsifier was used. However, polyethylene gel was produced in the absence of a sufficient amount of emulsifier. The rate of polymerization was proportional to the 0.5 power of dose rate and increased slightly with increasing emulsifier concentration. The rate of seeded polymerization followed a similar trend to that for conventional polymerization. Kinetic analysis of these results suggests that the escape of radicals produced by chain transfer of propagating radical with the emulsifier and the monomer from polymer particles into the aqueous phase plays an important part in the rate of polymerization. The melting temperature and the crystallinity of the polymer significantly decreased with increasing polymerization temperature in the range 40-60°C.
    Additional Material: 8 Ill.
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  • 161
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    Imidization during polymerization of acrylamide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 133-140 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The spontaneous imidization of acrylamide during polymerization has been studied in three media: benzene, diglyme, and water. The data indicate that neither medium, time, nor temperatures below 140°C cause imidization to occur. The ascription of the low nitrogen found in polyacrylamide by some investigators to imide formation appears to be in error. The low nitrogen is due rather to retained solvent and/or water, for which polyacrylamide has a strong affinity. Imidization may be brought about by strong acids. The solubility of an imidized polyacrylamide decreases with increasing imide content.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120112
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  • 162
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    Some aspects of graft polymerization of vinyl monomers onto cellulose by use of tetravalent cerium. IV (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 141-152 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intense agitation markedly decreased the homopolymer formation in homopolymerization reactions. Graft polymerization is similarly influenced, the main effect being on the propagation process. The results achieved in this work indicate that in grafting reactions, growing polymer radicals are produced mainly through the transfer of radicals formed at the cellulose backbone to the monomer where propagation takes place. The growing polymer radicals either recombine with active sites on the cellulose leading to grafting or react with each other through coupling and/or are oxidized with ceric ions to give homopolymer.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120113
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  • 163
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    Anionic polymerization initiators containing protected functional groups and functionally terminated diene polymersPresented in part at the Division of Polymer Chemistry, American Chemical Society, August 26-31, 1973, Chicago, Illinois. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 153-166 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organolithium reagents substituted with hydroxyl-carrying mixed acetals (i.e., tetra-hydropyranyl and α-ethoxyethyl ethers) have been prepared in high yields and used to polymerize 1,3-butadiene to various acetal-terminated polybutadiene polymers. A method is described for converting acetal-containing polymers into hydroxyl-containing polymers. The polybutadienes have been characterized with regard to endgroup types, quantitative functionalities, molecular weights, molecular weight distributions, and microstructures. Dihydroxyl terminated polymers are prepared anionically in the absence of gel. Such materials are more suitable from the standpoint of f(OH) and M̄w/M̄n for chain extension studies than are prepolymers prepared by radical methods.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120114
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  • 164
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    Temperature dependence on the binding of butyl orange by bovine serum albumin (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 191-200 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of 4′-dibutylaminoazobenzene-4-sulfonate anion (butyl orange) by bovine serum albumin has been examined quantitatively by an equilibrium dialysis method at 5, 10, 15, 20, 25, and 35°C. The first binding constants and the thermodynamic parameters for the formation of the first dye anion-protein complex have been calculated. The peculiar temperature dependence of the first binding constant could be observed. That is, the value of the first binding constant increases with increasing temperature until it reaches a maximum value at approximately 18°C and then decreases with raising temperature. Accordingly, this binding process is exothermic above 18°C and is endothermic below 18°C. Near 18°C the process exhibits athermal reaction. From the thermodynamic data obtained, it is evident that the favorable free energy of the binding is accompanied by an entropy gain and that the enthalpies of the binding vary from a positive (unfavorable) value below 18°C to a negative (favorable) one above 18°C. Furthermore an apparent temperature dependence of the thermodynamic functions was observed. That is, ΔF° becomes larger in absolute magnitude as the temperature increases. The positive quantity of ΔS° tends to decrease with increasing temperature. All these facts can be interpreted satisfactorily in terms of hydrophobic interactions between hydrophobic portions of the dye and nonpolar parts of the albumin.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120117
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  • 165
