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  • 1965-1969  (398)
  • 1966  (398)
  • Physics  (398)
  • 101
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 141-157 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization of vinylpyridine initiated by cupric acetate has been studied. The rate of polymerization was greatly affected by the nature of the solvent. In general polar solvents increased the rate of polymerization. Polymerization was particularly rapid in water, acetone, and methanol. The initial rate of polymerization of 4-vinylpyridine (4-VP) in a methanol-pyridine mixture at 50°C. is Rp = 6.95 × 10-6[Cu11]1/2 [4-VP]2 l./mole-sec. The activation energy of initiation by cupric acetate is 5.4 ± 1.6 kcal./mole. Polymerization of 2-vinylpyridine and 2-methyl-5-vinylpyridine with the same initiator was much slower than that of 4-VP. Dependence of Rp on monomer structure and solvent is discussed. Kinetic and spectroscopic studies led to the conclusion that the polymerization of 4-VP is initiated by one electron transfer from the monomer to cupric acetate in a complex having the structure, (4-VP)2Cu(CH3COO)2.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 102
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 71-82 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate of polymerization of styrene initiated by hydroperoxidized atactic polypropylene in a homogeneous toluene solution has been measured at 60 and 70°C. The reaction is first-order with respect to styrene concentration and independent of the polymeric hydroperoxide concentration above 2 × 10-5N hydroperoxide. The individual rate constants, length and frequency of the grafted polystyrene chains along the polypropylene backbone have been calculated and their significance discussed. The initiation rate constant compares closely with values reported for the analogous tert-butyl hydroperoxide-initiated polymerization. The rate constant for the chain transfer termination elementary step at 70°C., however, is 18 times the value reported for the tert-butyl hydroperoxide-initiated polymerization of styrene. This high constant accounts for the relatively low rates of polymerization observed and high termination rates. Chain deactivation is presumably accelerated by increased collisions between growing styrene chains and inactive propylene hydroperoxide and polystyrene molecules. Distribution of polystyrene grafts on polypropylene is estimated from knowledge of effects of styrene concentration, polymeric hydroperoxide concentration, and temperature upon the rate of polymerization.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 103
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 131-140 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Perfluoro-1,4-pentadiene was prepared by pyrolysis of sodium 3,5,6-trichloroperfluorohexanoate and subsequent dehalogenation. The monomer was polymerized under a number of conditions of temperature and pressure using various periods and various dose rates of γ-ray initiation. The compound was found to undergo doublebond migration producing perfluoro-1,3-pentadiene. The polymer samples, some of them rubbery, others grainy, are assumed to be copolymers of the 1,4-pentadiene and the 1,3 pentadiene, the 1,4-diene polymerizing according to a cyclic mechanism and the 1,3-diene undergoing the 1,4-addition that is characteristic of butadienes under certain conditions. Infrared and nuclear magnetic resonance studies tend to support these assumptions. Under polymerization conditions the monomer also produced four distinct dimers and traces of two monomeric substances.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 104
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 159-166 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Polyaddition reactions of 1,1′-tetramethylenebis(3,3-ethyleneurea) (IIa), 1,1′-octamethylenebis(3,3-ethyleneurea) (IIb), 1,1′-p-phenylenebis(3,3-ethyleneurea) (IIc), 1,1′-(4,4′-diphenylmethane)bis(3,3-ethyleneurea) (IId) and 1,1,3,3-diethyleneurea (III) with polymethylene dimercaptans were investigated. 1,1′-Polymethylenebis(3,3-ethyleneureas) and polymethylene dimercaptans successfully reacted at 80-95°C. in the presence of triethylamine to give poly(urea sulfides) with intrinsic viscosities up to 1.1 in about 90% yield when dimethylformamide, dimethylacetamide, or N-methyl-2-pyrrolidone containing lithium chloride as a solvent were used. The other ethyleneureas, however, failed to give high molecular weight polymers.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 105
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Crystalline and amorphous polymers have been obtained from the polymerization of phenyl glycidyl ether in the presence of tertiary amines. The crystalline fraction is high melting and insoluble at room temperature. The amorphous fractions are soluble at room temperature and their molecular weights are found to be ∼950 in benzene at 30°C. The yields of the crystalline fraction and the amorphous paste fraction decreased considerably with increasing the catalyst concentration and reaction temperature above 50°C. The yield of the liquid fraction, however, increased with increasing concentration of the catalyst and the reaction temperature. The x-ray diffraction analysis of the crystalline fraction shows that the fraction has 47-50% crystallinity and that its diffraction pattern is similar to that of poly(phenyl glycidyl ether) obtained by Noshay and Price. The infrared spectra of these fractions have been obtained in the region of 650-4000 cm.-1. These data are compared with those of polystyrene and poly(styrene oxide) and are used to make an assignment of the normal modes of the poly(phenyl glycidyl ether) molecule. On the basis of analyses of polystyrene and poly(styrene oxide), and a study of the combination bands, it has been possible to make a fairly satisfactory assignment of all of the benzene ring fundamentals of the CH2, CH, and skeletal modes.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 106
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 197-214 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The radiation-induced graft polymerization of styrene to poly(vinyl chloride) (PVC) was investigated. Relations between the rate of grafting and the dose rate when the polymer is irradiated in liquid monomer or in monomer vapor, and between the rate of grafting and monomer concentration absorbed in the polymer have been investigated. The rate of grafting in monomer vapor was found to be far larger than that in liquid monomer. A high rate of grafting in monomer vapor was thought to result from a lower concentration of monomer in PVC during irradiation. An experiment carried out on PVC containing the monomer at various concentrations showed that the rate is largest at a monomer concentration of about 3.5 mole/l. and is smaller for higher and lower concentrations. On the assumption that the theory of homogeneous homopolymerization can be applied to this grafting reaction, the value of kp2/kt has been obtained, where kp and kt are propagation constant and termination constant, respectively. The value of kt greatly increases when the monomer concentration exceeds 3.5 mole/l. This increase of kt can be accounted for if it is assumed that the monomer absorbed in the polymer works as a plasticizer and increases the molecular motion of the polymer. A measurement of the elastic modulus of PVC containing the monomer at various concentrations showed that this is, in fact, the case.
    Zusätzliches Material: 12 Ill.
