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  • 1945-1949  (148)
  • 1948  (148)
  • Polymer and Materials Science  (148)
  • Computational Chemistry and Molecular Modeling
  • Nuclear reactions
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  • 1945-1949  (148)
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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 32-38 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Physical and mechanical properties of copolymers from dienes and acrylic nitrile have been studied. The gradual increase of density is an indication of the strong intermolecular forces exerted by nitrile groups. The mutual interaction of nitrile groups and methyl groups leads to a reduction of the mobility of flow units. This can be deduced from a relative comparison of hardness, elastic recovery, stress-strain properties, and brittle point of the three polymer-homologous series.
    Additional Material: 8 Ill.
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  • 2
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recently published measurements of moisture sorption vs. relative humidity for a series of proteins have previously been analyzed in a way which permits calculation of the integral free energy of sorption for any final pressure of water vapor. The present paper is an extension of these calculations to additional proteins from the list reported by Bull; integral and differential free energies and integral and differential heats and entropies of sorption have been calculated as functions of the amounts of water sorbed onsilk, wool, egg albumin (unlyophilized and heat coagulated), salmine, collagen, gelatin and lactoglobulin (crystalline and lyophilized). All calculations are referred to saturated water vapor as the standard state. Some of the proteins show positive net differential entropies of sorption at low vapor pressures. It is postulated that the partial molal entropy of sorption is made up of two terms, a negative entropy of sorption proper and a positive entropy of solution. Partial rearrangements of the protein chains at the beginning of the sorption process would effectively be an incipient solution which would give rise to a positive partial molal entropy of sorption if the second term is greater than the first. This speculation has support in the fact that the differential entropy of salmine, which dissolves at a relative vapor pressure of about 0.7, begins to show positive values at a relative vapor pressure of 0.35.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Benzoyl, anisoyl, veratroyl, p-bromobenzoyl, p-phenylbenzoyl, p-benzoylbenzoyl, p-methylsulfonylbenzoyl, p(N,N-dimethylsulfonamido)-benzoyl and -naphthoyl disulfides are promoters of the emulsion copolymerization of butadiene and styrene, but exhibit little effect on the polymer properties. Furoyl, phenyl, p-chlorophenyl and p-bromophenyl disulfides are neither promoters nor modifiers.
    Additional Material: 4 Tab.
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ten series of model filaments with increasing orientation and swelling degrees ranging between 16 and 1.2 were prepared from three viscoses containing 4, 6, and 10.5% cellulose. Their birefringence was measured and their x-ray diagrams taken and quantitatively evaluated in order to determine the over-all orientation of the iiber substance and that of the crystalline portion. It is shown that a general relation exists between the orientation of the crystallites and that of the entire fiber substance which is the same in all fibers stretched in the swollen state. Once the birefringence of a filament is known, the orientation factor of its crystallitee can be computed without taking an x-ray photograph. From the data further evidence can be derived to the effect that the orientation of the crystallitm cannot be accounted for by the theory of affined deformation.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 157-166 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to study further the effect of structure on monomer reactivities in copolymerization the copolymer composition as a function of initial monomer mixture composition has been determined for the following monomer pairs: vinyl acetate-vinyl chloride, ethyl methacrylate-vinylidene chloride, butyl methacrylate-vinylidene chloride, vinyl acetate-tetrachloroethylene, allyl chloride-vinylidene chloride, vinyl acetate-vinylidenechloride, methyl methacrylate-vinyl chloride, pentene-1-vinyl chloride, allyl chloride-vinyl acetate, methyl methacrylate-2,5-di-chlorostyrene, vinyl chloride-vinylidene chloride, and vinyl chloride-dioctyl maleate.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 223-226 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystalline chymotrypsin has been inactivated by ultraviolet light (2537 Å.) with a quantum yield of 0.0032 based upon loss of ability to act upon casein as a substrate. The possible significance of this datum in terms of the duo-specificity of chymotrypsin, the integrity of the molecule as a whole and the quantum efficiency of cleavage of —CONH— linkages is discussed. The ultraviolet light absorption spectrum of the pure enzyme has been determined.
    Additional Material: 3 Ill.
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  • 7
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methods for the preparation of fiber-forming polymeric amides from ω-amino acids and The variation in melting points of the polymeric their amide-forming derivatives are described. The variation in melting points of the polymeric amides with increasing chain length of the recurring unit is discussed.
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 95-96 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 9
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been made of the swelling characteristics of Styrene-divinylbenzene gels containing from 0.02 to 0.12% of the cross-linking agent. Variation in swelling of samples containing the same amount of divinylbenzene was shown to increase with decreasing divinylbenzene concentration. The influence of amount of cross-linking agent, type of solvent, and temperature, on equilibrium swelling is reported. By assuming that μg is 0.44 for polymer-toluene, values of μg for over 50 different solvents have been obtained. No values of μg below 0.42 were found. A correlation of swelling values and of μg values with cohesive energy densities of the solvents is presented. The polymer appears to have a cohesive energy density of 82 cal. per cc. Equilibrium swelling decreases slightly in toluene and methyl ethyl ketone but increases markedly in cyclohexane with rising temperature. Efforts to calculate gel constants from the temperature coefficient of swelling failed completely in the case of cyclohexane, and were only moderately successful with toluene. These temperature studies, and the cohesive energy density correlations both appear to indicate a lack of complete understanding about the physical significance of μ, and why it depends so markedly on concentration.
    Additional Material: 11 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 144-144 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 302-303 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 303-303 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 314-324 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The construction and operation of the osmotic balance has been described. Because of the damping effect of the cell immersed in the solvent the sensitivity of the balance is diminished. This can be avoided if a suitable weight is placed above the central knife-edge of the beam of the balance. A way to calculate the dimensions of a cell which gives the lowest possible temperature sensibility has been discussed. The disadvantage of a thick cell wall with respect to reference point adjustments has been pointed out. The measurements made with the balance have shown that osmotic pressures of the magnitude 0.011 ± 0.001 g./cm.2 can be measured. An example of the use of the balance has been given for three samples of nitrocellulose.
    Additional Material: 10 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 336-344 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The polymerization of indene catalyzed by oxygen at 30° and 40°C., has been studied. Oxygen is absorbed and a labile “oxypolymer” or “polyindene peroxyde” is formed and can be separated from normal polymer by precipitation.
    Notes: Es wird die Polymerisation von Inden unter Sauerstoffeinfluss bei 30 und 40°C. untersucht. Sauerstoff wird absorbiert unter Bildung eines labilen “Oxydpolymers” oder “Polyindenperoxyds,” das vom normalen Polymer mittels einer Fällungsreaktion getrennt werden kann.
    Additional Material: 5 Ill.
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  • 15
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A redox-activated emulsion polymerization system has been developed in which benzoyl peroxide, sorbose and ferrous ammonium sulfate constitute the oxidation reduction system. Very rapid rates of reaction were obtained which permitted the use of lower polymerization temperatures. Redox polymers made at 10°C. had higher molecular weights and superior physical properties compared to standard GR-S as well as to polymers prepared in the redox system at higher temperatures.
    Additional Material: 6 Ill.
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  • 16
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The combination of a diazothio ether and a mercaptan in an emulsion copolymerization recipe of butadiene and styrene containing potassium ferricyanide as a “catalyst” has a very strong activating effect on the polymerization. p-Methoxyphenyl diazothio-(2-naphthyl) ether, designated as MDN, was found to be particularly suitable. In the present paper, ordinary household soap (S.F. flakes) and dehydrogenated rosin soaps of varying degrees of purity have been used as emulsifiers. By using various tertiary or primary mercaptans, polymers of any degree of modification were obtained. The recommended recipe at 40°C. gives about 80% conversion in 10 hours. The rate of conversion is greatly increased by adding to the recipe substances which have a strongly alkaline reaction in water, as sodium carbonate, trisodium phosphate, or sodium hydroxide. With such “alkaline” recipes attractive rates of conversion are obtained at around 0°C.
