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  • 2000-2004
  • 1985-1989
  • 1945-1949  (148)
  • 1948  (148)
  • Polymer and Materials Science  (148)
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  • 2000-2004
  • 1985-1989
  • 1945-1949  (148)
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Keywords
  • 101
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 113-119 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mit der von Sörensen und Haugaard zuerst angewandten Methode der Orzin-Reaktion wurde die Identifizierung der Kohlehydrate im normalen Tabakmosaikvirusprotein. in dessen Strahlenmutationsstämmen TM21, TM44, Ra88 sowie TM96 und im Aucubamosaikvirusprotein mit der Ribose der Hefenukleinsäure durchgeführt. Es liegt in allen Fällen das gleiche Kohlehydrat vor. Dieses Resultat wird in der Diskussion in Einklang gebracht mit den Annahmen von Kausche und Stubbe über die Entstehung der Strahlenmutanten sowie mit der Auffassung Casperssons über die Rolle der Nukleinsäure bei der Eiweißvermehrung.
    Additional Material: 2 Ill.
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  • 102
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 120-126 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Eine quantitative Aufteilung der Aminosäuren in gereinigtem Clupein und Salmine wurde mit Methoden der chromatographischen Adsorption erreicht. Es ergab sich ein molekulares Verhältnis von 10 Arginin : 2 Serin : 1 Valin : 1 Alanin : 1 Prolin für das Clupein und von 12 Arginin : 3 Serin : 1 Valin : 2 Prolin für das Salmin.
    Additional Material: 2 Tab.
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  • 103
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es werden die Reaktionsmöglichkeiten peroxydischer Katalysatoren bei der Polymerisation ungesättigter Verbindungen erörtert. Der Einbau kann prinzipiell beim Primärakt, bei der Wachstumsreaktion, beim Kettenabbruch oder bei einer Sekundärreaktion erfolgen. Beim Styrol erfolgt der Einbau von p-Brombenzoylperoxyd beim Primärakt. Die Bromatomzahl (Anzahl der eingebauten Bromatome pro Makromolekül) ist in geringem Umfange von der Peroxydkonzentration bei der Polymerisation abhängig. so daß man mit einer Nebenreaktion rechnen muß. Während Polystyrolmakromoleküle im Durchschnitt 4 Bromatome enthalten, ergeben sich bei der Polymerisation des Methacrylsäuremethylesters bei 50°C mit p-Brombenzoylperoxyd im Durchschnitt nur etwa 2 gekennzeichnete Endgruppen. Auch Vinylacetat zeigt bei der Polymerisation einen Einbau des peroxydischen Katalysators: doch ist die Bromatomzahl von der angewandten Peroxydkonzentration stark abhängig. Sie steigt mit wachsender Katalysatorkonzentration an; dieser Anstieg wird durch eine Sekundärreaktion oder eine Übertragungsreaktion verursacht.Der Einbau von p-Brombenzoylperoxyd konnte auch bei Polymethacrylnitril wahrscheinlich gemacht werden. m-Nitrobenzoylperoxyd ist als gekennzeichneter Katalysator für die Polymerisation des Vinylchlorids ungeeignet, da die Nitrogruppe die katalytische Wirkung des Peroxydes aufhebt.
    Additional Material: 7 Ill.
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  • 104
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 172-175 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Zur chemischen Molekulargewichtsbestimmung an Polyaminocapronsäuren ergab sich die Aufgabe, den Carboxylgehalt dieser hochmolekularen ω Aminocarbosäuren durch Titration mit großer Genauigkeit zu bestimmen. Diese Ziel wur nach Auffinden eines geeigneten Indikators durch Anwendung der photometrisch Titration erreicht. Das Verfahren erscheint geeignet, ganz allgemein die Titratioschwacher Säuren in Alkohol-Wassergemischen mit größerer Genauigkeit za ermöglichen.