    Materialart: Digitale Medien
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  • 107
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 167-188 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rules were evolved to predict elution of linear, branched, and polar compounds in GPC, based on testing of 130 compounds. With these rules and in tetrahydrofuran solvent, data for all but a few compounds correlated onto a single calibration line. With small molecules, elution often changed, due to hydrogen bonding to the solvent; this occurred with alcohols, acids, and some chlorinated compounds, but not with mercaptans. Branched and linear isomers usually eluted at about the same point. One may conclude that structural elements were additive in their effect on elution volume in this study.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 108
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 189-195 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A high-resolution proton magnetic resonance compositional analysis has been developed for propylene polymers containing 0-40 wt.-% ethylene as either homopolymer or copolymer blocks. The test is independent of tacticity and provides qualitative information on copolymer sequencing and propylene chain structure. The analysis was developed using a series of standard reference polymers synthesized to contain various ratios of C14-tagged ethylene and propylene. The compositional standards were established by radiotracer analysis for C14 and by preparing weighed physical mixtures of homopolymers. Spectra were obtained at 200 ± 10°C. by placing externally heated polymer solutions into a conventional probe of a Varian A-60 proton spectrometer. All measurements were made on ± 10% polymer solutions in diphenyl ether. Analyses are accurate to about ± 10% at higher ethylene concentrations. The method is sensitive, with less precision, to below 1% for ethylene either as blocks or homopolymer.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 109
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 434-437 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 110
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 444-446 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 111
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 447-448 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 112
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 440-443 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 113
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 449-457 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Methyl ethyl and n-propyl acrylates when polymerized by sodium in liquid ammonia, contain an average of one amino group per polymer chain, which is indicative of amide anion initiation and chain transfer to the solvent ammonia. Isopropyl acrylate and the higher homologs contain considerably less nitrogen than required by one amino group per chain indicative of another initiating and terminating mechanism. Three alternate mechanisms are discussed. Of these, alkoxide initiation seems to be the most plausible. Vinyl thiolacetate polymers prepared under the same conditions also contain less nitrogen than required by one amino group per chain. The polymer structure is predominantly poly(vinyl thiol) with intramolecular or intermolecular disulfide bridges. The acetate part of the molecule is concomitantly split off to form acetamide.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 114
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 475-488 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: It has been found practical to fractionate relatively monodisperse polystyrenes of molecular weights up to 4 × 106 by using a semiautomatic solvent extraction procedure. The fractionators consist of flow-through mixing chambers provided with settling regions for the removal of finely suspended solid material. Provision is made for accurate control of both temperature and solvent-nonsolvent ratio. Two such apparatus, operated in tandem, were used in the present work; in principle, several more stages could be employed if desired for most polymer systems. Results on polystyrenes prepared in well defined ways appear to be in good agreement with predicted distributions. Applicability to other polymer systems is discussed.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 115
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 489-510 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dilute solutions of DNA in neutral phosphate buffer and of polystyrene in toluene are degraded to limiting molecular weights by high speed stirring in a Virtis homogenizer equipped with special thin, highly sharpened blades. Results are interpreted and justified in terms of the hydrodynamic theory of laminar boundary layers. Estimates of critical stress values for chain scission are obtained at various limiting molecular weights for the two polymer systems, and the treatment is used to rationalize the dependence of degradation upon homogenizer speed. The agreement between the hydrodynamic theory and experimental data implies that limiting molecular degradation occurs entirely in the boundary layer region extending a distance equal to approximately the molecular contour length from the leading edge of the blade tip and that laminar flow conditions prevail in this region. It therefore seems likely that polymer molecules subjected to a critical shearing stress are essentially completely extended in the streamlines of flow. The hydrodynamic theory is finally used to explain the peculiar kinetics of molecular degradation in high speed rotary homogenizers.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 116
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Zinc dimethyl-, methylphenyl-, and diphenylphosphinate have been prepared by the reaction of Zn(C2H3O2)2·2H2O with the appropriate acid or salt and found to exist in amorphous and crystalline forms. Zinc methylphenylphosphinate, the most tractable, exhibits many of the physical attributes of polymeric materials, both in solution and bulk form, supporting our earlier suggestion that these compounds are double-bridged coordination polymers. Thermogravimetric analysis indicates initial decomposition temperatures of 440, 425, and 490°C., respectively, for the three polymers, but long-term studies show initiation of decomposition at somewhat lower temperatures.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 117
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The preparation, properties, x-ray powder patterns, and TGA curves are given for cobalt(II) dimethyl-, methylphenyl- and diphenylphosphinate. The polymeric character of cobalt(II) methylphenylphosphinate is demonstrated by its colligative properties and melt indexes. These cobalt(II) phosphinates along with hybrid copolymers of zinc(II) or cobalt(II) were prepared by the reaction of the metal acetate with the appropriate phosphinic acid or mixture of phosphinic acids. A consideration of the hybrid copolymers leads to the conclusion that both the zinc(II) and cobalt(II) dimethyl- and diphenylphosphinates are likewise polymeric. Thermal stability is discussed in terms of the structures suggested, and it is shown that crystallinity is related to polymer symmetry.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 118
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 631-637 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The triad distributions of 1,1-diphenylethylene (D)-methyl acrylate (M) copolymers have been determined from NMR measurements and examined according to the terminal and penultimate models of copolymerization theory. As expected from the diamagnetic shielding by the phenyl rings of the nearest D units, the methoxy proton resonances were found to appear as three resolved peaks at 6.4-6.6 τ, 6.7-7.0 τ, and 7.2 τ, and have been assigned to the central M units of the triads MMM, MMD or DMM and DMD, respectively. The copolymer composition and the triad distributions observed are shown to agree better with the terminal model with the methyl acrylate reactivity ratio of 0.092 ± 0.010 than with the penultimate model.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 119
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(ethylene terephthalate) was exposed in vacuo γ-radiation from a Co60 source at a dose rate of 0.02 Mrad/min., and an ambient temperature of 47°C. Gaseous products were analyzed in a mass spectrometer and carboxyl groups estimated by titration with NaOH and by infrared analysis. Initial G values were —COOH = 0.77, CO2 = 0.17, CO = 0.11, H2 = 0.015, and CH4 = 0.003. All these values decreased markedly with increasing dose except G(CO)2, which, roughly, was maintained up to 5000 Mrad. It was considered whether the dependence on dose of the yields of the major reaction products could be accounted for by the following set of first-order reactions: It was found that the rate of formation of —COOH groups at low doses was much too high to fit this simple reaction scheme. However, a better fit was obtained over a range of higher doses (ca. 100-5000 Mrad). A final conclusion could not be reached concerning the validity of the above reaction scheme.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 120
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 623-629 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Copolymers of vinyl acetate and vinyl alcohol were studied by differential thermal analysis. The melting points of the copolymers are not a simple function of the composition, but depend on the method of preparation of the copolymers. Partial saponification of poly(vinyl acetate) with sodium hydroxide leads to high melting, ordered copolymers, while reacetylation of poly(vinyl alcohol) leads to low melting, random copolymers. Catalytic alcoholysis of PVAc yields copolymers intermediate in melting point and order. The results are treated by assuming that equal melting points indicate similar sequence length distributions of crystallizable units.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 121
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 639-647 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A linear dimethylpolysilazane polymer has been prepared and its internal motion studied by the techniques of broadline nuclear magnetic resonance. Second moments and line widths are reported as a function of temperature from -196 to 30°C. The results are compared to those for linear dimethylpolysiloxane, as well as to those for the crosslinked siloxane and silazane. The experimental low-temperature second moment of 7.25 ± 0.5 gauss2 corresponds to a C3 reorientation of methyl groups about the silicon-carbon bond. The motions occurring in the silazane are found to be the same as those in the corresponding siloxane. The transition to low second moments occurs approximately 30°C. higher in the linear silazane than in the linear siloxane. This is attributed to a somewhat greater resistance to motion in the silazane.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 122
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Dissolution temperatures Ts have been determined for poly(vinyl alcohol) (PVA) samples of varying tacticity as a function of crystallization temperatures Tc. From the values of Ts and Tc, one can obtain values of (Tm)∞, the dissolution temperature of crystals of infinite stepheight. (Tm)∞ is a characteristic property of a given sample. This method of characterization is very sensitive and reliable for detecting differences in molecular regularity among PVA samples. The variation of (Tm)∞ with stereoregularity is attributed in part to differences in hydrogen-bonding characteristics. Determinations of the crystallinities of solution-crystallized PVA have shown that stereoregularity in PVA does not result in higher crystallizability.
    Zusätzliches Material: 1 Ill.
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  • 123
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 679-698 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structure-property relationships of poly(vinyl alcohol) have been studied by measuring the crystallinity and water resistance of films derived from samples of varying, known tacticity. Crystallinities of unannealed and annealed films were examined by means of density, infrared, and x-ray measurements. Higher tacticity did not lead to higher crystallinity. The apparent order of crystallizability was atactic ≧ syndiotactic-rich ≫ isotactic-rich. Water resistance of these films was determined by measuring the swelling index at 30°C. and solubility at 70 and 130-140°C. Water resistance increases as tacticity increases, with syndiotactic-rich PVA exhibiting the highest water resistance. Since water resistance also increases with crystallinity, both stereoregularity and crystallinity must be considered when evaluating structure-solubility relationships. Differential thermal and thermogravimetric analyses of these samples are also presented, together with a correlation of tacticity index as measured by an infrared technique with that of an NMR technique.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 124
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 771-781 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effects of γ-irradiation on two polysiloxanes in environments of air and vacuum at several selected temperatures were studied. The physical property monitored during the γ-irradiation of the two polysiloxanes was the change in dynamic modulus which, in turn, is proportional to the change in the number of elastically effective chains in the polymer network. The measurements were accomplished by recording in situ the freeend response of the polymeric cantilever reeds in forced resonance at and near their fundamental frequency of resonance. The apparent energy of activation of crosslinking for the polydimethylsiloxane polymer was found to be 0.56 kcal./mole in vacuum over a limited temperature range, and 3.5 kcal./mole in air. For the polydimethyl-diphenylsiloxane polymer, the apparent energy of activation was found to be about 1.3 kcal./mole in vacuum, whereas in air the polymer response was complex, displaying both scissioning and crosslinking reactions so that a value could not be obtained. The ability of the pendant phenyl groups to reduce the effective crosslinking rate was found to be sensitive to both temperature and environment.
