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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Schwefelvukanisation von Naturkautschuk mit der binären beshleunigermischung aus 2-Mercaptobenzthiazol (MBT) und Diphenyiguanidin (DPG) sowohl mit als auch ohne ZnO und Stearinsäure wurde mit und ohne Dicumylperoxid (DCP) eingehend untersucht. Dabei zeigte sich, daß die Zersetzungsgeschwindigkeit von DCP in Gegenwart von MBT und DPG derjenigen bei alleinigem Vorhandensein von MBT ganz ähnlich ist. Die verringerte Vernetzung ist nur von MBT abhängig. Obwohl DPG keinen Einfluß auf die Zersetzungsgeschwindigkeit ausübt, reagiert es mit MBT während der Vulkanisation und unterdrückt die von MBT verursachte Verzögerung. In Übereinstimmung mit der Anfangsadditivität der Vernetzung in DCP enthaltenden Systemen, der freien Schwefelabnahme und der Geschwindigkeit der Vernetzung wurde der Vulkanisierungsprozeß des MBT-DPG-S-NR-Systems durch einen durch MSH2NR′R″ induzierten polaren Mechanismus erklärt. In Gemischen, die DCP zusammen mit Schwefel, MBT, DPG, ZnO und Stearinsäure enthalten, ist das Anfangsstadium der Vernetzung additiv, was durch gemischte Reaktionen und durch Methyljodid-Behandlung der Vulkanisate bestätigt wird. Ein Vergleich rnit einzelnen Beschleunigern zeigt deutlich einen synergistischen Effekt. Dies wird von der gesteigerten Reaktivität des MBT-ZnO-Stearinsäure-Komplexes gegenüber DPG verursacht, das durch die Bildung des aktiven Komplexes MSH2NR′R″ auch eine polare Vulkanisation von Naturkautschuk induziert. Bei Anwesenheit von ZnO und Stearinsäure kann DCP die Vernetzungsdichte nicht vergrößern, es unterdrückt aber die bei seiner Abwesenheit deutliche Vernetzungsabnahme.
    Notes: Sulfuration of natural rubber (NR) by the binary accelerator 2-mercaptobenzothiazole (MBT) and diphenylguanidine (DPG) both in presence and in absence of ZnO and stearic acid with or without dicumylperoxide (DCP) was studied in detail. It was observed that the rate of decomposition of DCP in presence of both MBT and DPG is quite similar to that with MBT alone. The reduction of crosslinking depends also on MBT only. Through DPG has no influence on the decomposition rate, it reacts with MBT during the vulcanization process and suppresses the retardation caused by MBT on the DCP vulcanization. In accordance with the initial additiveness of crosslinking in systems containing DCP, the free sulfur decrease, and the rapidity of crosslink formation the vulcanization process of MBT-DPG-S-NR systems was interpreted in terms of a polar mechanism induced by the complex MSH2NR′R″. In mixtures containing DCP together with sulfur, MBT, DPG, ZnO, and stearic acid, the initial stage of crosslinking is additive as indicated by a mixed reaction as well as by a methyl iodide treatment of the vulcanizates. Comparison with single accelerators shows a pronounced synergistic effect. This is because of the enhanced activity of the MBT-ZnO-stearic acid complex due to DPG which also induces polar sulfuration of NR by forming the active complex MSH2NR′R″. In presence of ZnO and stearic acid, DCP cannot increase the net crosslink density but suppresses the reversion so much pronounced in its absence.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 6 (1969), S. 171-178 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Vernetzugsdichte von mit Dicumylperoxid (DCP) vulkanisiertem Naturkautschuk und Styrol-Butadien-Kautschuk wurde durch Quellversuche bestimmt. Die für dei Kettenenden korrigierte Anzahl an elastisch wirksamen Vernetzungsbrücken wurde gegen die Mole an zersetztem DCP aufgetragen; daraus wurde die Vernetzungswirksamkeit des Peroxids gefunden. Die g-Werte der FLORY-Gleichung wurden bei variierender Vernetzungsdichte berechnet; sowohl die FLORY-Gleichung als auch andere Gleichungen, die chemische und physikalische und physikalischen Vernetzungsbrücken aus Quellungsversuchen zufriedenstellend angewandt werden.