    Additional Material: 10 Ill.
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  • 17
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The German redox system of emulsion polymerization of butadiene and styrene has been found to be very sensitive to exact details of experimental procedure. Soap may be substituted for the alkanesulfonate used by the Germans; it is then unnecessary to add ferric laurate to the system.Careful investigation of the soap-emulsified mixture leads to the conclusion that 0.25 parts of benzoyl peroxide, 0.50 parts of ferrous sulfate heptahydrate, and 3.0 parts of sodium pyrophosphate decahydrate were the optimum concentrations of the essential ingredients for polymerization of an emulsion of 75 parts of butadiene and 25 parts of styrene in 200 parts of water and 5 parts of Procter and Gamble soap Flakes (S.F.) at 30°. At very low iron concentration the addition of a reducing agent as “booster” was beneficial; for this purpose sorbose can be replaced by fructose or, less satisfactorily, by a number of other reducing agents.
    Additional Material: 3 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 167-172 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ε-Caprolactam is converted to ε-aminocaproic acid polymer by heating under pressure with water followed, by distillation of the water and heating at atmospheric pressure. The lactam is also polymerized directly to this polymer by a catalytic method in which sodiocaprolactam is the initiator.
    Additional Material: 2 Tab.
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  • 19
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 216-222 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The emulsion polymerization of allyl acetate yields a polymer of the same average molecular weight as is obtained in bulk polymerization. The decomposition of potassimn persulfate is of the first order but is greatly accelerated by the presence of allyl acetate or of ethyl acetate. Three independent methods of analysis agree in indicating the presence of sulfate groups in 75% of the polymer molecules. It is concluded that the mechanisms of chain initiation and termination are analogous to those in the peroxide-induced bulk polymerization of allyl acetate. These facts do not serve to distinguish between different postulated loci reaction in emulsion polymerization.
    Additional Material: 2 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 227-230 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An estimate of the magnitude of the interference effect in a coil-like molecule is made by calculating the nearest neighbor density w around a given link as a function of the total number of contributing chain units. It is shown, for instance, that in a chain consisting of several hundred units, the first fifteen contribute about 75 % of the total nearest neighbor density at distances below the length of a link. The plots presented indicate that after about the first twenty links, the rate of increase of nearest neighbor density begins to flatten off. It is also possible to derive the modification of the distribution function of chain ends in real chains for a given form of w.
    Additional Material: 1 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 297-301 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental results are reported for the copolymerization of cis- and trans-dichloroethylenes and trichloroethylene with vinyl acetate and styrene. Unsymmetrical as well as symmetrical 1,2 polysubstituted ethylenes exhibit extremely small rate constants for self-propagation, but are easily attacked by vinyl-type radicals such as that formed by vinyl acetate. The attack of such monomers by vinyl “growing chain” radicals is retarded by substitution on the attacked carbon atom, but is favored by substitution on the other carbon atom of the double bond.
    Additional Material: 2 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 302-302 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 518-524 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymeric indene prepared in the presence of oxygen can be separated into two fractions by precipitation with methanol. Polyindene is insoluble while the methanol-soluble portion can be precipitated from benzene by petroleum ether as a white powdery “polyindene peroxide.” Fractionation yielded samples with molecular weights from 300 to 3000. Bromine titration indicated that the lower molecular samples contained about one double bond per polymer molecule. The polymer gave qualitative tests for peroxide, but iodimetric titration of one sample gave only some 42.5% of the calculated active oxygen content.
    Notes: Polymeres Indol, das in Gegenwart von Sauerstoff dargestellt wurde, kann durch Fällen mit Methylalkohol in 2 Fraktionen getrennt werden. Polyindol ist unlöslich. Die methylalkohollösliche Fraktion kann aus Benzol mit Petroläther als ein weisses, pulveriges “Polyindolperoxyd” ausgefällt werden. Fraktionierung führte zu Substanzen mit Molekulargewichten zwischen 300 und 3000. Bromtitration deutete darauf hin, dass die niedrigmolekularen Proben ungefähr eine Doppelbindung pro Polymermolekül enthielten. Die qualitative Prüfung für Peroxyd war positiv, aber die jodometrische Titration einer Probe ergab nur 42.5% des berechneten aktiven Sauerstoffgehaltes.
    Additional Material: 4 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 525-534 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The reaction of indene with sulfur has been shown to give a polymer containing one atom of sulfur per indene unit. The refraction and absorption characteristics of the polymer have been reported. The kinetics of the reaction of sulfur, with and without added accelerators, have been investigated with the view to establishing the influence of the accelerators on the rate and the temperature coefficient.
    Notes: Es wird gezeigt, dass die Reaktion von Indol mit Schwefel zu einem Polymer führt, das ein Schwefelatom pro Indoleinheit enthält. Der Brechungsindex und das Absorptionsspektrum des Polymers werden mitgeteilt. Die Kinetik der Schwefelreaktion, mit und ohne Zusatz von Beschleunigern, wird untersucht um den Einfluss der Beschleuniger auf die Reaktiongeschwindigkeit und die Temperaturabhängigkeit der Reaktion festzustellen.
    Additional Material: 6 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 652-662 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been demonstrated that the adhesion of high polymers to cellulose is a function of tack temperatures and dielectric constants, ∊, of the polymers and of dipole moments, μ, of polar groups. A plot of tack temperature versus mirror image force, μ1μ2/,of copolymers gives an area of adhesion bounded by a tack temperature of 100% and mirror image forces of 0.7 and 1.3 and opening toward lower tack temperatures. Outside of the area polymers do not adhere well to cellulose. By coating polymers on cellulose pretreated with Werner chromium complexes of acids bearing polar groups, it has been found that adhesion is a specific function of the polar groups within the polymer and on the modilied cellulose. Adhesion is strongest with approximately equal dipole moment substituents on the modified cellulose and in the copolymers.
    Additional Material: 2 Ill.
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  • 26
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peroxide-initiated polymerization of allyl methacrylate has been examined in the presence of certain additives. By the use of mercaptans and diisopropyl dixanthogen the extent of polymerization at the point where gelation occurs may be extended from about 6% to 20-30% polymerization. Examination of samples of polyallyl methacrylate, polymethyl methacrylate, and the copolymer of methyl methacrylate and allyl chloroacetate indicates that the postponement of gelation results largely from diminution of the molecular weight by the regulators. The effects of regulators on the composition of copolymers and the molecular weight of polymers, and the relation between molecular weight and extent of reaction at the gel point are discussed.
    Additional Material: 3 Tab.
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  • 27
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation of stress in polyisobutylene whole polymer of different average molecular weights has been investigated over the temperature range 30-100°C., and at different elongations. The shape of the relaxation curve is independent of elongation in a range of low elongations; above this range there is a gradual change in curve shape with increasing elongation. The shape of the relaxation curve for a given molecular weight is the same at different temperatures, when plotted as reduced stress vs. logarithmic time; a change in temperature essentially shifts the position of the curve along the logarithmic time scale. The activation energy for relaxation, calculated by use of the Arrhenius equation, is found to be independent of molecular weight in the molecular weight range investigated (M̄v = 665,00.0 to 1,420,000), the average value being 15.4 kcal. Straight lines are obtained when reciprocal viscosity-average molecular weight is plotted against log time required for the reduced stress to reach a certain arbitrary value, at a fixed temperature and elongation. Relaxation rate depends on molecular weight with sufficient sensitivity so that relaxation measurements may be a practical method of measuring molecular weight directly in the solid state.
    Additional Material: 11 Ill.
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  • 28
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 714-734 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 29
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 772-775 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Recently published data on copolymerization has been shown to correlate satisfactorily with the scheme of Q and e factors proposed by Alfrey and Price, thus lending further support to the utility and to the theoretical interpretation on which it was based.
    Additional Material: 1 Ill.