    Zusätzliches Material: 4 Ill.
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  • 125
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 811-820 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Some aspects of the condensation polymerization of silicic acid have been discussed in a systematic manner. Empirical relationships between the time of gelation and the catalyzer concentration, with both H+ and OH- catalysis, have been suggested. These are found to be consistent with the observations of various authors. Also the activities of both the ionized and un-ionized species present in the system account for some anomalous observations and the pH optimum for the maximum time of gelation. The idea of a secondary salt effect, introduced by Brönsted, has been found to be helpful in understanding catalyst function.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 126
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Cotton cellulose is decrystallized by periodate oxidation to essentially zero crystallinity index (CI) at 100% oxidant consumption. The decrease in CI is pseudo zero-order over 60% of the reaction and consistent with a diffusion-controlled mechanism. The attack on regions of high order is indicated to be 100% in the latter phase of oxidation and 13% in the initial phase. Data allow an estimate that approximately 60% of the structural segments of the cotton cellulose under investigation lies in highly ordered arrangements.
    Zusätzliches Material: 3 Ill.
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  • 127
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 801-810 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The difference x-ray diffraction pattern can reveal the presence of oriented, ordered material whose conventional diffraction pattern is masked by that of unoriented, disordered material. It is shown that this enhancement results from the fact that scattering from only oriented material contributes to the difference intensity, defined as the difference between the scattered intensity and its average over the polar angle in intensity space. Difference patterns of lightly crosslinked natural rubber, obtained as a function of elongation, show the development of crystallinity at smaller elongations than do the corresponding conventional patterns and indicate that nearly all the oriented material is crystalline. The difference and conventional patterns were obtained from the same diffractometer data. Photographically recorded diffraction patterns are intermediate between the conventional and difference diffractometer patterns in sensitivity to crystallinity. The difference diffraction pattern of a highly oriented atactic polystyrene fiber shows no evidence of crystallinity, the halos on the difference pattern being just as broad as those on the conventional pattern with no apparent tendency to break up into crystalline lines.
    Zusätzliches Material: 8 Ill.
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  • 128
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 821-828 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The copolymerization of ethylene with maleic anhydride was carried out with γ-radiation and a radical initiator, i.e., 2,2′-azobisisobutyronitrile and diisopropyl peroxydicarbonate under pressure at various reaction conditions. The homopolymerization of neither monomer was observed in this system. In the γ-ray-initiated copolymerization the G value (polymerized monomer molecules per 100 e.v.) was shown to be between 103 and 104. It was found that the dose rate exponent of the rate is approximately unity, and the rate is proportional to the amount of ethylene monomer. Apparent activation energies of 1.8 and 27.5 kcal./mole were obtained for γ-ray-initiated and AIBN-initiated copolymerization, respectively. Since the composition of copolymer is independent of monomer molar ratio and the molar ratio of ethylene to maleic anhydride in the polymer is approximately unity, the monomer reactivity ratios were obtained as rE ≃ 0 and rM ≃ 0 for γ-ray-initiated polymerization at 40°C. Alternating copolymerization was, therefore, concluded to occur. Infrared analysis of the copolymer is almost consistent with this. The copolymer in the solid state is amorphous. It is soluble in water, cyclohexane, and dimethylformamide and insoluble in lower alcohols, ether, and aromatic hydrocarbons. The aqueous solution of polymer gave a strong acid.
    Zusätzliches Material: 6 Ill.
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  • 129
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 829-846 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A wide variety of polyesters and polyamides was prepared from 1,2- and 1,3-disubstituted cyclobutane derivatives. In general, polyamides containing the trans-disubstituted cyclobutane ring were crystalline. Polyesters containing predominantly the trans-isomer tended to be crystalline but those containing mixtures of cis-trans isomers were amorphous. Mechanical properties have been determined wherever possible. Appreciable yields of cyclic dimers were isolated during the preparation of certain polyesters. These cyclic dimers readily polymerized when treated with dibutylzinc. Examination of acrylonitrile dimer (1,2-dicyanocyclobutane) by gas chromatography failed to reveal the presence of any 1,3-dicyanocyclobutanes.
    Zusätzliches Material: 7 Tab.
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  • 130
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 847-857 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of redox polymers was prepared by the addition of different redox groups to preformed, chloromethylated macroreticular styrene-divinylbenzene copolymers. These polymers contained the hydroquinone, hydroquinonesulfonic acid, methylhydroquinone, 2,5-dimethylhydroquinone, 2,5-dimethylhydroquinonesulfonic acid, 2,3,5-trimethylhydroquinone, tert-butylhydroquinone, chlorohydroquinone, benzyl mercaptan, anthraquinone, and the pyrogallol redox groups. Thus, a set of redox polymers is available having redox potentials that may range from approximately 150 to 700 mv.
    Zusätzliches Material: 1 Ill.
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  • 131
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 881-900 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Chain transfer constants in the homogeneous free-radical polymerization of ethylene at 1360 atm. and 130°C. have been determined for over 50 compounds, including nearly 300 hydrocarbons. The effects of substitution, unsaturation, and ring strain in the transfer agent molecule on the reactivity of its C—H bonds in chain-transfer reactions with a polyethylene growing chain are analyzed. Qualitatively, these trends parallel those found for simple radicals attacking simple molecules. However, the principle that the reactivity of a compound is the sum of the reactivities of all reactive bonds, which is well established for simple radicals and transfer agents, is found not to be true in ethylene polymerization. It is postulated that the deviations from this principle are due to steric factors which become very important when the free radical is bulky. The transfer constants measured in ethylene polymerization are also compared with transfer constants in other systems. A strong correlation is found between the transfer constants in ethylene and published data on rates of abstraction of hydrogen atoms by methyl radicals.
    Zusätzliches Material: 4 Ill.
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  • 132
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 907-916 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new class of polyacetals, poly(cyanoethyl)oxymethylene, was obtained by the polymerization of β-cyanopropionaldehyde at -78°C. with use of ionic initiators including boron trifluoride diethyl etherate, diethylzinc, triethylaluminum, and triethylaluminumtitanium tetrachloride complexes. The influence of temperature, initiator, and solvent upon the polymerization was studied. Infrared spectra of polymers obtained from different initiators are also illustrated. An attempt was made to fractionate the polymer by means of solvent extraction. The acetone-soluble polymer is an elastomeric material having a low solution viscosity. The acetone-insoluble, dimethylformamide-soluble polymer obtained as a white powder was found to have extremely high solution viscosity. Some amounts of insoluble fraction could be also separated. The latter two fractions were observed to have a reasonable stability.
    Zusätzliches Material: 5 Ill.
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  • 133
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1023-1029 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A simplified calculation of the CHD scissors vibration frequencies has been made for —(CHD)n— of various configurations. The correlation between the CHD scissors frequency and the local configuration has been established. On this basis the infrared absorption bands of poly-trans-CHD—CHD and poly-cis-CHD=CHD appearing in the region of 1350-1280 cm.-1 have been interpreted in greater detail.
    Zusätzliches Material: 1 Ill.
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  • 134
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1045-1055 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The amount of abnormal addition of phenoxide to epichlorohydrin and phenyl glycidyl ether was determined as a function of reaction conditions. The isomer distribution resulting from attack at either position of these unsymmetrical epoxides was quantitatively measured by vapor phase chromatography of the resulting product mixtures. While both epoxides reacted predominantly in the expected normal fashion, small quantities of abnormal addition products were found whose concentrations were temperature-dependent. The analytical method also permitted a study of the effect of temperature on side reactions involving hydrolytic solvents.
    Zusätzliches Material: 2 Ill.
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  • 135
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1057-1067 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A group of substituted phenols, quinone, and tropone were used to retard AIBN-initiated ethyl acrylate polymerization in ethyl propionate solution at 44.7°C. in the absence of oxygen. It was concluded that the efficiency of retardation depended upon the ability of the terminator to stabilize a positive charge on its reaction site in the transition state. Tropone was found to be a particularly good retarder. The radical-trapping efficiency of 2,2-diphenyl-1-picrylhydrazyl in this system was found to be 50-60%.