    Additional Material: 1 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 143-171 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1. Vanadinpentoxyd-GelAn Hand der elektronenoptischen Aufnahmen können wir uns ein anschauliches Bild vom Aufbau retikular disperser Kolloide machen. Es zeigt sich, daß die Gele durch ein zusammenhängendes Micellargerüst charakterisiert sind, dessen Maschen offen miteinander kommunizieren. Die Verzweigungen und Verschmelzungen auseinanderweichender und zusammenlaufender Stränge sind deutlich sichtbar.2. SchleimIm Epidermisschleim der Quittensamen werden feine Stränge von ca. 100 Ä Dicke nachgewiesen. Aus Analogie zu andern Samenschleimen, die Cellulosefäden von mikroskopischen Dimensionen enthalten (z. B. Cobaea scandens) darf geschlossen werden, daß diese Stränge die chemisch nachgewiesene Cellulose des Quittenschleims vorstellen.3. BakteriencelluloseMit Hilfe Cellulose aufbauender Bakterien konnte gezeigt werden, daß frisch gebildete Cellulose nicht sogleich in kristallisierter Form auftritt. Bei B. xylinoides erscheint sie zuerst in Form eines im El.-Mikr. strukturlosen Häutchens auf der Oberfläche der Kulturflüssigkeit. Dieser Film ist jedoch nicht stabil, sondern beginnt in dünnste Fäden auszukristallisieren.4. CellulosefasernEs wird über eine neue, von Heuberger (Eidg. Materialprüfungsanstalt St. Gallen) entwickelte Methodik zur schonenden Zerfaserung von Cellulosefasern mittels Ultraschallwellen berichtet. Die longitudinalen Schwingungen, die durch einen geeigneten Schallgeber in einer Flüssigkeit erzeugt werden, spalten die Faser ohne irgendwelche Querbrüche in allerfeinste Stränge bis 60 Å Dicke auf, die mit den Micellarsträngen von Frey-Wyßling identifiziert werden.
    Additional Material: 22 Ill.
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  • 106
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 201-212 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
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  • 107
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 187-200 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Streuintensität gelöster Teilchen, die nicht mehr vernachlässigbar klein gegen die Wellenlänge sind, zeigt Abweichungen von der Rayleighschen Gleichung. Auf Grund von Gleichungen, die Neugebauer kürzlich aufgestellt hat, kann man aus der Abhängigkeit der Streuintensität von der Wellenlänge die räumliche Größe der Teilchen berechnen. Ferner gewinnt man aus solchen Messungen einen Korrekturfaktor für die Rayleighsche Gleichung, so daß auch das Molekulargewicht der Teilchen berechnet werden kann.An einer Fraktion von Polymethacrylsäureester wird die Streuintensität bei 3 Wellenlängen gemessen. Hieraus ergibt sich ein Molekulargewicht von 1,7 · 106, welches mit dem viskosimetrisch (auf Grund osmometrischer Vergleichsmessungen) bestimmten Molekulargewicht annähernd übereinstimmt. Die Länge des ausgestreckten Moleküls wäre ca. 40 000 Å, während die Streulichtmessung 1 700 Å ergibt. Hieraus ist zu schließen. daß die Moleküle des Polymethacrylsäureesters ziemlich stark geknäuelt sind.
    Additional Material: 1 Ill.
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  • 108
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 176-186 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reine Kettenübertragung hat nur dann einen meßbaren Einfluß auf die Polymerisationsgeschwindigkeit, wenn der mittlere Polymerisationsgrad des gebildeten Polymeren klein ist (Größenordnung 10). Dies gilt auch dann, wenn die Bildung neuer Polymerisationskeime durch Radikale der übertragenden Substanz verhältnismäßig langsam erfolgt. Die starke Abnahme der Polymerisationsgeschwindigkeit bei Vinylacetat mit zunehmender Verdünnung durch Benzol. Toluol und Chlorbenzol kann gedeutet werden durch eine Kettenübertragung, bei der gleichzeitig eine Vermehrung des Kettenabbruchs durch die aus dem Lösungsmittel gebildeten Radikale erfolgt.
    Additional Material: 1 Tab.