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    Titration curves of some structurally and molecularly uniform polynuclear phenolic compounds with additional functional groups (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 211-219 
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    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120119
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  • 166
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    Inorganic coordination polymers. XIV. Chromium(III) phosphinate perfluorocarboxylate polymersFor Part XIII of this series, see Gillman, Nannelli, and Block.1 (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 221-229 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polymers, {Cr(OH)(OPRR′O)[OOC(CF2)nCF(CF3)2]}x has been prepared and studied. The polymers with R = R′ = C6H5 are soluble in CCl2FCClF2, whereas those with R = CH3 and R′ = C6H5 and with R = R′ = C8H17 are insoluble in all solvents. Attempts to prepare similar materials without hydroxyl groups gave the polymers {Cr(OH)r(OPRR′O)p[OOC(CF2)nCF(CF3)2]q}x with 0 〈 r 〈 1. The latter polymers are much more tractable than the former; however they are also less thermally stable. The perfluoro-carboxylate groups in these materials can either be chelating or bridging, depending on the other ligands present.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120120
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  • 167
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    Reaction of polystyrene with n-butyllithium-N,N,N′,N′-tetramethylethylenediamine (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 247-250 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120123
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  • 168
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    Note on the kinetics of methyl methacrylate emulsion polymerization (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 251-254 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120124
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  • 169
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    New imidazoisoquinoline ladder polymers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 265-272 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In previous studies on poly{(7-oxo-7, 10H-benz[de]imidazo[4′,5′:5,6]-benzimidazo-[2,1-a]isoquinoline-3,4:10,11-tetrayl)-10-carbonyl} it was observed that the polymer exhibits very unusual film-forming properties. The ladder polymer forms supermolecular aggregates in solution which translates to a high degree of interchain packing in the bulk. New ladder imidazoisoquinoline polymers have been prepared in an effort to relate the variance of molecular structure to the aggregation behavior of this class of polymers. The polymers were prepared from the solution polycondensation of 1,4,5,8-naphthalene tetracarboxylic acid or dianhydride with 1,2,5,6-tetraaminonaphthalene, 2,3,7,8-tetraaminophenazine and 2,3,7,8-tetraaminodibenzofuran. It was found that the extent of interchain packing in the bulk is dependent to a large degree on the molecular geometry of the polymer backbone.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120202
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  • 170
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    Studies on the photooxidation mechanism of polymers. II. The role of quinones as sensitizers in the photooxidative degradation of polystyrenePresented in part at IUPAC Symposium on Photochemical Processes in Polymer Chemistry, June 12-15, 1972, Louven, Belgium. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 295-306 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the quinone-sensitized photooxidative degradation of polystyrene film and its solution in benzene, an initial rapid decrease of average molecular weight has been observed by GPC and viscosity measurements. The reaction rates are strongly increased by quinones such as p-quinone, duroquinone, anthraquinone, and chloranil. It has been suggested that this photosensitized degradation of polystyrene occurs by a singlet oxygen reaction which might be related to an energy transfer mechanism from excited triplet states of quinones to molecular oxygen. The photooxidative degradation of polystyrene in solution can be diminished by addition of typical singlet oxygen quenchers such as 1,3-cyclohexadiene or β-carotene.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120204
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  • 171
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    Formation and flocculation of graft copolymer micelles (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 323-335 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Criteria for formation and flocculation of micelles from pure graft copolymers were investigated in single selective solvents by turbidimetry with the use of two series of graft copolymers from poly(vinyl acetate) (PVAC), i.e., PVAC-styrene graft copolymers with one branch and PVAC-methyl methacrylate graft copolymers with one and several branches. These graft copolymers could be completely coagulated through two processes in the selective solvents which had widely different ⊖ temperatures. The first process is the formation of micelles. One sequence, i.e., either backbone or branch of the graft copolymers, becomes desolvated under conditions similar to those for the corresponding homopolymer. This results in formation of the core of the micelle, the other soluble sequence extending from the surface of the core into the solvent phase. As the soluble chains cover the micelle core, no macroscopic phase separation occurs, but a stable dispersion is formed. The second process is that the micelle becomes too unstable to exist as dispersed when the solvency of the medium for the soluble sequence decreases to a certain degree. As a result, flocculation of the micelle finally takes place.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120206