    Zusätzliches Material: 1 Ill.
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  • 136
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1069-1079 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reactions of poly(vinyl chloride) and butyllithium in tetrahydrofuran were investigated. A deep purple color developed at first with addition of butyllithium to the THF-PVC solution, and a spontaneous color change of the misture occurred successively to blue, green, and finally pale vellow. In these reaction stages, the PVC might be butylated, dehydrochlorinated, and partially lithiated by BuLi. These facts were substantiated by the results of successive reactions with various substances such as Michler's ketone, carbon dioxide, and styrene.
    Zusätzliches Material: 3 Ill.
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  • 137
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1031-1043 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Studies were carried out on the grafting of acrylonitrile (AN) and acrylamide (AA) to starch by ceric ion. The variables affecting the grafting of AN and AA were investigated with granular wheat starch dispersed in aqueous N,N-dimethylformamide and ceric ammonium nitrate as catalyst. Results showed that the concentrations of monomer and catalyst are the major factors influencing the grafting of AN; thus the monomer content of the grafts can be regulated by these variables. The grafting of AA is also influenced by these variables, but to a much less degree. Increasing concentrations of monomer promote homopolymerization and increasing concentration of catalyst inhibit grafting. The extent of grafting of this monomer can best be controlled by reaction time. Under the most favorable conditions, maximum grafting efficiency (ratio of amount of grafted monomer to total amount of monomer converted to polymer) was 87% for AN and 43.8% for AA. Although the monomer content of the AN grafts was higher than that of AA grafts prepared under identical conditions, the number of branches in the grafts was almost the same; only the length of the branches was different. The AN-starch grafts have branches of higher molecular weight.
    Zusätzliches Material: 3 Ill.
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  • 138
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1093-1111 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: By choosing suitable approximations to Bueche's function, it is possible to calculate the viscosity versus shear stress for log-normal molecularly distributed linear polymers. For bulk polymers the mixing rules M̄w, M̄w, M̄z are considered. For values of η/η0 〉 0.1 and heterogeneities with M̄w/M̄n 〉 1.5 the result obtained with any mixing rule is η/η0 = erfc [(1/delta;) log (M0Qh/aK)], where a = π2/6pRT and where the δ and K values are dependent on the heterogeneity ratio Q = M̄w/M̄n and on the type of mixing rule; on the other hand, the h value is independent of the heterogeneity, but depends on the mixing rule. Most experimental data should fit the M̄w mixing rule as one would expect from the zero shear stress mixing rule. Experimental data are compared with the theoretical results.
    Zusätzliches Material: 9 Ill.
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  • 139
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The novel inorganic polymer poly(aquahydroxychromium diphenylphosphinate) was investigated to obtain information concerning its degree of polydispersity and properties when dissolved in organic solvents. Viscometric, infrared absorption spectroscopic, and electrical conductimetric techniques were employed to ascertain the characteristics of the polymer dissolved in benzene, chlorobenzene, and chloroform. Gel permeation chromatography was used to determine the degree of heterogeneity of the polymer. Results indicate that the polymer, as prepared, is quite polydisperse. The polymer main chains do not undergo radical reactions with the solvents. High values of the Huggins interaction constant K′ suggest that polymer-solvent association reactions involving chain-endgroups are probable. Such reactions are also indicated by association constant values and by the shapes of phoreograms obtained from electrical conductance data. Both “local” and “bulk” solvent properties, such as the dielectric constant, appear to influence the characteristics of the polymer when dissolved in the different solvents.
    Materialart: Digitale Medien
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  • 140
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1314-1316 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
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  • 141
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1323-1325 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 142
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1317-1322 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 143
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1326-1327 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
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  • 144
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1328-1328 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 145
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1329-1335 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The possibility of carrying out continuous fractionation of polymers by the thermodiffusion method was investigated. From the working space of a plate-type column, fractions of polymer were continuously withdrawn simultaneously with filling of the column with fresh solution from a storage vessel. After equilibrium had been established, the distributions of molecular weights of the fractions were determined by a modified Baker and Williams method. In the same apparatus, and at constant temperature and concentration, fractionation, which may be characterized by a limiting viscosity number, is dependent on the total rate of withdrawal and on the ratios of amounts of polymer withdrawn in various places on the column.
    Zusätzliches Material: 5 Ill.
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  • 146
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1337-1349 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Various α-halo-p-xylenes have been polymerized with base yielding p-xylylene polymers. The reaction involves a 1,6-dehydrohalogenation to give a xylylene which then polymerizes. α,α′-Dichloro-p-xylene forms poly-α-chloro-p-xylylene and polymers containing stilbene units; α,α,α′,α′-tetrachloro-p-xylene gives poly-α,α,α′-trichloro-p-xylylene; alkyl, aryl, and halogen ring-substituted α-chloro-p-xylenes give the corresponding ring-substituted poly-p-xylylenes. The more halogens in the α positions (up to five), the weaker the base necessary for dehydrohalogenation. Sodium hydroxide in methanol will polymerize tetrachloro-p-xylene, while potassium tert-butoxide in refluxing p-xylene is necessary to polymerize α-chloro-p-xylenes. Stilbenes are formed when α-halo-p-xylenes are reacted with potassium tert-butoxide in polar solvents such as dimethyl sulfoxide.
    Zusätzliches Material: 1 Ill.
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  • 147
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1359-1372 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Preparation and polymerization of lactam ethers which contain an amide and an ether group in the same ring are described. Seven-membered lactam ethers give relatively low molecular weight polymers with an anionic or cationic catalyst, while with diethylzinc as catalyst, the 2,7-dimethyl lactam ether of a seven-membered ring gives a crystalline polymer having a melting point of 220°C. A polymerization mechanism is discussed.
    Zusätzliches Material: 5 Ill.
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  • 148
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1563-1577 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Evidence is presented for the interaction of metal salts such as potassium iodide with polyethers such as poly(ethylene oxide). This interaction is sufficiently marked that the incorporation of 10-30% of the salt in the bulk polymer markedly reduces crystallinity while retaining compatibility. Examination of electroviscous effects in methanol demonstrates that the salt-polymer adduct behaves as a typical polyelectrolyte at low salt concentrations, while the polymer in absence of salt is essentially insoluble in methanol at room temperature. Measurements of the equilibrium between salt and polymer along with a study of various molecular weight polymers strongly suggest that one salt molecule associates with about nine ethylene oxide units. It is proposed that the association is due to an ion-dipole interaction, and the anion is tentatively postulated as the species directly associating with the polymer. The association of other metal salts and other polymers are interpreted in this light. The significance of these results in interpreting salting-in phenomena is also discussed.
    Zusätzliches Material: 12 Ill.
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  • 149
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1595-1607 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A mechanism for the formation of rubber particles in the polymerization of solutions of rubber in vinyl monomers is presented. A polymeric oil-in-oil emulsion is formed in the first phase of the polymerization. This polymeric oil-in-oil emulsion is transtormed into a solid dispersion of rubber in vinyl polymer in the second phase of the polymerization. A phase inversion takes place in the emulsion in the first phase of the polymerization. Rubber solution droplets are formed at the phase inversion point. These droplets harden as the polymerization proceeds and are gradually transformed into the solid, crosslinked rubber particles of the final polymer.
    Zusätzliches Material: 8 Ill.
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  • 150
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1689-1702 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Aromatic dinitriles cyclize to form aromatic polymers containing the s-triazine ring. In this paper, these polymers are compared thermally with each other and with aromatic melamine polymers prepared via the aromatic diamine and cyanuric chloride. One perfluoroaromatic melamine polymer was prepared and compared with the other two types of polymers. The polymers (triazines and melamine) in which biphenyl was the backbone were increasingly stable up to 1000°C. in nitrogen. The triazine polymers as a group were the most stable. The perfluoroaromatic polymer was the most stable melamine up to 500°C. in air but was very unstable above 700°C.
    Zusätzliches Material: 15 Ill.