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  • 109
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 217-226 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Skelettsubstanzen von 15 Laub- und 5 Nadelhölzern wurden fraktionierl. Es ergaben sich folgende Gruppen von Fraktionen: niedermolekulare Anteile mit DP (Durchsehnittspolymerisationsgrad) bis 150, die 13% - 30% der Hölzer umfaßten. hochmolekulare Anteile mit DP über 1 000 in einer Menge von 40% - 55% des betreffenden Holzes und in einigen Fällen auch Zwischenfraktionen mit DP 150 - 1 000, die höchstens 14% der Holzsubstanz ausmachten. Wie Untersuchungen von Proben der gleichen Holzart aber verschiedener Herkunft zeigten, sind die gefundenen Unterschiede als Art-Merkmale des betreffenden Holzes anzusehen.Die niedermolekularen Fraktionen bestehen aus den Holzpolyosen, d. h. nieder-polymeren Xylanen, Mannanen und Polyglucuronsäuren. Doch enthalten sie auch Glucane, die als solche oder als Mischketten aus Glucose- und Glucuronsäure-gruppen vorliegen.Die Holzcellulosen (Fraktionen mit DP über 1 000) enthielten 1,5% - 3% Fremdgruppen in Form von Xylose- und Glucuronsäureresten. Der Einbau dieser Gruppen in die Cellulose-Moleküle ergibt sich aus der Tatsache, daß sie weder durch alkalische Behandlung noch durch Teilhydrolyse des Holzes - unter Bedingungen, die für die Hydrolyse der Holzpolyosen genügen - aus dem Cellulosemolekül herausgelöst werden können. Mannan-Anteile, die bei der Fraktionierung zunächst in den hochmolekularen Fraktionen der Nadelholzskelettsubstanzen verblieben, sind gegen Hydrolyse nicht beständig. Die Holzcellulose-Anteile sind nicht einheitlich sondern bestehen aus mehreren Fraktionen. Mit steigendem DP werden die Fremdgruppengehalte der Fraktionen geringer.Die Höhe des Cellulose-Anteils der Hölzer bestimmt die Ausbeute und ihr Fremdgruppengehalt die Reinheit der aus den Hölzern zu gewinnenden Zellstoffe.
    Additional Material: 5 Tab.
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  • 110
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 227-247 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Die Grundlagen der statistischen Theorie makromolekularer Lösungen werden entwickelt. Das Problem der athermischen Lösung wird mittels der Methode der virtuellen Moleküle behandelt und insbesondere der Störungseffekt eingehend erörtert. Die allgemeinen Formeln werden auf die Spezialfälle der Kugelmoleküle, der starren gestreckten und der beweglichen Fadenmoleküle angewandt und die Ergebnisse diskutiert. Die statistische Theorie der Solvatation wird in ihren Grundzügen skizziert, und es werden einige Ergebnisse besprochen.
    Additional Material: 6 Ill.
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  • 111
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es wird eine elektrochemische Methode  -  die potentiometrische Titration  -  zur Molekülgrößenbestimmung der Polyamide theoretisch begründet und experimentell ausgearbeitet. Das beschriebene Verfahren ist bis zum Polymerisationsgrad 50 anwendbar, jedoch dürfte durch Verfeinerung der Arbeitsweise diese Grenze bis an den Polymerisationsgrad 80 heraufgeschoben werden können. Neben der Molekülgröße läßt sich auch die Dissoziationskonstante der Amidgruppe ermitteln, deren Kenntnis für das Verständnis der Kolloidstruktur der Polyamide von Wichtigkeit ist.
    Additional Material: 7 Ill.
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  • 112
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 10-15 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Expreiments have been carried out on the benzoyl-peroxide catalyzed polymerization of methyl isopropenyl ketone at 25 and 40°C. in cyclohexane, a solvent which dissolves the monomer but causes the polymer to be precipitated. It is shown that in solutions of suitable concentration (40-80%) the effect of the cyclohexane is to increase both the rate of polymerization and the intrinsic viscosity of the resulting polymer. The significance of these observations and of other recent experimental work is discussed.
    Additional Material: 3 Ill.
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  • 113
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Five twelve-carbon mercaptans of definite structure are prepared and used to demonstrate that the rate of diffusion of mercaptan regulators in emulsion polymerization varies inversely with the length of the longest straight chain of the mercaptan structure (including the sulfur). In a given class of mercaptans (primary, secondary, or tertiary) the mercaptan consumption during polymerization varies directly with the diffusion rate. Solution viscosities of the resulting polymers are in accord with these findings.
    Additional Material: 3 Tab.
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  • 114
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of plasticizer action has been discussed for linear, slightly and highly crosslinked polymers. The important factors considered are the flexibility of the polymer chain, the polar interaction of groups along the chain, the masking of these interactions by plasticizer molecules, and the importance of the relative shape of polymer unit and plasticizer in the effectiveness of separating the chains. For nonpolar polymers, without secondary valence cross links, the plasticization is largely an entropy effect since no secondary valence bonds are broken or formed.