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  • 30
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The second-order transition temperatures (Tm) for foruteen commercially available butadiene-acrylonitrile copolymers with 18-50% acrylonitrile have been determined refractometrically and found to be somewhat lower than the corresponding brittle temperatrues (Tb). The data show a linear relation between Tm and acrylonitrile content.
    Additional Material: 1 Ill.
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  • 31
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 897-898 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 32
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 899-900 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 33
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 141-142 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 34
    Electronic Resource
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 143-143 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 35
    Electronic Resource
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 143-144 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 36
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The initial rate of polymerization of highly purified styrene in bulk has been measured dilatometrically at 38.4, 56.4 and 70.1°C. For conversions up to one per cent a well-reproducible rate was observed for samples handled in complete absence of atmospheric gases. For samples saturated with air an equally reproducible, though higher rate, was observed initially. The duration of this higher rate decreases with increasing length of storage between saturation and measurement. After polymerization at higher rate, the sample continues to polymerize at the rate observed for the air-free samples.
    Additional Material: 7 Ill.
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  • 37
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 22-31 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A turbidimetric method has been developed for determining the styrene content in water and soap solution. The solubility of styrene in distilled water was 0.022% while in 2.0% potassium oleate solution it was 0.65 to 0.88%. The course of the polymerization of a saturated solution of styrene in 2% potassium oleate was followed by a colorimetric analysis based on reaction with dilute potassium permanganate. The rate of polymerization decreased rapidly after 50% conversion. The activation energy was estimated to be 17,000 kcal., somewhat less than in solution. The molecular weight of the polymer produced was 200,000. Occasional erratic results were ascribed to possible influence of various amounts of air sealed in the polymerization mixtures.
    Additional Material: 4 Ill.
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  • 38
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been demonstrated that the homogeneity in respect to molecular weight of emulsion copolymers of butadiene and styrene can be increased by the use of certain derivatives of n-dodecyl mercaptan rather than the mercaptan itself. These derivatives decompose and relase n-dodecyl mercaptan at an even rate during the polymerization reaction. Several new derivatives of n-dodecyl mercaptan are described.
    Additional Material: 1 Ill.
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  • 39
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Precise analytical methods are developed using iodine monochloride for the determination of unsaturation in polybutadiene and polyisoprene and their copolymers with styrene. The complicating side reactions, splitting out and substitution, as well as the influence of the solvent employed are investigated in detail. It is concluded that GR-S at various conversions has the theoretical unsaturation. Emulsion polybutadiene exhibits 97 to 98% of the theoretical unsaturation, emulsion polyisoprene 97% sodium polybutadiene 92%, and sodium polyisoprene 85%. The amount of unsaturation in these last two polymers as well as in the sodium copolymer of butadiene and styrene (75:25) is considerable less than theoretically expected.
    Additional Material: 8 Ill.
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  • 40
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystalline soybean trypsin inhibitor has been inactivated by ultraviolet light (λ2537 Å.) with a quantum yield of 0.0088 based upton loss of ability to inhibit the action of trypsin on casein. Inactivation involves a “one-hit” process.
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  • 41
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 303-303 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 42
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solid polyhexamethylene adipamide prepared by slow cooling of a melt is opaque as a result of formation of spherulites. Spherulites may also be formed by slow evaporation of a phenol solution of polyhexamethylene adipamide. Transparent, nonspherulitic polymer of a low degree of lateral order can be formed by cooling the polymer rapidly. Heat treatment or aging of this polymer increases the lateral order without the formation of microscopically visible spherulites. Spherulites usually reduce tensile strength, increase opacity, and decrease workability.
    Additional Material: 7 Ill.
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  • 43
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 325-326 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The rate constants for thermal polymerization of indene at 150° and 175° in the absence of oxygen have been found to be 6.0 × 10-6 and 3.16 × 10-5 min.-1, respectively. The average degree of polymerization at each temperature was slightly less than four.
    Notes: Die Geschwindigkeitskonstante der thermischen Polymerisation von Inden bei 150° und 175° in Abwesenheit von Sauerstoff wird zu 6.0 × 10-6 und 3.16 × 10-5 min.-1 resp., bestimmt. Der durchschnittliche mittlere Polymerisationsgrad war etwas geringer als 4 bei beiden Versuchstemperaturen.
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  • 44
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 358-364 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The densities of undrawn and drawn nylon filaments (6-6 Nylon) are found to be 1.1339 and 1.1384, respectively, at 25°C. Annealing either the drawn or undrawn forms to the highest temperature possible short of melting increases the room temperature density to 1.1564, the most rapid increase in density with temperatures annealing coming at 210°C. The temperature coefficient of the density as measured at room temperature is greater for the drawn form of the nylon than the undrawn after annealing has taken place. The density of nylon calculated by Bunn and Garner from x-ray diagram data is 1.24, considerably higher than the highest value obtained by us on annealing, namely 1.156.
    Additional Material: 1 Ill.
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  • 45
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    Journal of Polymer Science 3 (1948), S. 365-370 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: A brief review is given of the evidence for the existence of a long period of about five hundred glucosidic units in fibrous cellulose. The heterogeneity of the molecular weight distribution can be measured as a function of the extent of degradation and is found to increase much less rapidly than would result from random scission. The interpretation of kinetic studies by means of Ekenstam's equation leads to the evaluation of two different rate constants and activation energies in the degradation reaction. Finally, the electron microscope photographs reveal significant difference between individual fibers resulting from wet milling and those produced by hydrolytic reaction.
    Notes: Eine Übersicht wird gegeben für die Argumente, die für das Vorhandensein eines regelmässigen, langperiodischen Aufbaus von Einheiten von 500 Glukoseresten in Fasercellulosen sprechen. Die Uneinheitlichkeit des Gewichtsdurchschnittes kann in ihrer Abhängigkeit vom Abbaugrad gemessen werden und nimmt viel langsamer ab als unter der Annahme von statistischer Spaltung. Die Interpretierung der kinetischen Studien mit Hilfe der Gleichung von Ekenstam führt zu zwei verschiedenen Geschwindigkeitskonstanten und Aktivierungsenergien für die Zerfallsreaktion. Schliesslich zeigen elektronenmikroskopische Aufnahmen charakteristische Unterschiede zwischen Fasern die durch Nassmahlung und durch Hydrolyse gewonnen wurden.
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  • 46
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The inhibiting action of several phenols on the GR-S 10 (rosin soap) recipe for synthetic 2,5-Di-t-butylhydroquinone is shown to be a particularly powerful inhibitor rubber is reportor in this recipe.
    Additional Material: 7 Ill.
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  • 47
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 48
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 464-464 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 49
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An expression for the amount of chain transfer occurring in a copolymerization carried out in solvent media can be derived in a manner similar to the composition-kinetic treatment for tripolymer formation. As a result, the relative reactivity of the chain-transfer solvent can be determined.
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  • 50
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    Journal of Polymer Science 3 (1948), S. 465-480 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fine structures of emulsion polybutadiene prepared at temperatures ranging from 55°C. to -20°C. and of various butadiene-styrene copolymers prepared at -20°C. have been studied by x-ray methods. The ability of emulsion-polymerized butadiene to crystallize was found to depend to a large extent on the temperature of polymerization. Butadiene polymerized at 30°C. and above showed no evidences of crystallization when cooled unstretched to -70°C. as observed by x-ray diffraction methods; however, butadiene polymerized at 20°C. and below showed crystallization effects when cooled unstretched to -70°C. These crystallization effects became more pronounced for samples polymerized at lower temperatures. Layer-line diffraction patterns of butadiene polymerized at 30°C. and below were obtained by stretching the polymer at about 0°C. From these patterns the geometrical repeat distance along the polymer chains was found to be 5.1 ± 0.1 Å. This corresponds to a fully extended butadiene unit in the trans configuration. An anomaly was observed in the diffraction patterns of crystallizable polybutadiene stretched at 0°C. Some of the layer-line spots varied in position with per cent elongation of the sample. This suggests that the molecules in crystallites of the polymer are inclined to the stretch axis at low elongations and that they become more nearly parallel to the stretch axis at higher elongations. A small addition of styrene as comonomer at -20°C. polymerization temperature did not prevent crystallization and preferred orientation effects in the polymer, since these effects could still be found in a 90/10 charge copolymer. Larger amounts of styrene did prevent crystallinity and preferred orientation as shown by the amorphous nature of an 80/20 charge copolymer. The ability of a compounded vulcanizate of a given polymer to crystallize is less than that of the purified polymer under the same conditions. This may be due to the combined effects of milling, vulcanization, and the presence of carbon black particles in the polymer. A description of the apparatus and techniques used for cooling and stretching these polymers is given.