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  • 151
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1649-1664 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal properties of a series of polyhydrazides and corresponding poly-1,3,4-oxadiazoles have been investigated using differential thermometric and thermogravimetric techniques. In addition, the conversion rates of the polyhydrazides to the corresponding oxadiazole structures have also been measured. In general, weight loss in polyhydrazides occurs in three distinct stages corresponding, respectively, to loss of adsorbed water, cyclodehydration, and decomposition of the poly-1,3,4-oxadiazole formed in situ. The polyoxadiazoles generally exhibit only a single weight loss step (below 700°C.) corresponding to decomposition and volatilization of the substrate itself. These data clearly indicate that the presence of aliphatic carbon-carbon linkages in the polymer backbone reduces the temperature at which decomposition of the polyoxadiazoles is noted. Corresponding differential thermometry patterns give additional data on phase transitions in the polymers and indicate, in general, that the poly-1,3,4-oxadiazoles formed in situ decompose before reaching their intrinsic melting points (under the specific conditions of these experiments). Comparison of the poly-1,3,4-oxadiazoles prepared under the (rapid) dynamic conditions of the differential thermometry and thermogravimetry techniques employed (30°C./min.) with isothermal rate data clearly suggests subtle structural differences in the polyoxadiazoles prepared by the two different modes. In general, ΔE
    Zusätzliches Material: 6 Ill.
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  • 152
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1703-1708 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(styrenesulfonic acid) ion-exchange membranes having various degrees of porosity and flexibility have been prepared by using aliphatic and aromatic esters of p-styrenesulfonic acid. The membranes formed from the aliphatic ester monomers were found to exhibit an increase in water uptake, permeability, and flexibility with increase in the size of the alcohol group of the ester monomer. With membranes formed from the phenyl and β-naphthyl ester monomers the reverse trend was indicated. The flexibility of the membranes formed from the aromatic ester monomers was much greater than that obtained with the aliphatic esters.
    Zusätzliches Material: 1 Tab.
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  • 153
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1727-1730 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Anionically prepared block copolymers of butadiene and styrene exhibit solution properties which result from a two-dimensional ordering of the polymer molecules. The most notable of these properties is the iridescent colors of toluene solutions which are dependent on concentration and abruptly change on mechanical deformation. Electron micrographs of the surface of cast films indicate that the ordered structure is retained to some degree in the solid state.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 154
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1709-1726 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effects of variation in Al/Ti mole ratio, catalyst concentration, reaction time, and temperature on the yield and some physical properties of polymers of n-octadecene-1 obtained with the use of Ziegler catalyst systems derived from titanium tetrachloride and triethylaluminum have been investigated. Results show many features similar to those obtained by other workers with lower olefins. In general, the yield of polymer shows a distinct maximum at an Al:Ti mole ratio of 2.8:1 and total catalyst concentration (at the stated mole ratio) of 4%, based on monomer; the yield increases sharply with polymerization temperature to a maximum at about 40°C. and with time up to about 12 hr. at 25°C. Polymer intrinsic viscosity also shows a strong dependence on Al:Ti mole ratio and catalyst concentration, increasing between Al:Ti mole ratios of 2.0-3.4, and showing a maximum at catalyst concentration of 3.5% on monomer. Polymer intrinsic viscosity shows a decrease with increasing reaction temperature and an increase with time of polymerization. The polymer densities, melting points, and fraction soluble in hexane (at 25°C.) appear to show much less dependence on the variables under consideration, and no firm conclusions are drawn. An important reaction concurrent with polymerization is the formation of a trans nonterminal isomer of octadecene. This certainly affects the yield (the nonterminal isomer not being polymerizable under the same conditions); the effect of the presence during polymerization of isomerized monomer on the physical characteristics of the polymer is less clear, and further work is proceeding.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 155
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The concentration dependence of the specific conductivity of the complexes of aluminum trichloride with dibutyl ether, anisole, phenol, and diphenyl ether at equimolar ratios of the two compounds has been measured. Conductivity measurements have been carried out in ethyl chloride at -78.5°C. Except for dibutyl ether, all the complexes studied are associated over the whole concentration range and their degree of dissociation and molar conductivity are independent of the concentration. In the case of the BuOBu·AlCl3 complex these quantities begin to be independent of the concentration only at concentrations higher than 20 mmoles/l. The degree of polymerization or the molecular weight of polyisobutylene formed by the polymerization in the presence of given complexes is inversely proportional to the concentration of the anions present. This is especially evident from the fact that the relation between x and 1/M̄ is also linear in the case of the BuOBu·AlCl3 complex, whose degree of dissociation and therefore molar conductivity varies distinctly with the concentration of the complex. The comparison of the chain-breaking efficiency of the anions derived from phenol and diphenyl ether with those derived from phenetole and anisole shows that the mixed aryl alkyl ethers split after reacting with aluminum trichloride under these conditions, so that the phenyl group becomes a part of the cation and the alkyl group a part of the anion. On the basis of the different behaviors of the ions and the dipoles, the differences in the dependence of the degree of polymerization on the dielectric constant of the medium in the cationic polymerization have been explained.
    Zusätzliches Material: 3 Ill.
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  • 156
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1799-1811 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetics of the polymerization of styrene in the presence of benzene at 30°C., with chromium acetylacetonate in combination with triethylaluminum and also in combination with diethylaluminum bromide as catalyst, have been studied. Chromium acetylacetonate forms a homogeneous system with triethylaluminum, and chromium acetylacetonate with diethylaluminum bromide behaves as a heterogeneous system. This homogeneous catalyst system, though reported inactive in the polymerization of α-olefins, has been found effective with styrene. Depending on the homogeneity and heterogeneity of the system, the rate of polymerization is proportional to half order and first order of catalyst concentration. A probable reason for the effect of homogeneity on the order of reaction has been discussed. A study of the effect of diethylzinc as a chain-transfer agent has helped to confirm the mechanism of polymerization.
    Zusätzliches Material: 8 Ill.
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  • 157
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1813-1820 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Isobutyl vinyl ether has been polymerized under conditions well known to yield isotactic polymer, viz., with boron trifluoride etherate at 78°C. in a nonpolar hydrocarbon diluent. A particular mixed solvent ratio and previous dissolution of catalyst enabled the polymerization to proceed homogeneously at the beginning. By following the temperature rise in an initially thermostatted system, we showed that the progress of the reaction eventually proceeded via a homogeneous phase to a gellike phase. Isotactic polymer is shown to be produced in both steps by a mechanism of slow chain propagation.
    Zusätzliches Material: 3 Ill.