    Additional Material: 8 Ill.
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  • 115
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-4-vinylpyridine was precipitated from a toluene solution of the monomer after addition of benzoyl Peroxide. The sample used in these experiments had a molecular weight of 77,000, (DP 730) as determined by osmotic pressure in alcohol solution, and an intrinsic viscosity of 0.36 in this solvent. The hydrochloride is water soluble and behaves like the salt of an extremely weak base with an over-all average base dissociation constant of 0.011 × 10-9, about one thousandth that of 4-ethylpyridine. The decrease in apparent base strength is ascribed to the chain structure which produces high local concentrations of pyridine groups, independent of the total concentration. By addition of butyl bromide to the polymer in nitromethane, a long chain quaternary ammonium salt is formed which is also water soluble. Its conductance is not sensitive to concentration down to about 0.003 N, after which the conductance rises sharply with further dilution. Dissociation, calculated by the classical Arrhenius method, indicates that a minimum of about 20% of the bromide ions are free, the remainder being associated by Coulomb attraction to the chainlike positive ion. As the dielectric constant of the solvent is decreased by addition of ethanol, the relative amount of free bromide ions decreases. The viscosity of the polyelectrolyte in aqueous or alcoholic solution, when plotted in the conventional way (ηsp/c versus c), approaches infinity at zero concentration instead of approaching a limiting constant linearly. A plot of $ {{\eta _{sp} } \mathord{\left/ {\vphantom {{\eta _{sp} } {\sqrt c }}} \right. \kern-\nulldelimiterspace} {\sqrt c }} $ versus $ \sqrt c $ is, however, linear; this behavior is characteristic of strong electrolytes. The coefficient of the square root term in concentration for the polymer is larger, by orders of magnitude, than that for ordinary electrolytes. The coefficient of the linear term in the square root function is about equal to the intrinsic viscosity of the parent polymer.
    Additional Material: 7 Ill.
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  • 116
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 173-180 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The swelling of vulcanized copolymers from dienes and acrylonitrile is measured in various organic liquids. Equilibria change gradually as a function of nitrile concentration. The occurrence of ideal, regular and irregular systems is discussed, and intermolecular attraction is interpreted in terms of Langmuir's theory of independent surface action.
    Additional Material: 8 Ill.
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  • 117
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cobalt complex compounds exhibited varying degrees of activation and retardation in butadiene-styrene-soap emulsion polymerization systems at 20-50°C. An accompanying effect was the wasting of modifier, particularly by large concentrations of activator. The most active complexes for use with dodecyl mercaptan were those in which the cobalt was coordinated with two or more negative groups other than thiocyanate, and in which the neutral coordinated groups were not ethylenediamine.
    Additional Material: 17 Tab.
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  • 118
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 195-215 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffraction of x-rays at small angles occurs in the form of sharp interferences (discontinuous) or as diffuse scattering (continuous). The first effect is observed mostly in crystallized proteins and in protein fibers. New measurements on collagen were obtained by the author in collaboration with Sekora, and independently by Bear. Using these data, an attempt has been made to establish a connection between the orders of the intense reflections belonging to the giant period of 642 Å. along the fiber axis and the frequency of the amino acid residues (frequency is defined as the number of amino acid residues of a particular kind among the total 220 residues which constitute the basic period of 642 Å. along the fiber axis). With the exception of the most abundant amino acids, glycine and proline, it is possible to assign to each frequency a corresponding reflection, and vice versa. This indicates a high degree of regularity in the arrangement of these amino acid residues. But the relationships are apparently more complex than would be expected from the Bergmann-Niemann rule. For example, the frequencies of 11 and 20 (corresponding to an identical residue at each 220/11 or 20th location or at each 220/20 or 11th location, respectively) appear to play a role. Fundamentally, however, we arrive at a picture in accordance with the comprehensive investigations and results of Astbury. It has not yet been possible to arrive at a detailed structure.In the theory of diffuse low-angle scattering, it is necessary to distinguish between densely packed systems and dilute systems. For the latter case, molecular scattering is computed in accordance with Debye's theory of scattering. It is shown how size factor and form factor may be separated. Both of these properties can be approximated without making previous assumptions, though the accuracy of the form factor determination can be improved appreciably if the particle weight is known. Preliminary trial measurements on solutions of edestin, tobacco mosaic virus, and hemocyanin are in agreement for the first two substances mentioned. The measurements on insulin indicate associated particles that deviate strongly from spherical shape (however, these measurements were made at an earlier date and require checking). Those on hemocyanin indicate an association similar to a string of pearls, a result which probably explains the contradiction of the substance appearing as spherical particles under the electron microscope, while exhibiting flow birefringence when in solution. When this method is developed further it will undoubtedly become a valuable tool for the determination of form and size of polymer molecules and other colloidal particles.