    Additional Material: 10 Ill.
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  • 51
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    Journal of Polymer Science 3 (1948), S. 503-517 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of decomposition of benzoyl, lauroyl, bis(p-chlorobenzoyl), and bis(2,4-dichlorobenzoyl) peroxides, 0.0133 molar in styrene, have been determined at 34.8, 49.4, 61.0, 74.8, and 100°C., and the corresponding rates of polymerization of styrene have also been determined. Assuming the initial rate of polymerization of styrene, produced by benzoyl peroxide at an initial concentration of 0.0133 m./l. at each of the five temperatures used to be unity, the relative initial rates of polymerization produced by the peroxides studied are as follows: bis(2,4-dichlorobenzoyl) 2.15, lauroyl 1.52, and bis(p-chlorobenzoyl) 0.87. The rate data have been subjected to an approximate kinetic analysis, from which one may conclude that the order of intrinsic effectiveness of the peroxides as chain-initiating agents in styrene is benzoyl 〉 bis(p-chlorobenzoyl) 〉 lauroyl 〉 bis(2,4-dichlorobenzoyl), and that the effectiveness increases with increasing temperature. The activation energy for the peroxide-initiated polymerization of styrene was found to be 21 kcal. per mole. The molecular weight of polystyrene appears to be an inverse function of the temperature, the polymerization rate, the peroxide decomposition rate, and the extent of wasteful decomposition of the peroxide.
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  • 52
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    Journal of Polymer Science 3 (1948), S. 535-538 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: A sample of polyindene (number average molecular weight, 400) was carefully fractionated into nine fractions with molecular weights varying from 300 to 800. The observation by Whitby and Katz that bromine titration indicated one double bond per polymer molecule was substantiated. However, this double bond is no longer active for polymerization since the molecular weights of various fractions did not change significantly on exposure to polymerizing conditions (heating for 500 hours under nitrogen at 175°C.).
    Notes: Eine Probe von Polyindol (mittleres Molekulargewicht 400) wird sorgfältig in 9 Fraktionen von steigendem Molekulargewicht von 300 bis 800 zerlegt. Die Beobachtung von Whitby und Katz, dass Bromtitrierung zu einer Doppelbindung pro Polymermolekül führt wird bestätigt. Diese Doppelbindung ist aber nicht länger zur Polymerisation fähig, da sich die Molekulargewichte verschiedener Fraktionen nicht mehr wesentlich änderten, wenn sie Polymerisationsbedingungen - Erhitzen für 500 Stunden bei 175° in Stickstoffatmosphäre - ausgesetzt wurden.
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  • 53
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    Journal of Polymer Science 3 (1948), S. 539-548 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The evidence for the nature of the side chains in lignin resulting from investigations of the reactions of model substances has been summarized. The studies have involved investigation of the reactions with (a) sulfite, (b) alkali and nitrobenzene, and (c) hot alkali. (a)Reaction with sulfite occurs readily for model substances with β-hydroxyl or α,β unsaturated keto groupings (“aldol type”). Hydroxyl groups adjacent to a ring are somewhat reactive but or-hydroxyketo groupings (“acyloin type”) do not react.(b)Alkaline oxidation to aldehyde or carboxyl with nitrobenzene is effective in degrading a side chain para to a free hydroxyl group having an oxygen atom on the α-carbon atom. Conversion of the para-phenolic hydroxyl to a methyl ether neutralizes its promoting influence.(c)Cleavage to an aldehyde with hot alkali in the absence of air is specific for the “aldol type” grouping in the side chain. This is regarded as a reverse aldol condensation and it has been demonstrated that acetaldehyde can be isolated from such degradations.These results, together with the behavior of lignin and its derivatives, are interpreted in terms of probable structures for the side-chain units in lignin.
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  • 54
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    Journal of Polymer Science 3 (1948), S. 602-603 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 55
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    Journal of Polymer Science 3 (1948), S. 603-604 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 56
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A large-scale precise fractionation of GR-S (X-55) was performed using the fractional precipitation technique at 25°C. 9 fractions, each weighing approximately 150 g. and comprising approximately 11% by weight of the original unfractionated sample, were obtained and a detailed study was made showing the effect of number-average molecular weight and related sol-gel properties on various physical and chemical properties of the crude and vulcanized fractions. Using a Santocure tread-type recipe, preliminary compounding work indicated the sulfur ratios required to give vulcanizates with 300% modulus values of 1000 p.s.i. All fractions were recompounded using these indicated optimum sulfur values. Generally, as the number-average molecular weight increased, better stress-strain and quality index data were obtained. These and other physical properties of the vulcanizates of these fractions are discussed in detail. As found in past fractionation studies pertaining to unsaturated high polymers, the higher molecular weight fractions, obtained from the unfractionated sample which was totally soluble in benzene, undergo considerable gelation when isolated and vacuum dried at 25°C. in the dark. As the indicated molecular weight of the fraction increased, higher per cent gel contents were obtained. Compared to unfractionated butadiene-styrene copolymers of similar gel contents, the gel portions of the higher molecular weight fractions had unusually high swelling indices. indicating qualitatively that the average molecular weights between points of effective cross linking in the three-dimensional gel structure were higher than those encountered in the past in unfractionated samples of similar gel contents. Other data are given pertaining to these fractions, such as the bound styrene content, per cent shrinkage of the compounded unvulcanized stocks, and the rate of gel breakdown with cold milling.
    Additional Material: 7 Ill.
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  • 57
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    Journal of Polymer Science 3 (1948), S. 607-608 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 58
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    Journal of Polymer Science 3 (1948), S. 642-645 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymeric oxidation products of indole act like typical peroxides in polymerization reactions. Due to their relatively high stability the increases of the reaction is small, while fragments of the degraded peroxide enter the polymer molecule.
    Notes: Polymere Oxydationsprodukte des Indens verhalten sich in Bezug auf Polymerisationsreaktionen wie typische Peroxyde. Ihre verhältnismässig hohe Stabilität bedingt eine relative geringe Reaktionsbeschleunigung, wobei Bruchstücke des zerfallenden Peroxyds in die polymere Molekel eintreten.
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  • 59
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    Journal of Polymer Science 3 (1948), S. 646-646 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 60
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A refractometric technique for determination of second-order transition temperatures (Tm) of polymers has been extended to include a series of alkyl acrylate and methacrylate polymers with transitions at temperatures down to -50°C. A convenient technique for determining refractive index down to -75°C. is described. Certain long-chain alkyl polymers are birefringent below Tm. Correlations of brittle point with Tm and relations between viscosity and Tm are reported.
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  • 61
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    Journal of Polymer Science 3 (1948), S. 663-668 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Verdet constants of nine polyethylene glycols, three polypropylene glycols, and nine silicone polymers have been measured at 25°C. It was found that the Verdet constant increases with increase in molecular weight in each of the series, and approaches a constant value. A similar increase in the molecular magnetic rotation was noted. The results are in contrast with those on polystyrene, and the effect of end groups on the measurements is discussed in explanation.