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  • 158
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1821-1828 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly-α-chloroacrylonitrile, which may be regarded as a hybrid of poly(vinyl chloride) and polyacrylonitrile, is, like these polymers, insoluble in its own monomer. Its bulk polymerization is thus heterogeneous, showing abnormal kinetic features by comparison with homogeneous polymerizations. The polymerization exhibits autocatalytic properties. The initiator exponents at 0 and 5% polymerization are 0.45 and 0.44, respectively, and the overall energy of activation is 23.0 ± 2 Kcal./mole. There is no significant change in molecular weight with catalyst concentration in the range 0.057-0.90% nor with conversion up to 12%, but the reaction is accelerated by addition of polymer. Bulk polymerization results in colored products, the color deepening with conversion. These results have been compared with those of Bamford and Jenkins for acrylonitrile and Bengough and Norrish for vinyl chloride and are found to be in closer accord with the latter. They can be accounted for satisfactorily by Bengough and Norrish's suggestion that transfer occurs between growing polymer radicals and dead polymer molecules, the radicals thus formed on the surface of the polymer being removed by transfer to monomer.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 159
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1927-1950 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The surface product formed in the reaction between TiCl3 and Al(CH3)3 has been studied. Stoichiometric data, CH3/CD3 exchange, and infrared spectra permit the conclusion that the surface product is essentially a compound having the formula A model structure is proposed for this compound, valid for the 001 face of α-TiCl3. In it the titanium and chlorine atoms maintain the positions which they occupy in the α-TiCl3 lattice. One of the methyl groups protrudes from the surface whereas the other occupies the chlorine vacancy created during the reaction in the chlorine surface layer. A different sterism of the methyl groups is compatible with the experimental result that half of the methyl groups are very easily exchanged whereas the other half are not touched by the exchanging agent. According to this model it has to be assumed that the titanium atoms in the 001 plane, by far the largest face of the α-TiCl3 crystal, are not accessible. A similar model, loading to equivalence conclusions is proposed for β-TiCl3. The infrared spectra of Al(CH3)3, Al(CD3)3, AlCl(CH3)2, AlCl(CD3)2, AlCl2CH3, AlCl2CD3, TiCl3CH3, TiCl3CD3, Hg(CD3)2, and Zn(CD3)2 are discussed. Spectra of surface products formed on interaction of some of these compounds with TiCl3 are given.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 160
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1951-1969 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The determination of the number of sites active in the polymerization of ethylene on the surface of α-TiCl3-Al(CH3)3 dry catalysts leads to the conclusion that this number is small in comparison to the total surface of the catalyst. Qualitatively this conclusion is also reached by two other independent methods. Infrared spectra of the catalyst before and after polymerization do not show a change in the type of bonds present in the surface. Electron microscopy proves that no active sites are formed on the basal plane of the α-TiCl3 which constitutes 95% of the total surface. The results strongly favor the lateral faces of α-TiCl3 as the preferred location of active centers. The lateral faces contain chlorine vacancies and incompletely coordinated titanium atoms. This must then be the essential conditions for the formation of active centers. The propagation of the polymer chain has been repeatedly shown to follow an insertion mechanism. The active site, therefore, necessarily contains a metal-carbon bond. The study of catalysts derived from TiCl3CH3 leads to the conclusion that a Ti—C bond on titanium of incomplete coordination is the active species in these cases. The alkylation of surface titanium atoms was proven to be an intermediate step in the catalyst formation from TiCl3 and AlR3. Survival of titanium-alkyl bonds on the lateral faces, where titanium atoms are incompletely coordinated explains best, in the light of our data, the activity of Ziegler-Natta catalysts. Coordination of aluminum alkyl compounds in or around the active center probably complicates the structure of the active centers.
    Zusätzliches Material: 3 Ill.
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  • 161
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2028-2029 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 162
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2031-2031 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 163
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2041-2049 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of bulk polymerization of acrylonitrile, leading to a transparent polymer, was studied. The reaction was followed by a dilatometer specially designed for high degrees of conversion and for continuous supply of monomer during the reaction. The last stages of polymerization were followed by density determinations. It was found that the kinetic scheme did not show any irregularities, and that the major condition for obtaining a transparent polymer is a continuous supply of monomer to fill up the gaps formed by the contraction during the polymerization process.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 164
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2033-2040 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method for studying the thickness of adsorbed polymer films, based on the reduction in effective cross section for liquid flow caused by the deposition of such a film on the interior of a capillary, is described. A sintered disk is used instead of a single capillary to raise the flow rate to an easily measured level, to avoid the difficulties of obtaining or fabricating the extremely fine capillaries which would be required, and to eliminate the extreme precautions needed to prevent plugging of a single capillary. Techniques for characterizing the sintered disks are presented. When applied to benzene solutions of stearic acid and of polystyrene, film thicknesses of 30 and 312 A., respectively, were obtained. This is in good agreement with present knowledge of fatty acid adsorption, and suggests that the polymer is adsorbed in a highly extended configuration. The application of this method to solutions of poly(vinyl acetate), poly(methyl methacrylate), and polystyrene in several solvents at various temperatures is described in a following paper.
    Zusätzliches Material: 2 Ill.
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  • 165
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2051-2062 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A radiochemical technique involving the use of 36Cl has been described previously for the measurement of butyl rubber unsaturations. This method has now been applied to the estimation of the much lower concentration of double bonds present in polyisobutene prepared by the cationic polymerization of isobutene at a low temperature. The nature of the reaction of polyisobutene with radiochlorine in the absence of air is examined, and the experimental results are discussed in relation to present theories of the mechanisms of chain termination in cationic polymerization.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 166
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 2063-2079 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The radiation-induced copolymerization of styrene with liquid formaldehyde in bulk and in solution has been studied at low temperatures. In bulk and in methylene chloride solution copolymerization took place, whereas in diethyl ether solution only homopolymerization of the formaldehyde was found. At -78°C., in bulk and in methylene chloride solution, no evidence of polystyrene blocks could be found, whereas at -30°C. in bulk about 30% of the styrene content of the copolymer was in the form of high molecular weight blocks. The rate of copolymerization in methylene chloride solution was found to be first-order with respect to dose rate and third-order with respect to formaldehyde concentration similar to results reported for formaldehyde in toluene solution. The thermal stabilities of the copolymers were found to be intermediate between those of pure polyoxymethylene and commercially stabilized polymers. Since the latter were of higher molecular weight and contain added stabilizers, the increased thermal stabilities of the copolymers were considered to be particularly significant.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 167
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Symmetrical diamines, containing preformed carbonamide linkages, were prepared by reacting nitrobenzoyl chlorides with aromatic diamines and reducing the dinitro intermediates. The diamines were polymerized with aromatic diacid chlorides to give wholly aromatic ordered copolyamides of exceptionally high thermal stability. Ordered diamines were prepared containing only phenylene units as the aromatic portion, and others containing phenylene and naphthylene or biphenylene groups. Low-temperature solution polymerization of these diamines with isophthaloyl chloride, 4,4′-bibenzoyl chloride, or 2,6-naphthalenedicarbonyl chloride, gave thirteen ordered copolyamides, each containing a naphthylene and/or biphenylene group in its repeating unit. Differential thermal analyses and thermogravimetric analyses showed these polymers to have melting points or decomposition temperatures of from 420 to over 500°C. Films of one of the polymers had a breakdown voltage of 3000 v./mil at 180°C. Fibers of the same composition had tenacities of up to 8 g/den.; a 5.5 g/den. sample retained 85% of its tenacity after 17 hr. at 300°C. and 21% after 9 days.
    Zusätzliches Material: 4 Ill.
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  • 168
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 245-247 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 169
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 215-232 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electrical conductivity of several trialkylaluminum and alkyl-aluminum halides was investigated in dry benzene at 25°C. within the concentration range of 10-1-10-3M. The equivalent conductance of the trialkylaluminum systems decreased in the following order: Al(n-C6H13)3 〉 Al(n-C10H19)3 〉 Al(n-C4H9)3 〉 Al(i-C4H9)3 〉 Al(n-C3H7)3 〉 Al(C2H5)3. The conductance (1/R) of a given series was also examined and found to decrease as each alkyl group was successively replaced by a chlorine atom, thus: Al(C2H5)3 〉 Al(C2H5)2Cl 〉 Al(C2H5)1.5Cl1.5 〉 Al(C2H5)Cl2 and Al(i-C4H9)3 〉 Al(i-C4H9)2Cl 〉 Al(i-C4H9)Cl2. The ion pair dissociation constants K were calculated and show in a qualitative manner the difference between various organoaluminum systems. The relative rate of olefin polymerization was related to the conductivity of various organoaluminum-transition metal catalyst systems used. The effect of Lewis bases such as monoglyme, diglyme, triglyme, and tetraglyme on triethylaluminum indicated that the first-mentioned base forms a 1:1 type of complex as ordinary ethers do, whereas the remaining three bases utilize only two of their available oxygen atoms to coordinate with triethylaluminum. The effect of TiCl3 (in the presence of an ether) on the conductance was also determined.
    Zusätzliches Material: 11 Ill.
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  • 170
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The soluble cyanoethyl ether of cellulose, prepared by reaction in the presence of NaOH catalyst to high degrees of substitution (DS = 2.95), can be precipitated by various organic media and contains more nitrogen than can be accounted for by simple addition of acrylonitrile at each cellulose hydroxyl group. Infrared absorption spectra of such samples and of the reacted residues show various types of vibrational absorption bands, characteristic of amino groups. At advanced stages of the reaction the characteristic broad unresolved band of cellulose extending from 1200-950 cm.-1 largely disappears, leaving only a few weaker bands which likely overlap those due to C-N stretching. Comparison is made of the spectra of the partially cyanoethylated cellulose and the polyacrylonitrile which forms in the stock acrylonitrile, to characterize the products. It is inferred that the highly cyanoethylated cellulose, partly dissolved in the acrylonitrile, further degrades and changes under a complex mechanism to various forms of amines. The yellow to orange color of the samples is assumed to be due to these by-products. The thermogravimetric analysis reveals that these products are more heat-resistant than the cyanoethylated cellulose.