    Additional Material: 15 Ill.
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  • 119
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Apparatus and technique have been described for the polymerization of 1,3-butadiene in the vapor phase with sodium as catalyst. Research grade butadiene or that obtained from alcohol is necessary for production of high molecular weight polymers by this method. Unmodified polymerizations with increased sodium surface go faster and produce polymers of lower gel content and inherent viscosity. Increase in polymerization temperature reduces the rate, gel content, and inherent viscosity. The chemical structure of the modifier seems to be the predominant factor in its efficiency within a concentration range of 0.1 to 1.0 %. Ethyl chloride is the most powerful modifier of those examined, followed in order by dimethylamine, acetaldehyde, and acetoue. Gelfree polymers with average inherent viscosities of the whole sol between 0.4 and 4.6 were vulcanized and evaluated. The weight distribution was found to be rather narrow for the low viscosity polymers but to become broader as the average inherent viscosity of the polymer increased. Optimum processing and tensile properties were obtained on the polymers of medium viscosity. The dynamic properties of the vulcanizates improve with increase in average inherent viscosity of the raw polymer; the ethyl chloride modified polymer is exceptionally good. The physical properties of the vulcanizate of a blend of equal parts of five polymers of inherent viscosity 1.0 to 4.6 were near those of the lowest molecular weight polymer.
    Additional Material: 2 Ill.
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  • 120
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the polymerization of ally1 methacrylate in the presence of benzoyl peroxide at 75°C., gelation occurs after about 6% reaction. By carrying out the polymerization a t 1°C. to 25°C. in the presence of biacetyl or benzoyl peroxide and photoflood or ultraviolet radiation, we have been able to postpone gelation until 19 to 39% reaction. In the presence of biacetyl the extent of reaction a t the gel point is increased as the temperature is lowered and as the light intensity is raised.Biacetyl is activated by radiation in the 400-460 mμ region; benzoyl peroxide is activated by radiation in the 350-380 mμ region.Hydrolysis and bromination of the soluble polymer did not indicate any marked difference in the composition of the samples prepared at 75°C. and 15°C. The soluble polymer which is prepared at 75°C. appears to have an intrinsic viscosity which may be three to twenty times as great as that of the polymer which is prepared at 1-25°C.The polymerization of methyl methacrylate and allyl acetate under the two sets of conditions indicated that the reaction of the methacrylate was affected more than that of the allyl compound by the change in conditions. The copolymerization of methyl methacrylate and allyl chloroacetate indicated that somewhat more allyl monomer was incorporated into the copolymer at the lower temperature than a t the higher temperature.The increased extent of reaction at the gel point at the lower temperatures appears to be due almost entirely to diminished molecular weights. The decrease in molecular weight a t low temperatures is probably due to the decreased rate of chain growth, the rate of initiation remaining high because of irradiation, and the rate of termination being little dected because of its low activation energy. The effects of temperature on the composition of the copolymer, and of molecular weight on the point of gelation, are discussed briefly.
    Additional Material: 3 Ill.
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  • 121
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rapid low-temperature butadiene-styrene emulsion copolymerization may be effected by a redox-activated system composed of carbonatotetramminocobaltic nitrate and dodecyl mercaptan. This system reaches 75% conversion of monomer to polymer in 0.8 hour at 50°C., 2.8 hours at 30°C., or 27 hours at 0°C., and is thus about fifteen times as fast as standard recipes now in use. The modifying effect of dodecyl mercaptan improves as the polymerization temperature is lowered, producing loosely cross-linked polymers at 30°C. and well-modified polymers at 0°C.
    Additional Material: 6 Ill.
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  • 122
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 438-443 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adiabatic technique of making kinetic measurements has been applied to published time--temperature data concerning the vulcanization of Buna S with 6% sulfur. The kinetic parameters of the rate-determining step are calculated within stated limits of accuracy; the rate-determining step is thereby identified as the reaction S8 (ring) → S8 (chain biradical) which has been speculatively advanced as the first step in vulcanization by some investigators.