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  • 62
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    Journal of Polymer Science 3 (1948), S. 798-798 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 63
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The fundamental basis of our work is the application of statistics involving both the energy of interaction between solute and solvent molecules and the effect of steric hindrances: the statistics of freely rotating chains (sometimes called the statistics of Kuhn) are a special limiting case. Using this we can show that in the law [η] = KNα the coefficient is a function of N having a value close to 2 for small values of N, and approaching on first approximation a value of 0.5 when N increases infinitely. This statistical method has the advantage of permitting an approach to the important problem of the variation of the intrinsic viscosity as a function of the temperature T. The behavior of intrinsic viscosity with degree of polymerization and temperature as predicted by the theory check with experiment, and, in the case of the hemipolystyrenes, it has been possible to obtain very satisfactory quantitative verification. In view of numerous experiments which show that, at a given temperature, the limiting value of α for very large N is greater than 0.5, we have altered the theory of the equivalent particle accordingly. As a basis for the change the concept of porosity is examined with several other concepts, and it is shown that it is likely to apply only with reservations when the molecular structure of the solvent is taken into account.
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  • 64
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    Journal of Polymer Science 3 (1948), S. 850-865 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The decrease of the limiting viscosities of unfractionated and fractionated polystyrene with time has been studied over a range of temperatures from 248 to 340°C. in vacuo. Distribution curves of several degraded samples have been determined. It has been established that the theory of random breaking of links is not applicable in the case of polystyrene. Three major deviations from the random theory have been found. The experimental results have been evaluated employing the weak link theory. The mechanisms proposed account satisfactorily for the deviations from the random theory, and give a fair representation of the experimental results, only the experimental distribution curves still showing deviations from those predicted by theory. The elementary steps for the degradation in vacuo have been discussed and the role of oxygen during polymerization has been indicated.
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  • 65
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    Journal of Polymer Science 3 (1948), S. 891-894 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Additional data relating to the mechanism of the emulsion copolymerization of styrene and copolymerization of styrene and acrylonitrile are presented. These results show the influence of varying the emulsifier and of varying the water-monomer ratio upon the relationship between monomer composition and the composition of the initial copolymer molecules formed. The composition of the initial copolymer produced in emulsion is the same as that which would be predicted if polymerization occurred in the oil droplet.
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  • 66
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Evidence is presented to show that either sodium ferri- or ferropyrophosphate with hydrogen peroxide effectively initiates emulsion copolymerization of butadiene and styrene. The hydrogen peroxide appears to be destroyed as such before polymerization begins, thus indicating that it converts some other constituent of the recipe into the effective catalyst for polymerization.
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  • 67
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    Journal of Polymer Science 3 (1948), S. 371-375 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rosin can be modified by two fundamentally different methods. which usually are combined to get the best results. These methods are based on neutralization of the carboxyl group and reaction with the unsaturated part of the rosin molecule. The products are used as a filler to improve gloss and hardness of the paint or varnish film. They are easily soluble in the common solvents and the harder types promote drying. Depending upon the method of treatment, they are more or less liable to oxidation. The molecular weight increases most for the phenolic- and maleic-modified ester gums and especially when esterified with penta-erythritol.
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  • 68
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    Journal of Polymer Science 3 (1948), S. 463-463 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 69
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    Journal of Polymer Science 3 (1948), S. 304-304 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 70
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    Journal of Polymer Science 3 (1948), S. 327-335 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: A sample of polyindene has been fractionated by precipitation from benzene by butyl alcohol or from ether by methanol into fractions varying from 200 to 1200 in molecular weight. These data have been used to estimate the distribution function for polymer of this low molecular weight range.
    Notes: Polyindenpräparate werden durch Ausfällung mit Butylalkohol aus Benzol oder mit Methylalkohol aus Äther in Fraktionen von Molekulargewichten von 200-1200 zerlegt. Diese Werte werden benutzt um die Verteilungsfunktion dieser Polymeren mit extrem niedrigen Molekulargewichten zu berechnen.
    Additional Material: 4 Ill.
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  • 71
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    Journal of Polymer Science 3 (1948), S. 345-349 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface tension of polyoxyethylene glycol in water leads to a value for the area per molecule which shows that the polymer molecules lie approximately flat in the surface. Molecular weight determinations by end-group analysis and freezing-point depression are compared with values of the intrinsic viscosity and limiting area per molecule.
    Additional Material: 3 Ill.
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  • 72
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    Journal of Polymer Science 3 (1948), S. 549-563 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence has been studied of systematic alterations in the amount of cross linking in elastomers upon diffusion coefficients and permeability constants in elastomers of homologous paraffin hydrocarbons. In a number of such media the influence of chain length of the paraffins upon the transport phenomena has also been investigated, using CH4, C2H6, C2H4, C3H8, and n-C4H10.Apparent activation energies for permeation (Ep) and for diffusion (ED) for degrees of vulcanization up to 11.3% combined sulfur are in the decreasing order: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm butane } 〉 {\rm propane } 〉 {\rm }_{{\rm ethylene}}^{{\rm ethane}} {\rm } 〉 {\rm methane } 〉 {\rm nitrogen}$$\end{document} For low vulcanizates, EP is not very sensitive to the per cent sulfur. However for higher percentages of sulfur, EP tends to rise, especially when the migrating molecule is a large one. ED is rather more sensitive both to molecular size and to per cent combined sulfur.Both EP and ED for natural rubber vulcanizates show definite temperature coefficients, manifested as curvature when log10 D or log 10 P is plotted against 1/T. Such curvature was absent, however, in butyl rubber.The results have been interpreted in terms of the molecular nature of elastic networks and in terms of the kinetic-statistical (zone) theory and the transitionstate theory. All treatments indicate the need for a considerable zone of activation for each unit diffusion process, confirming an earlier investigation. When, in the Arrhenius equation, D = D0e-ED/RT, one plots log10D0 against ED/T, the clear functional relationship: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm }D_0 {\rm } = {\rm } - 3.6{\rm } + {\rm }0.14{\rm }{{E_D } \mathord{\left/ {\vphantom {{E_D } T}} \right. \kern-\nulldelimiterspace} T}$$\end{document} emerges. A simple interpretation of this and of similar functional relationships for other “activated” physical and chemical rate processes has been given.
    Additional Material: 12 Ill.
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  • 73
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    Journal of Polymer Science 3 (1948), S. 564-575 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solubility of nitrogen, ethylene, and the n-paraffins from methane to pentane has been measured in a series of natural rubber vulcanizates in relation to chain length of paraffin, temperature, and degree of cross linking of vulcanizates which contained between 1.7 to 21.9% combined sulfur.For smaller, less soluble paraffins the degree of vulcanization had little influence upon the solubility but for higher molecular paraffins such as pentane this influence became significant. A qualitative interpretation of the effects observed was given. The solubility data are in all cases represented by a statistical theory of one of the authors for a mean frequency of vibration of the solute in the medium corresponding to the infrared (0.5 to 1.0 × 1012 sec.-1). The solubility constants, σ, and critical temperature, Tc, are also empirically related by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm }\sigma {\rm } = {\rm }a{\rm } + {\rm }bT_c {\rm }\left( {a{\rm and }b{\rm are constants}} \right)$$\end{document} Heats and standard free energies of solution for the earlier homologous paraffins show steady trends as the chain length increases. The heats are exothermal and are adequately interpreted as the sum of the heats of liquefaction together with a small heat-of-mixing term for liquid and rubber which was usually close to that given by Hildebrand's cohesive energy density equation: \documentclass{article}\pagestyle{empty}\begin{document}$$q{\rm } = \;\left[ {\left( {{{E_1 } \mathord{\left/ {\vphantom {{E_1 } {V_1 }}} \right. \kern-\nulldelimiterspace} {V_1 }}} \right)^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} {\rm } - {\rm }\left( {{{E_2 } \mathord{\left/ {\vphantom {{E_2 } {^2 V_2 }}} \right. \kern-\nulldelimiterspace} {^2 V_2 }}} \right)^{{\raise0.7ex\hbox{$1$} \!\mathord{\left/ {\vphantom {1 2}}\right.\kern-\nulldelimiterspace} \!\lower0.7ex\hbox{$2$}}} } \right]^2 V_1 v_2^2$$\end{document} As anticipated from statistical theory, entropies were usually several entropy units more negative than those for solutions of gases in monomeric solvents.