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  • 172
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    Polymerization of vinyl acetate retarded by 4-methyl-2,6-di-tert-butylphenol: Kinetic and ESR studies (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 347-356 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Methyl-2,6-di-tert-butylphenol strongly retards the free radical polymerization of vinyl acetate initiated by azobisisobutyronitrile. The chain transfer constant, estimated from rate data, is 0.020 ± 0.004 at 35°C and does not vary significantly with temperature. Molecular weight data lead to transfer constants of 0.023, 0.020, and 0.024 at 35, 45, and 55°C, respectively. A mean kinetic isotope effect of 9.8 ± 1.0 is observed for the phenol deuterated at the OH group, showing that the main attack of poly(vinyl acetate) radicals on the phenol involves hydrogen abstraction from this group. The activation energy for hydrogen abstraction is estimated to be 7.8 kcal/mole, and the rate constant at 50°C is 160 ± 40 1./mole-sec. The stationary concentration of 4-methyl-2,6-di-tert-butylphenoxyl in the polymerization mixture is proportional to the phenol concentration and is independent of the initiator concentration, as shown by electron spin resonance studies. Cross termination of poly(vinyl acetate) and phenoxy radicals occurs to a greater extent than mutual termination of these radicals. The rate constant for cross termination is close to 1 × 108 1./mole-sec at 50°C; the activation energy for cross termination is 2.9 ± 1.3 kcal/mole.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120208
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  • 173
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    Photopolymerization of methyl methacrylate with the use of iodine as the photoinitiator (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 375-386 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetics of photopolymerization of MMA at 40°C with the use of iodine as the photoinitiator was studied. At low range of iodine concentration (〈 0.0004M), the rate of polymerization was proportional to square root of iodine concentration and the monomer exponent was 2.5, while at a higher range of iodine concentration, (0.0005-0.002M) the initiator exponent and monomer exponent were zero and 3.6-3.8 (i.e., close to 4), respectively. The chain-transfer constant of iodine at 40°C was found to be 6.0. Polymerization was found to be largely inhibited in the presence of relatively high concentrations of iodine (〉 0.005M) and also in presence of hydroquinone. Kinetic and other data indicate a radical mechanism of polymerization involving complexation of monomer molecules with iodine prior to radical generation, and termination is believed to take place bimolecularly at low iodine concentrations and unimolecularly, involving reaction with iodine, at high iodine concentrations (initiator termination).
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120210
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  • 174
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    Kinetics of radiation-induced bulk polymerization of vinyl chloride in the temperature range of -50 to 90°c (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 411-432 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic investigations on the bulk polymerization of vinyl chloride initiated by exposure to 60Co γ-rays were carried out in the temperature range of -50 to 90°C at dose rates varying from 0.15 to 50 rad/c. Some polymerization runs were also carried out in a centrifugal field. As generally reported for this polymerization system, in which the polymer is insoluble in the monomer, the polymerization rate was found to change as a function of the amount of the polymer formed in a special fashion. This particular function has been shown to be greatly influenced by the polymerization temperature and to be independent of the rate of initiation, or, more rigorously, of the dose rate. Thus, at any given temperature the equation of the polymerization conversion rate could be written in the form of the product of two separate functions, one for the polymerization conversion and the other for the dose rate. While for the latter the results gave an essentially square-root dependence on dose rate as is normally found for homogeneous polymerization, the former has been discussed in the terms of recently advanced kinetic schemes, based on a two-phase polymerization model. The kinetic parameters found in this work are in agreement with previous authors' data.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120213
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  • 175
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    Olefin polymers derived from Diels-Alder adducts of 1,7-octadiene and hexachlorocyclopentadiene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 921-924 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120421
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  • 176