    Additional Material: 3 Ill.
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  • 123
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 462-463 
    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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  • 124
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A refractometric method for determination of second-order transition temperatures of polymers has been extended to include a series of polymers for which the transition occurs between 0° and 75°C. Refractive index data within ±30° to 50°C. of the transition temperature are given for some acrylate, methacrylate, vinyl chloride, vinylidene chloride, and styrene polymers and copolymers. These data show discontinuities which locate the second-order transition temperatures for these polymers. Deviation from the linear relation near Tm has been related to a time effect.
    Additional Material: 4 Ill.
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  • 125
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 481-486 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The attempt to replace chlorine in polyphosphonitrilic chloride with alkoxyl groups is successful except that oxygen rather than alkoxyl substitution occurs to some extent. The amount of oxygen substitution and the extent of degradation are minimized if the polyphosphonitrilic chloride is swollen prior to alcoholysis. The substituted product is insoluble until treated with boiling tetrachloroethane. The final products, the esters, are very tacky when pure but can be incorporated with other polymers to give desirable products.
    Additional Material: 5 Tab.
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  • 126
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new method is investigated to determine by means of potentiometric titration the degree of ripening of viscose. It is found that when the e.m.f. of a characteristic inflection in the potentiometric titration curve is plotted against a measure of the degree of viscose ripening a sharp minimum occurs at a point corresponding to the optimal degree of ripening. Moreover, evidence is offered to indicate the formation of sodium dithiocarbonate in viscose during ripening. This last fact leads to a reasonable postulation of the complete scheme of reactions taking place in a ripening viscose.
    Additional Material: 7 Ill.
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  • 127
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: n-Octyl mercaptan has been found to be a better modifier for emulsion copolymerization of butadiene and styrene at 110° than is either n-butyl mercaptan or n-dodecyl mercaptan. Physical test data on vulcanized copolymers modified with n-octyl mercaptan are presented.
    Additional Material: 3 Tab.
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  • 128
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 376-388 
    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 complete calculation of the deviation of the quadratic mean between the ends of a molecular chain has been made in the case of freely rotating aliphatic chains. Partial solutions have been proposed in the case of an aliphatic chain with steric hindrances or interactions between the groups. The purpose of this work is to present a method of general calculation which can be applied to certain special examples. (Aliphatic, cellulose, polypeptide chains as well as substances of the natural rubber type.)
    Notes: Le calcul de l'écart quadratique moyen entre les extrémités d'une chaîne moléculaire a été fait de façon complète dans le cas de la chaîne aliphatique à rotations libres. Des solutions partielles ont été proposées dans le cas de la chaîne aliphatique avec empěchements stériques ou intéractions entre les chaînons. Le but du présent travail est de donner une méthode de calcul général que l'on applique aux exemples particuliers les plus usuels. (Chaînes aliphatiques, cellulosiques, polypeptidiques ainsi qu'aux substances type caoutchouc naturel.)
    Additional Material: 14 Ill.
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  • 129
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 410-420 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The changes in the viscosity-average size distribution of polystyrene under conditions of simultaneous degradation and polymerization in toluene solutions have been observed. The appearance of the differential distribution curves for the degraded polymers and the polymerized monomer in the steady-state viscosity region are nearly identical. Osmotic pressure data on fractions of the degraded polymers do not show evidence for the occurrence of chain branching.
    Additional Material: 6 Ill.
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  • 130
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of different peroxides as catalysts and different polyhydroxy compounds as reducing activators both in the presence and absence of metals in a standard emulsion copolymerization of butadiene and styrene has been determined. The results of this study further emphasize the importance of a careful balance of all ingredients in any reduction-activation system.
    Additional Material: 6 Tab.
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  • 131
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 444-447 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: m-Nitrostyrene, prepared from m-nitrocinnamic acid in 60% yields, has been converted to polymers of low molecular weight in bulk and in solution with benzoyl peroxide, boron fluoride, and aluminum chloride initiators, and in aqueous emulsion with persulfate initiator.
    Additional Material: 3 Tab.