    Zusätzliches Material: 4 Ill.
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  • 171
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 248-251 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 172
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 252-254 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 173
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 255-256 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 174
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 257-274 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Complicated NMR spectra of vinyl polymers provide conformational and configurational knowledge of the polymers in solution. Explicit expressions for the spectral frequencies and intensities are obtained by the analysis of vinyl polymers and their model compounds as weakly coupled systems. The classified spectra expected for common vinyl polymers are presented by using the results of the analysis. The analysis is applied to model compounds of poly(vinyl alcohol) and poly(vinyl acetate) in solution. The results show that conformations of poly(vinyl alcohol) are determined by the intramolecular hydrogen bonding so that the syndiotactic isomer forms a helical structure, the isotactic one a planar zigzag structure. The poly(vinyl acetate) produces a helical structure for isotactic isomer by the repulsion of side chains and a planar zigzag for the syndiotactic isomer.
    Zusätzliches Material: 22 Ill.
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  • 175
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 275-282 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the presence of organoboron compounds, free-radical polymerization of vinyl monomers can proceed in spite of the presence of excess of typical radical inhibitors. The concept of free radical-organoboron complex formation is introduced to explain the unique role of organoboron compounds in such a polymerization system.
    Zusätzliches Material: 4 Tab.
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  • 176
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 431-433 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 177
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 593-602 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The permeability of ethyl cellulose to water vapor and liquid water was measured as a function of temperature. A change of slope was found in the Arrhenius plots at about 50°C., close to the glass transition. The sorption isotherms showed essentially zero heat of mixing in agreement with other workers. The diffusion constants were measured in four ways, viz., sorption, desorption, time lag, and by dividing the permeability constants by the equilibrium solubility coefficients. The time lag method gave diffusion constants which were independent of concentration, whereas the other three methods led to diffusion constants which steadily decreased with concentration. All the methods, however, extrapolated to about the same value at zero concentration. The decreasing diffusivities are believed to be due to the clustering of water molecules in the polymer. However, no clustering appeared to take place under the conditions of the time lag measurements.
    Zusätzliches Material: 5 Ill.
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  • 178
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 603-611 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effect of small amounts (0.01%-1%) of dimethyl sulfoxide on base-catalyzed polymerization and equilibration of methylsiloxanes has been examined. The addition of 0.5% of the sulfoxide increases the rate of potassium hydroxide-catalyzed polymerization of octamethylcyclotetrasiloxane by factors of 100-1000 and amounts as low as 0.01% have a large effect when low (12 ppm) catalyst concentrations are used. The rate of basecatalyzed equilibration of hexamethyl disiloxane with octamethylcyclotetrasiloxane is similarly enhanced by dimethyl sulfoxide. The equilibration occurs rapidly at 80°C. with 0.01% of potassium hydroxide and 1% of dimethyl sulfoxide, but does not proceed at a measurable rate with potassium hydroxide alone. The combination of 0.01% potassium hydroxide and 1% dimethyl sulfoxide is more effective than 0.1% of tetramethylammonium hydroxide. The large accelerating effect of the sulfoxide is believed to be due to solvation of the cation, which promotes ionization of the metal silanolate, increasing the concentration of silanolate anions.
    Zusätzliches Material: 3 Ill.
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  • 179
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The solubility properties of poly(vinyl alcohol) (PVA) vary with the method of preparation of the poly(vinyl acetate) (PVAc) from which it is derived. PVAc was prepared with free-radical catalysts over a range of temperatures from -78 to 90°C. with solvents of varying chain-transfer ability. The corresponding PVA samples varied in their resistance to dissolution in water. Their high-resolution proton nuclear magnetic resonance spectra showed on differences in tacticity. Data on 1,2-diol content showed only minor differences. Hence, the increase in resistance of PVA to dissolution in water arising from changes in chain-transfer activity of the solvent used in vinyl acetate polymerization is largely attributable to a decrease in molecular weight, and the increase in resistance of PVA to dissolution in water arising from a decrease in the temperature of the vinyl acetate polymerization is largely attributable to a decrease in both long and short branches. Evidently, with polar polymers having small side groups, tacticity is not the only factor influencing property variation; that is, variations in stereoregularity influence more the crystallinity of the sample as measured by density or x-ray methods than the ultimate crystallizability under conditions of mechanical and thermal treatment. In this regard polar polymers having small side groups differ from nonpolar polymers.
    Zusätzliches Material: 5 Ill.
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  • 180
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 699-706 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly(vinyl alcohol) single crystal platelets having a stepheight of approximately 100 A. were obtained by isothermal crystallization from dilute triethylene glycol solution. Material crystallized at temperature Tc redissolved in the same solvent at a higher temperature Ts. A plot of Tc versus Ts gave a straight line of slope 0.47. Extrapolation of this line to Tc = Ts gave (Tm)∞, which may be regarded as the dissolution temperature of the crystal of infinite stepheight. (Tm)∞ for this sample in triethylene glycol was 220°C. The crystalline nature of the platelets was established by electron and x-ray diffraction techniques. A total of three Bragg d spacings having the values of 3.9, 4.4, and 4.6 A. (±0.05 A.) were measured. These spacings were indexed as the (200), (101), and (101) reflections, respectively, of the monoclinic unit cell of Bunn. The x-ray diffractogram exhibits sharp intensities of the (101) and (101) reflections. The crystallinity calculated from the density of the poly(vinyl alcohol) precipitated from dilute solutions in triethylene glycol was 42%. Although the overall degree of crystalline perfection of this poly(vinyl alcohol) is low, the linear relationship between Ts and Tc and the formation of definite shaped single crystals when crystallized from dilute solution suggest that poly(vinyl alcohol) crystallizes in the same manner as other semicrystalline polymers.
    Zusätzliches Material: 4 Ill.
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  • 181
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 707-712 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Samples of poly(vinyl trifluoroacetate) with differing stereosequences have been prepared. The NMR signals at 56.4 Mc./sec. corresponding to the three types of triadstereosequences of the trifluoroacetate groups (isotactic, heterotactic, and syndiotactic) can be resolved. The results for specific polymers are discussed.
    Zusätzliches Material: 1 Ill.
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  • 182
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 713-716 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 183
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 717-721 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Tab.
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  • 184
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 722-727 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 185
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 728-729 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 186
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 730-732 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 187
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 733-736 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 188
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 737-750 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Equations are derived for the differential molecular weight distribution curve and for the heterogeneity index for several types of delayed initiator addition in anionic polymerization. All the results are in closed and easily used form, and depend only upon the product of the rate constant of the propagation reaction, the total initiator concentration, and a parameter representative of the rate of initiator addition. The results are plotted versus the above-mentioned product, so that one can determine the heterogeneity index to be expected under a wide range of the variables involved.
    Zusätzliches Material: 3 Ill.
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  • 189
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 751-760 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Linear polymers containing oxazolidone rings in the main chain were prepared from difunctional urethans and epoxides by the synthetic method previously used for reaction of monofunctional urethans and epoxides. The similarity of the infrared spectra of polymers and model compounds, bisoxazolidones, showed the presence of oxazolidone rings in a polymer chain. The solubility and softening temperatures of the polymers varied with the urethan unit but not with the bisepoxide structure. Polymers prepared from p-phenylenedimethylurethan and variable bisepoxides were insoluble or partially soluble in dimethylformamide, dimethyl sulfoxide, and m-cresol and had higher softening temperatures. Polymers from m-phenylenediethylurethan or toluenediethylurethan and bisepoxides were soluble in the organic solvents mentioned above, and had lower softening temperatures.
    Zusätzliches Material: 3 Ill.
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  • 190
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 761-769 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Nitrobenzene refluxed over a variety of solid catalysts near its standard boiling point of 211°C. Polymerizes to give compounds whose structure appears to be that of a triaryl amine polymer. Under similar conditions aniline gives polymers whose structure appears to be a mixture of diaryl and triaryl amine bonds.