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    Polyurethane-polyacrylate interpenetrating polymer networks. I (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 885-896 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two-component topologically interpenetrating polymer networks (IPN) of the SIN type (simultaneous interpenetrating networks) composed of a melamine-cured polyacrylate and five different polyether-based polyurethanes were made. The linear polymers and prepolymers were combined in solution, together with the necessary crosslinking agents and catalysts; films were cast, chain-extended, and crosslinked in situ. Infrared spectroscopy indicated that little or no reaction between the different networks occurred. In all cases, except for one IPN which was made from a very highly crosslinked polyurethane, maxima in tensile strength, significantly higher than the tensile strengths of the components, occurred. This was explained by an increase in crosslink density resulting from interpenetration. Some enhancement in other physical properties (impact strength and thermal resistance) was also noted.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120418
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  • 177
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    H2O2-photosensitized emulsion copolymerization of tetrafluoroethylene with propylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 911-920 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The H2O2-photosensitized emulsion copolymerization of tetrafluoroethylene with propylene was carried out at room temperature in the presence of gaseous monomers of 50 mole-% tetrafluoroethylene content. The conversion increased almost linearly with irradiation time. The rate of polymerization was proportional to the 1.0 power of H2O2 concentration up to 3.5 × 10-3M H2O2 and the 0.46 power of H2O2 concentration above 3.5 × 10-3M H2O2. The result obtained at low H2O2 concentration was almost consistent with that obtained in the radiation-induced method. The rate of polymerization was proportional to the 0.58 power of the emulsifier concentration, and the degree of polymerization was independent of the emulsifier concentration. The H2O2-photosensitized emulsion copolymerization of tetrafluoroethylene with propylene is terminated mainly by degradative chain transfer of the propagating radical to propylene at low H2O2 concentration and by the reaction of the propagating radical with OH radical from photolysis of H2O2-aqueous solution at high H2O2 concentration.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120420
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  • 178
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    Copolymerization of acrylonitrile. III. Copolymerization with α-cyanocinnamamide (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 945-951 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acrylonitrile was copolymerized in solution with α-cyanocinnamamide up to low conversions. The conventional scheme of copolymerization fitted this copolymer. The basic properties, such as solubility, viscosity, and thermal behavior, of the copolymer prepared in bulk and in solution were determined.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120503
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  • 179
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    Influence of covalently bonded dyes on the photooxidative destruction of poly(vinyl alcohol) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 939-944 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the dye and type of polymer bond on the rate of photo-oxidation in poly(vinyl alcohol) (PVA) films was investigated. C. I. Reactive Yellow 4 and C. I. Reactive Blue 4 dyes and their inactive forms were used as ultraviolet light absorbers. It was shown that in the case of PVA samples dyed with these dyes, the processes of structurizing due to the secondary reactions take place, as it can be supposed on the basis of the changes in the radical concentration yield and growth of intrinsic viscosity. The kinetics of PVA photo-oxidative destruction was investigated by ESR and infrared spectroscopy methods. The loss of strength under photodestruction was checked viscometrically.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120502
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  • 180
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    Preparation of new reactive methylene monomers (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 985-992 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acryloylacetone, methacryloylacetone, and related monomers have been synthesized by using cyclopentadiene as a blocking agent during the Claisen condensation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120506
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  • 181
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    Cationic polymerization of styrene by acetyl perchlorate: Molecular weight distribution of polystyrene and nature of the propagating species (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 967-984 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To clarify the nature of the propagating species in cationic polymerization of styrene catalyzed by acetyl perchlorate, the molecular weight distribution of the polymer was investigated under various conditions. The molecular weight distribution curve for the polymer obtained in methylene chloride at 0°C showed a double peak phenomenon. This suggests that two or more kinds of propagating species participate simultaneously in the propagation reaction. The weight fraction W(H) of the polymer corresponding to the higher molecular weight peak increased with increasing polarity of the solvent. W(H) decreased when the concentration of the ionic species was increased either by an increase of the catalyst concentration or by the addition of the common salt such as tetra-n-butylammonium perchlorate. On the other hand, the position of the peak in the molecular weight distribution curve was independent of polymerization conditions. It was concluded that the higher molecular weight part of the polymer was produced under conditions for conductive to dissociation of the propagating species and the less dissociated propagating species was responsible for the lower molecular weight part of the polymer.