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  • 132
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 763-771 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Depolarization measurements on solutions of polystyrene, polyvinyl chloride, polyvinyl acetate, polvdieblorostyrene, and tobacco mosaic virus have been made in order to examine various aspects of the qualitative theory proposed in the foregoing paper. In the case of the polymers the variation Of Ph and p, with concentration and solvent ability have been verified. The value of P, for tobacco mosaic virus is quite small as expected, and the value of ph for different virus preparations increases with decreasing molecular length as predicted.
    Additional Material: 4 Ill.
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  • 133
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper represents an attempt to review the general interpretation of the phenomenon of depolarization of light scattered from colloidal solutions and to combine this with other recently acquired knowledge in order to predict the qualitative behavior of the depolarization ratios, as well as the individual components which make up these ratios, with respect to concentration, solute-solvent interaction, and the characteristics of the macromolecules. The ratio ρv depends inversely on the turbidity of the solution, the behavior of which is now understood due to the investigations of the light scattering method relative to molecular weight determinations. If allowance is made for turbidity changes and the effects of intramolecular interference ρv reflects the optical anisotropy of the segments of polymer molecules and of rigid molecules as a whole. The values of ρh will generally diminish from a value of unity as the size of the scattering particle increases. Sniall rodlike particles appear to be an exception to this behavior according to the works of Gans and Neugebauer but experimental confirmation is lacking notwithstanding recent claims to the contrary.
    Additional Material: 7 Ill.
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  • 134
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 735-749 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: PartI. It was confirmed that certain cellulose nitrates in 1% solution in acetone become more viscous and finally gel on standing over CaO, PbO, the basic salts of weak acids and strong bases, and certain other materials. The gels, whose formation was facilitated by increased temperature, were broken by the addition of a small amount of acid. The rate of gelling increased with the nitrogen content of the cellulose nitrate, indicating that residual hydroxyl groups were not involved. Nor did gelling occur under the same conditions in 1% solutions of cellulose acetate and ethyl cellulose of comparable degree of substitution. The rate of gelling was enormously increased when COOH groups were artificially introduced into the cellulose before nitration. Gelation is most probably due, therefore, to the cross-linking of different cellulose nitrate chains through COOH or possibly SO3H groups.Part II. Dilute (〈 0.2%) cellulose nitrate solutions on standing over CaO show a fall in viscosity with time (contrast 1). By ultracentrifuge examination this was shown to be due (for CaO and PbO treated solutions), not to degradation of the cellulose nitrate chains, but to association processes leading to the formation of aggregates of higher sedimentation constant and molecular weight. Sedimentation constants corresponding to molecular weights of several millions were observed from a cellulose nitrate of initial molecular weight ca. 100,000. Untreated control solutions showed no change in the state of aggregation. The association processes followed an approximately first-order law at room temperature and were made more rapid by increase in temperature. After sedimentation, the association products could not be redispersed. Calcium introduced into cellulose nitrate before solution in acetone did not cause association or any other noticeable effect at low concentration.
    Additional Material: 5 Ill.
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  • 135
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymerization rate constant ratios have been determined as a function of temperature for the monomer pairs: styrene-acrylonitrile and dichlorostyrene-acrylonitrile. The temperature dependence, which represents the difference of the activation energies of the respective addition reactions, is of the magnitude expected, except for the styrene-dichlorostyrene system.
    Additional Material: 3 Tab.
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  • 136
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Swelling and rate of crystallization from solution and gels of raw and vulcanized guttapercha have been studied. Sulfur vulcanization of gutta-percha causes a reduction in the amount of crystalline phase that becomes evident from typical changes in mechanical and swelling properties. Liquid-polymer interaction of the crystalline phase in gutta-percha, raw rubber, and “racked” rubber lead to different equilibria, which are probably due to differences in the free energy contents of the crystalline phases. A series of vulcanized rubber hydrochlorides with gradually increasing chlorine content show analogous changes in rate of elastic recovery and swelling equilibria that are also due to the gradual formation of a crystalline phase. Correlations between molecular structure and rate of crystallization in plastics and elastomers are discussed. Symmetry of the shape, as well as of inter molecular forces in the molecular units, size of substituents, and regularity of the polymer chain all have an essential influence on the rate and ease of crystallization.
    Additional Material: 4 Ill.