    Notes: The cross-link density of dicumyl peroxide (DCP) vulcanizates of NR and SBR has been determined by the equilibrium swelling method. From a plot of elastically effective cross-links corrected for chain ends against the moles of DCP decomposed, the efficiency of crosslinking has been found. The values of g in the FLORY equation have been calculated at varying densities of cross-links, and it has been found that both the FLORY equation as well as other equations relating chemical cross-links to physical ones can be satisfactorily empolyed for the calculation of chemical cross-links from the physical cross-links determined by swelling measurement.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 199 (1992), S. 1-6 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(phenylphosphindiylterephthaloyl), ein neues phosphorhaltiges Polymeres, wurde durch Lösungspolykondensation von Dilithium(phenyl)phosphin mit Terephthaloylchlorid bei niedriger Temperatur hergestellt. Es ist in polaren aprotischen Lösungsmitteln löslich; die inhärente Viskosität in DMF bei 30°C beträgt 19 ml/g. Das Polymere wurde mittels Elementaranalyse sowie IR- und 1H-NMR-Spektroskopie charakterisiert. TGA-Messungen ergeben, daß das Polymere in Luft bis 250°C stabil ist; es ist selbstverlöschend.
    Notes: Poly(phenylphosphinediylterephthaloyl), a novel phosphorus-containing polymer, was synthesized by low-temperature solution polycondensation of dilithio(phenyl)-phosphine with terephthaloyl chloride. The resulting polymer is soluble in polar aprotic solvents, having inherent viscosity of 19 ml/g in DMF at 30°C. The polymer was characterized by elemental analysis, IR and 1H-NMR spectroscopy. TGA data show that the polymer is stable up to 250°C in air. The polymer was found to be self-extinguishing.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die mit 2-Mercaptobenzthiazol und Zinkoxid mit und ohne Stearinsäre beschleunigte Vulkanisation von Naturkautschuk und Styrol-Butadienkautschuk wurde untersucht; die Ergebnisse wurden mit den Untersuchungen verglichen, in denen anstelle des Thiazols dessen Zinksalz verwendet wurde. Für die Geschwindigkeit der Vulkanisation, die aus der Abnahme an freiem Schwefel oder aus der Vernetzung bestimmt wurde, ergab sich eine Reaktionsordnug von 1, während in Bezug auf die Beschleunigerkonzentration eine Ordnung kleiner 1 gefunden wurde.Ohne Zusatz von Stearinsaure ist das Zinksalz wesentlich weniger wirksam fur die Beschleunigung der Vulkanisation als das Thiazol und das Thiazol merklich wirksamer mit Zinkoxid als ohne. Der Zusatz von Stearinsiiure hebt nicht nur die Wirksamkeit beider Systeme auf das gleiche Niveau, sondern bewirkt auch eine Erhohung der Vulkanisationsgeschwindigkeit und des Vernetzungsgrades sowie die Vermeidung einer Reversion und fuhrt zu erheblich verbesserten mechanischen Eigenschaften des Vulkanisats. Es wurde versucht, die Ergebnisse uber die Annahme einer Komplexbildung zwischen dem Zinksalz des Thiazols und Zinkstearat zu deuten.
    Notes: Sulfur vulcanization of natural rubber (NR) and styrene-butadiene rubber (SBR) accelerated with 2-mercaptobenzothiazole and zinc oxide with or without stearic acid has been studied and the results compared with those obtained by replacing the thiazole with its zinc salt. The order of the rate of vulcanization as measured from free sulfur decrease or crosslink formation is observed to be unity with respect to time and less than one with respect to accelerator concentration. In absence of stearic acid, the zinc salt is much less efficient than the thiazole in promoting vulcanization, and the efficiency of the latter shows a noticeable improvement over what is attained in absence of zinc oxide. Addition of stearic acid not only raises the efficiency of both the systems to the same level but also leads to a faster rate of vulcanization, a much higher degree of crosslinking, avoidance of reversion, and production of vulcanizates with considerably improved mechanical properties. The formation of zinc sulfide also reveals interesting variation. Attempts have been made to interprete these results in terms of complex formation between zinc salt of thiazole and zinc stearate.
    Additional Material: 33 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 37 (1959), S. 469-483 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vinyl benzoate was polymerized in bulk as well as in solution, using benzoyl peroxide and azobisisobutyronitrile initiator at a temperature of 79.6°C. The overall rate of polymerization was found to be proportional to the concentration of the monomer and to the square root of the initiator concentration. Polymerization progressed to a normal extent, except that it increased with conversion, probably because of transfer with polymer. The value of the transfer constants with the monomer, initiator, and some solvents are reported.