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  • 74
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    Journal of Polymer Science 3 (1948), S. 606-607 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 75
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 76
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    Journal of Polymer Science 3 (1948), S. 631-634 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An empirical method of correcting the sedimentation constant of high polymers for its concentration dependence is proposed. It should be possible to determine the sedimentation constant at infinite dilution with reasonable accuracy from experiments at concentrations where reliable measurements can be made.
    Additional Material: 1 Ill.
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  • 77
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    Journal of Polymer Science 3 (1948), S. 635-641 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By denaturation of potato albumin by pyridine or by heat the viscosity increases; simultaneously the capability of the denatured protein t o reduce iodine increases, which, according to Anson, is due to the liberation of SH groups. A similar increase of viscosity was observed by the conversion of legumin into a water-soluble modification, and further by heating the solution of this protein; the volume of iodine required for oxidation of the denatured protein is greater than that of the native legumin. This denatured protein can be reconverted into its native state, whereupon the reducing capacity again decreases. Several fractions of green pen and horse bean legumin were denatured by urea and it was found that the viscosity and the reducing capacity thereby increase. In the case of legumelin the viscosity is low but the reducing power high; this indicates that legumelin is a degradation product having globular molecules.
    Additional Material: 9 Tab.
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  • 78
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    Journal of Polymer Science 3 (1948), S. 609-630 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The chemical structure of a large number of linear condensation polymers is correlated with their ability to assume a polycrystalline form possessing the right degree of thermal stability, and with the possession of fiber-forming properties. Certain structures lead to the absence of crystallinity and of fiber-forming properties, while, under certain conditions, a low degree of crystallinity or its complete absence leads to polymers possessing rubberlike properties, which may form highly elastic threads. Some properties of fibers such as solubility, sensitivity to mositure, and certain dyeing characteristics, can be correlated to some extent with chemical structure. These effects are considered on the basis of the introduction of various polar links and ring structures, according to regular patterns, into the polymethylene chain (polythee). The ehter (R—O—) and ester (—CO·O—) links lower the crystallite melting point to such an extent that some polymers containing them are completely noncrystalline at normal room temperatures. Urethan (—O·CO—NH—), amide (—CO·NH—) and urea (—NH·CO·NH—) links raise the crystallite melting point to an extent which increases in the order named. Most other polar links raise the melting point. The introduction into the aliphatic chain of ring structures, particularly aromatic rings directly attached to polar groups, raises the crystallite melting point, but in this case symmetry exerts an over-ruling effect. A low degree of symmetry may lower the melting point and even eliminate crystallinity entirely to the detriment of fiber-forming properties. Inert side chains lower the melting point considerably, and in some cases render the polymer completely noncrystalline at normal room temperatures.
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  • 79
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    Journal of Polymer Science 3 (1948), S. 798-798 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 80
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 81
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    Journal of Polymer Science 3 (1948), S. 804-811 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experiments with cross linking of nitrocellulose in butyl acetate solution by means of titanium tetrachloride are described. The gels have been examined by means of sedimentation in the ultracentrifuge and measurements with a consistometer. The yield value of the flow curves and the extent of cross linking were studied as functions of nitrocellulose concentration, amount of cross-linking substance, and time of reaction.
    Additional Material: 7 Ill.
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  • 82
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray diffraction patterns of stretched crystallized polybutadiene polymerized at -20°C were obtained using molybdenum, copper, and chromium characteristic x-radiations on the same sample. The pattern obtained using molybdenum radiation showed diffraction effects in the 0, 1st, 2nd, 3rd, and 4th orders. The lack of detail in this pattern is partly due to the relatively intense background. By using the longer wavelength copper and chromium radiations the diffraction effects of the zero- and first-order layer lines were brought out in considerable detail. The diffraction data obtainable from these layer line patterns may be useful in carrying out a structural analysis of crystalline polybutadiene.
    Additional Material: 1 Ill.
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  • 83
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    Journal of Polymer Science 3 (1948), S. 834-849 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: It has been found, by interpretation of the curve for the potentiometric titration of viscose with 0.1 N AgNO3, that the sulfur compounds of the viscose exist in the “ortho” form. This leads to a new theory for the ripening of viscose.
    Notes: En cherchant à interpréter la courbe expérimentale de la titration potentiométrique de la viscose par l'AgNO3, 0.1 N, on a découvert que les composés sulfurés de la viscose devaient se trouver sous la forme “ortho.” Ceci a permis de proposer une nouvelle théorie du mürissement de la viscose.
    Additional Material: 8 Ill.
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  • 84
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    Journal of Polymer Science 3 (1948), S. 829-833 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: It is shown that the ratio of the ultrasonic velocity to the density of various polymers (u/p) is related to the form of the molecules. In particular, it is shown that: (1) in compounds with a rigid, straight paraffin chain, u/p increases with increasing molecular weight from 1.69 at 20° for low-molecular hydrocarbons to 1.92 for high-molecular polythenes; (2) in cross-linked compounds with ethyl and methyl groups, u/p is practically a constant for all compounds up to a molecular weight of 15,000; (3) in compounds containing large radicals in the side chain (as phenyl or hydroxyisobutyl), u/p is much smaller for high polymers than for low-molecular compounds; (4) in general, the compressibility is higher for polymers with frequent and large cross linkages than for compounds with little or no cross linking.
    Notes: Il est montré que le rapport entre la vitesse de propagation des ultra-sons et la densité (u/p) des polymères est fonction de la forme des molécules. En particulier on trouve: (1) dans les composés à chaîne rigide paraffinique non ramifiée, ce rapport à la température de 20° s'accroît sensiblement avec le poids moléculaire de 1.67 pour les hydrocarbures du poids moléculaire bas à 1.92 pour le polythène à poids moléculaire élevé; (2) dans les composés ramifiés ayant des groupes méthyliques ou éthyliques, ce rapport est pratiquement constant pour tous les composés examinés jusqu'au poids moléculaire 15.000; (3) dans les composés linéaires contenants des groupes latéraux de dimensions plus grandes (p.e., phényliques ou oxybutyliques), ce rapport est plus petit pour les hauts polymères que pour les composés à poids moléculaire bas; (4) en général la compressibilité est plus élevé pour les polymères avec des ramifications fréquentes et longues que pour les polymères peu ou pas du tout ramifiés.
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  • 85
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    Journal of Polymer Science 3 (1948), S. 866-879 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By using the methods which have been developed to describe the activation energy of chemical reactions in terms of bond energies and the repulsing energies between reacting centers, the factors influencing the activation energies of reactions between radicals and monomers are discussed. Calculations are reported on a number of simple prototype reactions involving radicals and atoms and ethylenic bonds. It is found that the heat of reactions is a most important factor in determining the activation energies of such reactions and this result is extended to a wide variety of substituted radicals and monomers. The variation in the heat of reaction is expressed in terms of the resonance energies of the reacting radicals and molecules. Another important factor is the energy of repulsion between the reacting centers, and this energy is affected by (a) the charge distribution on the reacting centers and (b) the steric effect of substituent groups. The effect of substituents on the charge distribution is discussed in terms of the molecular orbital method, an attempt being made to distinguish between the influence on the π electrons of the inductive and mesomeric effect of substituents.
    Additional Material: 4 Ill.