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  • 137
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 792-794 
    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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  • 138
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 790-791 
    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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  • 139
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 794-794 
    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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  • 140
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 794-794 
    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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  • 141
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 795-796 
    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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  • 142
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    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 3 (1948), S. 796-797 
    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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  • 143
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Series of bulk and solution polymerizations of vinyl chloroacetate have shown that the properties of the polymer vary widely with variation in polymerization conditions. The highest viscosity polymer, intrinsic viscosity polymer, intrinsic viscosity of 1.32, is prepared by bulk polymerization with 0.028% benzoyl peroxide initiator at 70°C. At polymerization temperatures sdover 70°C. and at catalyst concentrations over 0.14%, the polymer is discolored, insoluble, or has relatively poor aging characteristics. Polymerization in an equal volume of methyl isobutyl ketone at 80°C. and with 0.013% benzoyl peroxide gave 93% yield of polymer of intrinsic viscosity 0.15. In nitrobenzene, toluence, trichloroethylene, or ethyl acetate, only traces of polymer are obtained. In carbon tetrachloride, unstable telomers are produced.
    Additional Material: 3 Ill.
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  • 144
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 267-270 
    ISSN: 0025-116X
    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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  • 145
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 271-278 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Messungen an Polyvinylacetaten verschiedener Herstellungsart (Block-, Band- und Perlpolymerisate von verschiedener Polymerisationstemperatur) und verschiedener Molekulargewichtsverteilung ergeben gleiche Makromolekülgestalt in Lösung. Die Bezichung zwischen osmotischem Molekulargewicht und Viskositätszahl wird für fraktionierte Produkte in Aceton durch die Gleichung: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Z}_\eta = 1,0 \cdot 10^{ - 5} M^{0,75} {\rm\ wiedergegeben} $$\end{document}
    Additional Material: 2 Ill.
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  • 146
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    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 2 (1948), S. 279-288 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Osmotische und kryoskopische Messungen an wäßrigen Lösungen polyacrylsaurer Salze haben ergeben, daß polyvalente Anionen eine starke Inaktivierung ihrer Gegenionen bewirken. Elektrometrische Messungen mit Hilfe der Natriumamalgamelektrode bestätigen dieses Ergebnis; weniger als 1/3 der Natriumionen erweist sich als potentiometrisch wirksam. Die Natriumsalze ein- bis vierbasischer, niedermolekularer Carbonsäuren zeigen dagegen ein unter sich ähnliches, normales Verhalten, das von demjenigen des polyacrylsauren Natriums stark abweicht.
    Additional Material: 5 Ill.
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  • 147
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    Die Makromolekulare Chemie 2 (1948), S. 289-297 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Es wird ein Verfahren zur Darstellung der d-Galakturonsäure unmittelbar aus Pektin beschrieben. Der Abbau wird mit „Pectinol“, einem im Handel erhältlichen Filtrationsenzym, ohne Verwendung von Säuren oder Basen, beim Eigen-pH des Pektins und bei 40°C durchgeführt. Zur Isolierung der Galakturonsäure wird aus den zum Sirup eingeengten Lösungen die Galakturonsäure mit Äthanol oder mit Methanol herausgelöst, wobei die Enzyme und die nicht vollständig hydrolysierten Pektine ausfallen. Es wurden Ausbeuten bis zu 71% der Theorie erreicht. Durch kinetische Messungen wurden die günstigsten Bedingungen für den Abbau ermittelt.
    Additional Material: 4 Ill.
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  • 148
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Durch Untersuchung der Kettenlängenverteilung in polymerhomologen Reihen von oxydativ in Kupferoxydammoniaklösung mittels Luftsauerstoff abgebauten Baumwoll- und Ramiecellulosen wird gezeigt, daß ebenso wie bei Säureeinwirkung eine erhebliche Vereinheitlichung der Substanzen bei Polymerisationsgraden zwischen 400 und 500 eintritt. Es wird daraus geschlossen, daß im Abstand von ca. 500 Glucoseresten Bindungen vorhanden sein müssen, die ca. 3000 mal schneller gespalten werden als die normalen β-glucosidischen Bindungen. Zum Unterschied von den Ergebnissen bei dem hydrolytischen Abbau ist das Verhältnis der Spaltungsgeschwindigkeiten bei beiden Cellulosearten fast gleich. Es läßt sich noch nicht entscheiden, ob die hydrolytischen und oxydativen Lockerstellen identisch sind, oder ob sich zwei gleich große Periodizitäten überlagern.
    Additional Material: 9 Ill.
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