    Additional Material: 10 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2971-2983 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diphenylguanidine (DPG) raises the rate of decomposition of dicumylperoxide (DCP) and the crosslinking maxima due to DCP is lowered to some extent by DPG. When the molar proportion of DPG-S is approximately 1:1, no additive results of crosslink formation (as reported for NR) are observed. Zinc oxide and stearic acid increase the rate of crosslinking as well as the crosslinking maxima. In the present study it appears most probable that DPG-accelerated sulfuration of SBR is an ionic process. At a constant level of DCP and sulfur crosslink density increases when the amount of DPG is increased; a constant level of DCP and DPG crosslinking increases with rising sulfur concentration.An increase in the concentration of DPG or sulfur leads to greater formation of the complex as well as a change in its composition. The effect of DPG is more pronounced, for by reducing the number of sulfur atoms more sulfur is available for crosslinking. Sulfur absorbs little SO2 or H2S; if it is already saturated, there is no perceptible effect. DPG does absorb H2S or SO2 and the rate and maxima of crosslinks is increased. The effect of SO2 is higher because of the higher Ka values of H2SO3 and consequently higher concentration of HSO3-. Reversion is a free-radical process inhibited by free DPG present in the system. In the presence of zinc oxide and stearic acid the reaction follows a polar mechanism as well as a radical mechanism.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Letters Edition 21 (1983), S. 263-270 
    ISSN: 0360-6384
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The salient features of nonelemental sulfur vulcanization by tetramethylthiuram disulfide (TMTD) and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. In stock containing TMTD, a higher rate constant value for dicumyl peroxide (DCP) decomposition was observed. TMTD decreases the crosslinking density due to DCP depending on its concentration. An entirely radical mechanism has been advanced in the absence of ZnO. ZnO or ZnO-stearic acid seems to alter the entire course of reaction. The rate of crosslinking increases in the presence of ZnO or ZnO-stearic acid. Moreover, crosslinks are formed additively (further supported from the activation energy data), and mixed crosslink formation has been confirmed by the methyl iodide test of the vulcanizates. Stearic acid has no effect on crosslink formation. An ionic chain mechanism has been postulated in the presence of ZnO, as suggested by British authors.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2773-2784 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study embodies the results and discussion of a comprehensive and systematic investigation of the mechanism of sulfuration of styrene-butadiene rubber accelerated by N-cyclohexylbenzothiazole-2-sulfenamide (CBS) with and without activators. Dicumyl peroxide (DCP) has been taken as a chemical aid to distinguish between free-radical and polar mechanisms of sulfuration. The rate constant for DCP decomposition in presence of CBS and the reduction in crosslink density by CBS have also been studied. With a constant amount of DCP and sulfur the crosslink density increases with increasing CBS concentration. In the presence of ZnO and stearic acid, crosslinking proceeds faster than in a similar system without these ingredients, and with DCP the crosslinks are found to be formed nearly additively as confirmed by methyl iodide treatment of the vulcanizates. In the absence of DCP, the crosslinking is characterized by an induction period, even in presence of ZnO and stearic acid. In the presence of sulfur, the 2-mercaptobenzothiazole (MSH) or amine or amine salt form crosslinkins by ionic reaction.
    Additional Material: 8 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 23 (1979), S. 185-200 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The sulfur vulcanization of NR by a MBT-TMTD mixed accelerator system both in the presence and absence of ZnO and stearic acid with or without DCP has been studied. The rate of decomposition of DCP in the presence of both MBT and TMTD is quite similar to that in the MBT system alone. The reduction in crosslinking due to DCP is dependent mainly on MBT. The decomposition product of TMTD may contribute to it only at the later stage of vulcanization. Though TMTD has no influence on the decomposition rate, it reacts with MBT at least in the initial stage of vulcanization and suppresses the retardation caused by MBT on DCP vulcanization in accordance with the free sulfur decrease, the nature of crosslinking formation both in the presence and absence of DCP, and the methyl iodide treatment of the vulcanizates. The vulcanization process of the MBT-TMTD-S-NR system has been interpreted in terms of both free radical and polar mechanisms. The domination of either of these depends on the dominant amount of either MBT or TMTD in the acclerator ratio. According to the initial high rate of crosslink formation, free sulfur decrease and also the initial additiveness of crosslinking in stocks containing DCP, the vulcanization process of MBT-TMTD-ZnO-St. acid-S-NR system has been explained in terms of an ionic mechanism. The pronounced synergistic nature of such systems has been interpreted by the enhanced activation of MBT-S-ZnO-St. acid complex due to the dithiodicarbamate ion formed in the initial stages of vulcanization, and also by the activation of TMTD accelerated vulcanization due to the mercaptobenzothiazylion.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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