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120505
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  • 182
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    Free-radical grafting of monomers to polydienes. II. Kinetics and mechanism of styrene grafting to polybutadiene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1011-1021 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic analysis of the grafting reaction has shown that, provided rubber radicals are not involved in termination reactions, the observed normal kinetics of styrene polymerization are to be expected. An expression relating the graft fraction with the rubber and monomer concentrations has been derived and its validity verified from the results reported in Part I. The observation that the molecular weight of the ungrafted PBD falls during the reaction has been explained on a theoretical basis.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120509
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  • 183
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    Applications of ESCA to polymer chemistry. IV. The composition and structure of copolymers of ethylene with tetrafluoroethylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1049-1063 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular core binding energies have been measured by ESCA for a series of copolymers of tetrafluoroethylene and ethylene. Detailed analysis of the results demonstrates the utility of ESCA for determination of copolymer compositions and for providing information on important structural features for these copolymers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120512
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  • 184
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    Photoreversible reactions of poly(vinyl cinnamylideneacetate) and its model compound (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1125-1130 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical reactions of poly(vinyl cinnamylideneacetate) and its model compound were studied. The irradiation of these compounds with light of wavelength longer than 300 nm produced dimeric forms of cinnamylideneacetyl groups, which were effectively dissociated into the monomeric forms by the irradiation with 254 nm light.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120516
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  • 185
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    Anionic polymerization of a series of five-membered cyclocarbosiloxanes (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1109-1123 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was conducted of the anionic polymerization of a series of methyl- and/or phenyl-substituted five-membered cyclocarbosiloxanes. The polymerization was initiated by lithium n-butyldiphenylsilanolate in the presence of tetrahydrofuran. The rate of conversion of monomer to polymer was measured in an NMR spectrometer. The rate of polymerization was largely dependent upon the structure of the growing chain ends. The apparent activation energies were in the range 10-14 kcal/mole for the series.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120515
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  • 186
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    Anionic polymerization of 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1089-1107 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the first of a two-part series, a study has been made of the anionic polymerization of a five-membered cyclocarbosiloxane, 2,2,5,5-tetramethyl-1-oxa-2,5-disilacyclopentane. The polymerization was initiated by lithium n-butyldiphenylsilanolate in the presence of tetrahydrofuran. The chemical shifts of the protons of the cyclic monomer and the polymer were found to be different, and therefore the rate of polymerization was obtained in an NMR spectrometer. The effects of varying the concentrations of THF, initiator, and water upon the rate of polymerization and upon the molecular weight and the molecular weight distribution were investigated. At a constant concentration of monomer and initiator, the rate of polymerization increased when the THF concentration was increased. At a constant concentration of monomer and THF the rate of polymerization reached a constant value when the initiator concentration was varied. The molecular weight and the molecular weight distribution were dependent upon the initiator to water ratio, whereas water concentration had little effect on the rate of polymerization. Essentially monodispersed polymers were obtained when the concentration of initiator was in large excess to that of water or vice versa. A bimodal distribution in molecular weight was obtained when the concentration of initiator was approximately equal to that of water. The apparent activation energy of polymerization was 12.7 kcal/mole.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120514
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  • 187
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    Polymerization of methyl methacrylate by organic isocyanate-triethylamine systems (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1135-1140 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120518
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  • 188
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    Near-infrared spectrum of cellulose: A new method for obtaining crystallinity ratios (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1143-1150 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absorption bands in the near-infrared (NIR) spectrum of cellulose were correlated with crystalline and noncrystalline regions and used to derive a new crystallinity ratio. NIR crystallinity ratios of both natural and regenerated celluloses were measured and compared with x-ray diffraction values. The data indicates that the NIR crystallinity ratio may also depend upon crystallite size.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/pol.1974.170120601