    Zusätzliches Material: 4 Ill.
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  • 191
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 783-791 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method for the direct measurement, by means of the heat of reaction, of essentially instantaneous polymerization rates is described. The polymerization is carried out isothermally, and the evolved heat is measured electrically over short time intervals. Applied to emulsion polymerization, the technique reveals several previously unobserved features.
    Zusätzliches Material: 6 Ill.
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  • 192
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 859-868 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of hydroquinone-quinone redox polymers on highly and lightly crosslinked macroreticular styrene-divinylbenzene matrices was characterized for redox capacity, reactivity, equilibria, and redox potential. The effects of cerium(IV), iron(III), and oxygen on determinations of redox capacity are described.
    Zusätzliches Material: 3 Ill.
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  • 193
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 869-879 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The polymerization and the polymerizabilities of indene, benzofuran, and 1,2-dihydronaphthalene are discussed from the point of view of ring strain, ring stabilization, and steric hindrance in the transition state. Monomer reactivities of these olefins were estimated from copolymerization with styrene and from the rate of addition of iodine bromide in acetic acid. Rates and degrees of polymerization are compared with monomer reactivities and resonance energies of indene, 1,2-dihydronaphthalene, and benzofuran as a measure of ring strain and stabilization. It is found that indence is 1.5-2.0 times more reactive than styrene. This high reactivity of indene is attributed to the ring strain in the monomer state and to the low amount of steric hindrance in the transition state of the coplanar five-membered cyclic olefin. 1,2-Dihydronaphthalene is strained and therefore reactive, but propagation to higher molecular weight products is impeded due to the steric hindrance. The reactivity of benzofuran is decreased by conjugative stabilization of C=C double bonds at the reaction site.
    Zusätzliches Material: 6 Ill.
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  • 194
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 901-906 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Polymerization of methyl methacrylate was carried out in aqueous and nonaqueous media in the presence of some sulfonated and carboxylic organic compounds, hydroxyl radicals generated from hydrogen peroxide being used as initiators of polymerization. The occurrence of radical transfer reactions by way of hydrogen atom abstraction from the organic substrates by the ȮH radicals was demonstrated by the detection of sulfonate and carboxyl endgroups in the respective polymers. It was found that the radical transfer reactions were more favored in aqueous media than in nonaqueous systems.
    Zusätzliches Material: 2 Tab.
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  • 195
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1151-1161 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The anionic heterogeneous polymerization of methacrylonitrile by butyllithium in petroleum ether was investigated. The polymerization was of the “living” type, as seen from the linear dependence of the molecular weights on [MAN]/[BuLi]. This behavior was further supported by block polymerization experiments in which the monomer was added in two portions and the molecular weights obtained were directly proportional to the total monomer concentration. The initiator efficiency was low, and initiator consumption was only about 2%. This fact, together with the results of the block polymerizations showed that there was preferential addition of monomer to the growing chain ends rather than to the initiator. The molecular weights were independent of the rate of monomer addition. This as well as the “living” behavior of the polymerization of methacrylonitrile on a wide range of monomer and catalyst concentrations and the absence of chain transfer to monomer was essentially different from that of the similar heterogeneous polymerization of acrylonitrile by butyllithium previously investigated. This is due to the absence of an α-acidic hydrogen in methacrylonitrile.
    Zusätzliches Material: 5 Ill.
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  • 196
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1179-1190 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the graft polymerization of acrylamide initiated by ceric nitrate - dextran polymeric redox systems was studied primarily at 25°C. Following an initial period of relatively fast reaction, the rate of polymerization is first-order with respect to the concentrations of monomer and dextran and independent of the ceric ion concentration. The equilibrium constant for ceric ion - dextran complexation K is 3.0 ± 1.6 l./mole, the specific rate of dissociation of the complex, kd, is 3.0 ± 1.2 × 10-4 sec.-1, and the ratio of polymerization rate constants, kp/kt, is 0.44 ± 0.15. The number-average degree of polymerization is directly proportional to the ratio of the initial concentrations of monomer and ceric ion and increases exponentially with increasing extent of conversion. The initial rapid rate of polymerization is accounted for by the high reactivity of ceric ion with cis-glycol groups on the ends of the dextran chains. The polymerization in the slower period that follows is initiated by the breakdown of coordination complexes of ceric ions with secondary alcohols on the dextran chain and terminated by redox reaction with uncomplexed ceric ions.
    Zusätzliches Material: 5 Ill.
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  • 197
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1291-1301 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Radiation-induced solid-state copolymerization of the maleic anhydride-acenaphthylene system was carried out for the purpose of studying the solid-state polymerization of vinyl compounds in a binary system. Melting point measurement confirmed that this binary monomer system forms a eutectic mixture in the solid state. The solid-state polymerization of these monomers proceeds at maximum rate at the eutectic composition, and the polymerization products consist of a mixture of polyacenaphthylene and 1:1 maleic anhydride-acenaphthylene alternating copolymer. Since the 1:1 copolymer was obtained in solution polymerization also and maleic anhydride did not homopolymerize in solid state, it is considered that the solid-state copolymerization of maleic anhydride and acenaphthylene occurs in a liquidlike state at the boundary of the two monomer crystals.
    Zusätzliches Material: 9 Ill.
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  • 198
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1303-1309 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three series of polyamides were prepared from diamines (hexamethylenediamine, bis-5-aminoamyl ether, p-xylylenediamine) and α,ω-oxaalkanedioic acids of formula HOOC(CH2)mO(CH2)nCOOH, where m = n = 3-10, in symmetric structures, but m = 3 or 4 in unsymmetric structures. The melting points of these polymers were plotted against the number of carbon atoms of the oxaalkylene groups. The melting points of polymers from each diamine fell on three different curves according to the structures of the dicarboxylic acids: symmetric —(CH2)nO(CH2)n—; unsymmetric —(CH2)3O(CH2)n—, and unsymmetric —(CH2)4O(CH2)n—. A minimum melting point is observed at about the same point of the acid structure in every curve of the unsymmetric dicarboxylic acids. The marked depression in the polymer melting points around the minimum point is attributed to the increase of the entropy of fusion.
    Zusätzliches Material: 4 Ill.
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  • 199
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    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1351-1357 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Poly-p-xylylenes were prepared by electrolytic reduction of α,α′-dihalo-p-xylenes at controlled cathode potentials (c.p.). Polymers and halides are formed at the cathode; at the anode the halide is oxidized to halogen. Poly-p-xylylene was prepared from α,α′-dichloro-p-xylene (c.p. -1.2 v.) and α,α′-dibromo-p-xylene (c.p. -1.2 v.); poly-p-2-chloroxylylene from α,α′,2-trichloro-p-xylene (c.p. -1.4 v.) and α,α′-dibromo-2-chloro-p-xylene (c.p. -1.2 v.); poly-α,α,α′,α′-tetrachloro-p-xylylene from α,α,α,α′,α′,α′-hexachloro-p-xylene (c.p. -0.7 v.), and poly-α,α,α′,α′-tetrafluoro-p-xylylene from α,α′-dibromo-α,α,α′,α′-tetrafluoro-p-xylene (c.p. -1.1 v.). The cathode potentials were measured and controlled with respect to a saturated calomel electrode. Current efficiencies up to 96% were observed. α,α,α′,α′-Tetrachloro-p-xylylene was identified as an intermediate in the reduction of α,α,α,α′,α′,α′-hexachloro-p-xylene. A general mechanism for these reactions is suggested and discussed. It involves elimination of halide by a two-electron charge transfer with formation of a xylyl anion, followed by an elimination of halide in α′-position yielding xylylenes which then polymerize.
    Zusätzliches Material: 1 Tab.
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  • 200
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1391-1399 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of very well defined four- and six-branched polystyrene has been carried out. Anionic polymerization initiated by butyllithium in benzene-tetrahydrofuran medium gave single chains of narrow distribution. Coupling this living polystyryllithium with bis(trichlorosilyl)ethane gave a maximum of four branches. Coupling with the cyclic trimer of phosphonitrilic chloride gave a maximum of six branches. The reaction procedures have been discussed and mechanisms suggested for some of the reactions.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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