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  • 86
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyvinyl alcohol prepared by hydrolyzing polymerized vinyl acetate is partially degraded within a few minutes by reagents known to attack 1,2-glycol structures. The degree of degradation is limited, however, the final molecular weights of the degraded products being in the range of 3700 to 6500 (viscosity averages). The extent of degradation seems to depend solely on the temperature at which the vinyl acetate was polymerized. Mole percentages (based on the structural unit —CH2—CHOH—) of 1,2-glycol structures, corresponding to head-to-head unit arrangements, have been computed from the degree of degradation with periodic acid. They increase from about 1.23% for polymerization at 25°C. to 1.95% at 110°C. The occurrence of head-to-head structures is attributed to occasional “abnormal” addition of monomer in the chain-growth phase of the polymerization. The activation energy for the abnormal addition reaction is 1250 calories higher than for the normal (preferred) addition; the steric factor for the abnormal addition is about one-tenth that for the normal addition.
    Additional Material: 6 Ill.
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  • 87
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    Journal of Polymer Science 3 (1948), S. 895-897 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 88
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    Journal of Polymer Science 3 (1948), S. 900-900 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 89
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    Die Makromolekulare Chemie 1 (1948), S. 199-208 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molekularer Sauerstoff spielt bei der Polymerisation ungesättigter Verbindungen eine eigenartige Doppelrolle. Er bildet mit diesen ungesättigten Verbindungen Peroxyde, die wie andere Peroxyde polymerisationsbeschleunigend wirken. Er lagert sich aber auch an radikalartige Polymerisationskeime oder an wachsende Ketten an und wirkt dadurch polymerisationshemmend. Die Autoxydation der ungesättigten Verbindungen und die Hemmungsreaktion konkurrieren miteinander und bestimmen das Reaktionsgeschehen.
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  • 90
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    Die Makromolekulare Chemie 1 (1948), S. 209-228 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Polymerisation ungesättigter Verbindungen mit Hilfe von Peroxyden wird durch Zusatz von Reduktionsmitteln, die die Polymerisation nicht hemmen, beschleunigt. Polymerisationen werden durch Redoxreaktionen ausgelöst. Es werden einige wirksame Redoxsysteme für die Polymerisation in Emulsion, in Substanz und in Lösung behandelt. Zur Deutung der Redoxbeschleunigung wird die Bildung freier Radikale bei der Redoxreaktion angenommen. Diese Radikale sind die Reaktionskeime des Kettenwachstums.
    Additional Material: 9 Ill.
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  • 91
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    Die Makromolekulare Chemie 1 (1948), S. 229-248 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Der Primärakt der peroxydischen Polymerisation ungesättigter Verbindungen besteht wahrscheinlich in der Bildung freier Radikale, die bei der Umsetzung des Peroxydes mit der ungesättigten Verbindung oder einem anderen H-Donator entstehen. Diese Anschauung steht in übereinstimmung mit derjenigen über die Polymerisation mit Hilfe von Redoxsystemen; sie kann ferner den Einbau der Peroxyde in die Polymerisatketten erklären. Es werden die Hypothese der Bildung „aktiven“ Sauerstoffes, der Peroxydzerfall nach Gelissen, Böeseken und Hermans, Wieland, Hey und Waters, ferner die Anschauungen von Breitenbach über die peroxydische Polymerisation diskutiert.
    Additional Material: 1 Ill.
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  • 92
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    Die Makromolekulare Chemie 1 (1948), S. 169-198 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Polymerisation des Methacrylsäuremethylesters mit Benzoylperoxyd erfolgt nach einer Periode stationärer Geschwindigkeit, beginnend bei etwa 20 bis 25% Umsatz mit starker Beschleunigung (explosionsartiger Polymerisationsverlauf nach G. V. Schulz und Blaschke). Ursache für diese Erscheinungen ist das im Monomeren gelöste Polymerisat, das die Diffusion der wachsenden Molekülketten hemmt und dadurch den Abbruch der Kettenreaktion durch gegenseitige Absättigung zweiér wachsender Molekülketten verhindert, während die Diffusion des Monomeren nicht gestört wird. Infolgedessen nimmt die Reaktionsgeschwindigkeit und gleichzeitig der Polymerisationsgrad der entstehenden Makromoleküle zu. Hemmung der Diffusion und damit beschleunigte Polymerisation wird auch durch andere im Monomeren gelöste, hochmolekulare Substanzen oder durch Festlegung der Lage der wachsenden Makromoleküle durch Vernetzung mit Verbindungen mit zwei polymerisationsfähigen Doppelbindungen erreicht. Nach diesem Schema laufen Block-und Perlpolymerisation ab.Bei der Polymerisation im guten Lösungsmittel für das Polymerisat wird die Diffusion für die wachsenden Molekülketten durch die Anwesenheit des Lösungsmittels aufrechterhalten, es erfolgt keine explosionsartige Polymerisation. In schlechten Lösungsmitteln bzw. Fällungsmitteln für das Polymerisat wird die Diffusion besonders stark behindert, da schon die wachsenden Molekülketten ausflocken. Infolgedessen ist die Explosion heftiger und der Polymerisationsgrad höher als bei Polymerisation des unverdünnten Monomeren. Während Block- und Perlpolymerisate, die in zwei unterscheidbaren Phasen, also mit explosionsartigem Verlauf, entstanden sind, zwei Maxima der Massenverteilung zeigen, wird bei vor der Explosion abgetrenntem Polymerisat und bei Lösungspolymerisaten in guten Lösungsmitteln nur ein Maximum gefunden.Die Emulsionspolymerisation erfolgt in zwei Phasen, zuerst über die wässrige Lösung, wobei rasche Polymerisation erfolgt, weil Wasser ein Fällungsmittel für das Polymerisat ist, dann auch in den in Wasser suspendierten Polymerisatteilchen, in denen sich Monomeres löst. Diese beiden Phasen und die Unterschiede zur Perlpolymerisation lassen sich durch Versuche mit verschiedenen wasser - bzw. organisch löslichen Stabilisatoren und Beschleunigern nachweisen. Wesentlich ist der Einfluß des Rührens bei der Emulsionspolymerisation, veranlaßt durch Sauerstoffhemmung.Der gefundene Reaktionsmechanismus hat auch für andere Polymerisationen mehr oder weniger Bedeutung, eine Verallgemeinerung ist jedoch unmöglich.
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  • 93
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    Die Makromolekulare Chemie 2 (1948), S. 5-36 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Durch Vergleich osmotischer Messungen mit Bestimmungen der Sedimentationskonstante in der Ultrazentrifuge s und der Diffusionskonstante D wird versucht, die Molekulargewichtsbestimmung mit der Ultrazentrifuge so zu leiten, daß man bei polymolekularen Stoffen mit möglichst guter Näherung das mittlere Molekulargewicht (Zahlendurchschnitt) erhält. Es werden die Methoden diskutiert, in welcher Weise die Durchschnittswertbildung für s und D zweckmäßig ausgeführt wird, und wie aus den bei endlichen Konzentrationen erhaltenen s- und D-Werten deren Grenzwert für die Konzentration 0 erhalten wird. Verwendet man für s den Wert des Massenmaximums und berechnet D nach der Halbwertsbreitenmethode, so bekommt man Molekulargewichte, welche bei nicht zu uneinheitlichen Polystyrolen nahe am osmotisch bestimmten wahren Mittelwert liegen.Die so bestimmten Molekulargewichte werden mit den nach der Staudingerschen Methode erhaltenen verglichen. Ferner wird die Abhängigkeit des Fikentscherschen k-Wertes vom Polymerisationsgrad untersucht. Annähernde Molekulargewichte lassen sich für Polystyrole nach beiden viskosimetrischen Methoden ermitteln, da die Staudingersche Viskositätszahl dem Molekulargewicht und der Fikentschersche k-Wert der Wurzel aus dem Molekulargewicht annähernd proportional sind. Die bei Polystyrolen auftretenden Ungenauigkeiten sind teils durch die Verzweigung, teils durch die wechselnde Polymolekularität der verschiedenen Präparate bedingt.Es wird versucht, aus den gemessenen Reibungsgrößen Aufschluß über die physikalische Gestalt der Moleküle zu erhalten. Für die Abhängigkeit der Diffusionskonstante, der Sedimentationskonstante und der Viskositätszahl vom Molekulargewicht ergeben sich in Methyl-Isopropylketon als Lösungsmittel dieGesetzmäßigkeiten, welche W. Kuhn für undurchspülte Knäuel voraussagt. In Toluol geßen die Gesetzmäßigkeiten durchspülter Knäuel. Dem Versuch, aus diesen Daten den Knäuelungsgrad bzw. das Volumen der Knäuel zu berechnen, stehen noch große Schwierigkeiten entgegen. Es wird darauf hingewiesen, daß zur Ermittelung der Gestalt der Moleküle noch andere makroskopische Eigenschaften herangezogen werden müssen.