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  • 189
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    Identification of the principal high molecular weight fragments in the thermal degradation of poly(methyl acrylate) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1163-1171 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of poly(methyl acrylate) has been studied with identification of the major pyrolysis products. The degradation mechanism of Cameron and Kane involving random homolytic scission of the polymer chain followed by a series of intermolecular and intramolecular transfer reactions is extended and confirmed, and it is apparent that a series of saturated and unsaturated oligomers of methyl acrylate are produced.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120603
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  • 190
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    Some applications of gel-permeation chromatography in investigations of structure and the solution properties of radical-initiated poly(vinyl chloride) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1181-1191 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The applicability of the published universal calibration parameters for gel-permeation chromatography on polystyrene standards and poly(vinyl chloride) samples with a defined structure has been compared. It was shown experimentally that of several theoretically possible molecular weight averages attributed to the elution volume at the position of the peak maximum, the root mean-square average molecular weight MRms = (MwMn)0.5 shows the best accordance. The molecular weights obtained by gel-permeation chromatography were compared with those determined by viscometry, osmometry, and the light-scattering method. The reproducibility of gel-permeation chromatography measurements is 3%, and the average variance of the results as compared with results obtained by the above methods is about 8%. It was also found that the gel-permeation chromatography does not involve any anomalies interfering with results obtained by other methods.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120605
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  • 191
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    An electrochemical route to phenol-formaldehyde precursors (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1193-1202 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With the aid of VPC and NMR, the electroinitiated polymerization of phenol or p-tert-butyl phenol with formaldehyde in the presence of basic electrolytes has been investigated over a range of current densities. Results from an electroinitiation study were contrasted with base-catalyzed thermal polymerizations and, except for yield, found to be essentially invariant. GPC of the electroinitiated and thermally polymerized resins indicates similar results with low molecular weight species of relatively narrow molecular weight distribution being the principal products. An electroinitiation mechanism, in agreement with the mechanism for base-catalyzed thermal polymerization is proposed to describe these experimental results.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120606
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  • 192
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    Cyclopolymerization of isoprene with VCl4-AlEt2Br catalyst system (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1257-1262 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isoprene was polymerized at 30°C with VCl4-AlEt2Br catalyst system in n-hexane. A linear dependence of rate of polymerization on the monomer and catalyst concentrations was found. The overall activation energy was 8.96 kcal/mole. Infrared spectra of polyisoprene showed the presence of cyclic structure, indicating a cationic mechanism of polymerization.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120611
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  • 193
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    Effect of primary radical termination on chain length and initiator efficiency (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1263-1268 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In polymerization with primary radical termination, when reaction between primary radicals, which escape from solvent cage, is not negligible, a relation between chain length and polymerization rate is found regardless of tractable approximate procedures. Such a relation is applied to the kinetic data obtained in the polymerizations of methyl methacrylate (MMA) and vinyl acetate (VA) initiated by 2,2′-azobis(2,4-valeronitrile) at 50.0°C. Further, when the primary radical termination is high, an initiator efficiency can not be approximated to a ratio of the primary radicals escaping from the cage to the total primary radicals formed in the cage. In the polymerization of MMA, after the primary radicals escapes from the cage, they immediately react with the monomer. Thus, the reaction between the primary radicals is not significant. However, in the polymerization of VA, the rate of reaction between the primary radical and the monomer might be comparable to the rate of reaction between the primary radicals when the initiator concentration is quite high.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120612
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  • 194
