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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 190 (1989), S. 777-788 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the emulsion polymerization of butadiene was investigated using Dresinate 214 as emulsifier and three dissociative initiators, viz. potassium peroxodisulfate, 4,4′-azobis-(4-cyanopentanoic acid) and 2,2′-azoisobutyronitrile. All experiments were conducted in the presence of a thiol as chain transfer agent, as usual in diene-polymerizations. The polymerization rate in interval II, Rpol, was found to be highly insensitive to changes in the initiator concentration (Rpol ∝ [I]0,08). Primary radicals are generated in large abundance in interval I as compared with the final particle number, indicating that the initiator efficiency with regard to particle nucleation is very low. The development of particle number as a function of conversion at several emulsifier concentrations shows that limited coagulation is occurring in the present system. Rpol depends on the emulsifier concentration with an exponent of 0,61, while the final particle number after cessation of coagulation depends on the emulsifier concentration to the 1,6th power. As a consequence the average number of radicals per particle must be a function of particle size, because the monomer concentration in the latex particles is approximately constant in interval II. A certain analogy in behaviour between the emulsion polymerization of various polar monomers, kinetically dominated by radical desorption, and the emulsion polymerization of butadiene, suggests that similar events determine the kinetic course in the present system.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The role of thiols of low water solubility, commonly used in the emulsion polymerization of butadiene, has been considered. The following effects have become apparent: (1) dodecanethiols act as efficient chain transfer agents in limiting the formation of heavily cross-linked polymer networks; (2) the monomer concentration within the particles is not influenced by such thiols; (3) C12-thiol radicals do not desorb because of their extremely low water solubility. The ‘promoting effect’ of thiols in emulsion polymerizations of diene-hydrocarbons is still poorly understood, but it appears to be related to impurities present in the emulsifier, as it was found completely absent in emulsifier-free polymerizations.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 192 (1991), S. 1993-2008 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The stirring speed n influences the emulsion polymerization of butadiene, (1) by reducing the effective emulsifier concentration [E]eff available for particle nucleation and stabilization at high n, and (2) by limiting diffusion of monomer to the latex particles at low n. The large density difference between butadiene and water promotes the breaking up of droplets at high n, while the same condition constitutes a large driving force for (partial) phase separation at low n. Increasing the monomer/water ratio at constant [E] decreases [E]eff, and thus the final particle number. At monomer volume fractions 〉0,6 mixed emulsions are likely to be formed initially, reducing [E]eff even further. In the presence of mixed emulsions, polymerization in the monomer phase may no longer be neglected, giving rise to a complex kinetic behaviour.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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