    Additional Material: 9 Ill.
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  • 94
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 1 (1948), S. 249-268 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Polymerisation ungesättigter Verbindungen in Substanz, Lösung und Emulsion mit Hilfe von Oxydationsmitteln (Peroxyden) und Reduktionsmitteln (Redoxsystemen) wird durch Zusatz von kationischem 2- oder 3-wertigem Eisen stark beschleunigt. Die Erklärung wird in einer übertragungskatalyse der Redoxreaktion durch das reversible Fe-Fe-Redoxsystem gesehen, wobei Fe monovalent oxydiert wird und Peracylradikale gebildet werden; Fe wird durch das Reduktionsmittel reduziert. Die Polymerisation in Substanz und in Lösung mit Hilfe von Redoxsystemen wird außer durch Eisenverbindungen auch durch andere lösliche Metallverbindungen, insbesondere solchen der Schwermetalle, beschleunigt. Es können „Wirksamkeitsreihen“ aufgestellt werden. Die Deutung der Metallredoxkatalyse ist schwieriger als diejenige der Eisenredoxkatalyse, da die Annahme eines Wertigkeitswechsels der Metalle nicht in allen Fällen möglich ist.
    Additional Material: 3 Ill.
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  • 95
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 37-47 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Wie das Elektronenmikroskop zeigt, gliedert sich die 640 Å große Strukturperiode des Kollagens in einen schattendichten D-Teil und einen durchstrahlbaren H-Teil. Der D-Teil ist nicht gleichmäßig gebaut, sondern läßt stets eine Aufteilung erkennen, die nach Einwirkung von Schwermetallen deutlicher sichtbar wird. Im D-Teil findet man entweder zwei schattendichte δ-Scheiben und ein helles Zwischenstück oder vier schattendichte δ-Lamellen und drei helle Zwischenstücke. Das Scheibenstadium ist der Normalzustand. Das Lamellenstadium fand sich physiologischerweise in untrainierten Kollagenfibrillen jugendlicher Individuen und unter pathologischen Bedingungen bei der trockenen Gewebsnekrose und bei der Myxomviruserkrankung des Kaninchens. Unter bestimmten Bedingungen kann das Scheibenstadium künstlich in das Lamellenstadium übergeführt werden, indem sich bei geringer Schrumpfung der Kollagenfibrille die δ-Scheiben in je zwei δ-Lamellen spalten. Es wird die Vermutung ausgesprochen, daß im Bereich der δ-Scheiben andere Bindungsformen der Kollagenmoleküle vorliegen als im Bereich der übrigen Abschnitte der Strukturperiode. Das Lamellenstadium wird als Symptom der Strukturschwäche aufgefaßt.
    Additional Material: 3 Ill.
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  • 96
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molekularer Sauerstoff kann unter geeigneten Bedingungen in Redox- und Metallredoxsystemen, welche die Polymerisation ungesättigter Verbindungen auslösen, die Rolle des Oxydationsmittels übernehmen. Die Autoxydation des Reduktionsmittels löst also die Polymerisation aus (Autoxkatalyse). Durch Zusatz von kationischem 2- oder 3-wertigem Eisen tritt eine starke Beschleunigung der Polymerisation ein (Eisenautoxkatalyse). Zur Deutung wird angenommen, daß bei der Autoxydation der H-Donatoren Radikale entstehen, die polymerisationsauslösend wirken. In kleinen Konzentrationen wirkt molekularer Sauerstoff in Verbindung mit autoxydabeln Reduktionsmitteln stark polymerisationsbeschleunigend, in hohen Konzentrationen aber polymerisationshemmend, da er dann die wachsenden Ketten abbricht.
    Additional Material: 5 Ill.
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  • 97
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 66-76 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es wird die Mikromorphologie der Proteine des kontraktilen Systems der Kaninchen-Muskelfibrillen untersucht. Das Sphärokolloid G-Actin und das Linearkolloid F-Actin sowie der Übergang des einen in das andere werden dargestellt, weiter die Aggregate des Myosins sowie der Habitus des Actomyosins. Endlich wird die Struktur der Filamente der frischen Muskelfibrille sowie die einer getrockneten gezeigt, aus der das Myosin extrahiert ist.
    Additional Material: 15 Ill.
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  • 98
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 63-65 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mit Hilfe von molekularem Sauerstoff oder Peroxyden und reduzierend wirkenden Zuckern (z. B. Dioxyaceton) in Verbindung mit kationischem, 2- oder 3-wertigem Eisen oder anderen Übertragungskatalysatoren können Polymerisationen in sehr kurzen Zeiten durchgeführt werden. Es wird die Möglichkeit der Polymerisation von Isopren zu Kautschuk unter biologischen Bedingungen in der Pflanze diskutiert.
    Type of Medium: Electronic Resource
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  • 99
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 77-87 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Essigsäure wurde aus Rübenpektin isoliert und als Acetanilid nachgewiesen. Durch Verseifung von Pektin mit Alkali und Säuren bei verschiedenen Temperaturen wurde gezeigt, daß die Entstehung von Essigsäure  -  im Gegensatz zu der auch bei der Verseifung gebildeten Ameisensäure  -  nicht auf einen oxydativen Abbau zurückzuführen ist; wie kinetische Messungen der Verseifungsreaktion erwiesen, muß das Vorliegen einer Acetylgruppe angenommen werden. Die Frage, ob die Acetylgruppe der Galakturonsäure oder den Begleistoffen Araban-Galaktan des Pektins zugehört, wurde dahin entschieden, daß sowohl die Pektinmoleküle wie die Begleitstoffe Essigsäure enthalten, da der Essigsäuregehalt bei steigendem Galakturonsäuregehalt eines Präparates weder zu- noch abnimmt. Zur Bestimmung der Essigsäure in Pektin wurde eine einfache und rasch ausführbare Methode angegeben.
    Additional Material: 3 Ill.
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  • 100
    Electronic Resource
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 88-108 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Glykogene verschiedener Herkunft zeichnen sich durch folgende konstitutionellen Eigentümlichkeiten aus:Das Muskelglykogen verschiedener Tierarten besitzt ein durchschnittliches Molekulargewicht von etwa 1,5 Millionen. Es ist einheitlich. Es enthält chemisch gebundene Phosphorsäure.Das Molekulargewicht des Leberglykogens verschiedener Tierarten ist um so größer, je glykogenreicher die Leber ist. Das Leberglykogen ist uneinheitlich. Die im Leberglykogen gefundenen Moleküle mit einem Molekulargewicht von etwa 23 Millionen sind die größten bisher bekannten chemisch definierten Moleküle. Das Leberglykogen enthält keine chemisch gebundene Phosphorsäure.Das Herzglykogen vom Meerschweinchen und von der Katze hat ein Molekulargewicht von etwa 2, beziehungsweise 1 Million. Es ist nicht einheitlich.Die spezifischen Drehungen aller untersuchten Glykogene stimmen innerhalb der Fehlergrenze der Messungen miteinander überein. Der bisher anerkannte Wert von 196,5° konnte bestätigt werden.
    Additional Material: 6 Tab.
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