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    Modification of poly(vinyl chloride). XXIV. Graft polycondensation of p-(2-chloroethyl)thiophenol on poly(vinyl chloride) (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1291-1300 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new graft reaction, the graft polycondensation of p-(2-chloroethyl)thiophenol (CETP) onto poly(vinyl chloride) (PVC) in ethylenediamine (EN) and its mixed solvents was studied under various graft conditions. Two graft procedures which is different with addition operations of CETP were tried. The per cent grafting G and the grafting efficiency E in procedure A were generally higher than those in procedure B. G and E also increased with increase in temperature and time. The increase of the weight of PVC and in the concentration of CETP increased G and E, respectively. Mixed solvents composed of EN and benzene, tetrahydrofuran, or dimethylformamide also increased G and E. The grafted products thus obtained have a gel fraction and contain nitrogen. However, on grafting in the presence of C12H25SH, higher G′ and E′ were obtained, and the products contained no gel fraction or nitrogen. The degree of polycondensation and the number of grafts in the grafted PVC were about 4-12, and 0.64-1.71 mole-%, respectively, as estimated from elemental analysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120614
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  • 195
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    Polymerization characteristics of ferrocenyl vinyl ketone (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1313-1320 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120616
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  • 196
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    A new synthetic route to a poly-p-xylylene (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1321-1322 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120617
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  • 197
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    Synthesis of polyamides from succinimide derivatives (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1327-1331 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120619
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  • 198
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    Ion ⇄ ester equilibria in the living cationic polymerization of tetrahydrofuranThis paper was presented in part at the International Symposium on Cationic Polymerization, Rouen, France, 1973. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1333-1336 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120620
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  • 199
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    Electronic Resource
    Crystallite structure of cellulose (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1349-1374 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystallite structure of cellulose has been elucidated through analyses of the degradations of model compounds by gel-permeation chromatography. These compounds include single crystals of cellulose triacetate, regenerated cellulose from single crystals, precipitated celluloses from solutions, and commercial regenerated cellulose. The corresponding distribution profiles are found to follow the Keller transformation, which is a characteristic behavior of the folded crystals of synthetic polymers. It is also found that the leveling-off DP of cellulose is a first-order approximation of the corresponding fold length. A detailed folding chain model for the regenerated cellulose was constructed, and the various aspects of the structure are discussed. The kinetic data and the degradation products of native celluloses were also analyzed and found to obey the ruling of the chain fold model but not the conventional fringe-micellar model. In addition, an iodine-staining experiment pinpoints a minimum of 1.5% of true amorphous material; this is in quantitative agreement with the conformation analysis for the six-fold helical β-loop bonds. It is therefore suggested that the same chain-fold conformation is applicable to the native polymer. The hydrolysis of cellulose is found to be composed of a triple mode of degradation, i.e., a first-order random scission at the folds, a zero-order peeling reaction at the ends of the crystallites, and a first-order random scission on the lateral surfaces of the cellulose.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120701
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  • 200
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    Effects of mercaptides on anionic polymerization. III. Polymerization of methyl methacrylate by thiophenoxides in polar aprotic solvents (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1395-1406 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sodium thiophenoxide initiated the polymerization of methyl methacrylate in polar aprotic solvents (DMF, DMSO, HMPA). The active species that initiated the polymerization of the monomer was found by spectrophotometric measurements and by the sodium fusion method to be sodium thiophenoxide itself. The activation energy for the polymerization of the monomer in DMF solvent obtained was E = 3.4 kcal/mole below 30°C, and E = -3.3 kcal/mole above the temperature. The phenomena were reasoned as the result of the formation of two active species: a solvent-separated ion pair and a contact ion pair. The effects of counterions on the reactivity of thiophenoxide increased with increasing electropositivity of the metals: Li 〈 Na 〈 K. Sodium phenoxide, the oxygen analog of thiophenoxide, was also found to initiate the polymerization of the monomer in the solvents. The relative reactivity of thiophenoxide to phenoxide for the monomer in HMPA at 30°C was thus determined: phenyl-SNa 〉 phenyl-ONa. The relative effect of the polar aprotic solvents on the reactivity of thiophenoxide was also as follows: HMPA 〉 DMF 〉 DMSO. The kinetic studies were made by the graphical evaluation of rate constants. The following results were obtained for the monomer at 20°C in DMF solvent: Kp = 3.5 × 102 1./mole-hr and Kt = 9.8 × 10-2/hr.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170120704
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