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  • radical polymerization  (1)
  • transfer reaction  (1)
  • Wiley-Blackwell  (2)
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  • Wiley-Blackwell  (2)
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  • 1
    Digitale Medien
    Digitale Medien
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 2687-2697 
    ISSN: 0887-624X
    Schlagwort(e): free radical polymerization ; transfer reaction ; addition-substitution-fragmentation mechanism ; end-group functionalisation ; allylic peroxyketal ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new chain transfer agent, ethyl 2-[1-(1-n-butoxyethylperoxy) ethyl] propenoate (EBEPEP) was used in the free radical polymerization of methyl methacrylate (MMA), styrene (St), and butyl acrylate (BA) to produce end-functional polymers by a radical addition-substitution-fragmentation mechanism. The chain transfer constants (Ctr) for EBEPEP in the three monomers polymerization at 60°C were determined from measurements of the degrees of polymerization. The Ctr were determined to be 0.086, 0.91, and 0.63 in MMA, St, and BA, respectively. EBEPEP behaves nearly as an “azeotropic” transfer agent for styrene at 60°C. The activation energy, Eatr, for the chain transfer reaction of EBEPEP with PMMA radicals was determined to be 29.5 kJ/mol. Thermal stability of peroxyketal EBEPEP in the polymerization medium was estimated from the DSC measurements of the activation energy, Eath = 133.5 kJ/mol, and the rate constants, kth, of the thermolysis to various temperature. © 1994 John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    ISSN: 0887-624X
    Schlagwort(e): chain transfer ; addition-fragmentation ; peroxysilane ; radical polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ethyl 2-[1-(trimethylsilylperoxy)ethyl]propenoate 1, ethyl 2-[1-(dimethylvinylsilylperoxy)-ethyl]propenoate 2, ethyl 2-[1-(1-(2-ethoxycarbonyl-1-methyl-2-propenylperoxysilyl)-1-methylethylperoxy)ethyl]propenoate 3, and 2-phenyl-2-trimethylsilylperoxypropane 4 were synthesized and added to the free radical polymerization of vinylic monomers. 1 and 2 were found to show no homopolymerizability but act as effective chain transfer reagents in radical polymerizations of methyl methacrylate (MMA), styrene (St), and n-butyl acrylate (BA). The estimated chain transfer constants (Ctr) are as follows: Ctr (1) = 0.15 for MMA, 0.90 for St, and 2.03 for BA at 60°C; Ctr (2) = 0.12 for MMA, 1.16 for St, and 1.9 for BA at 60°C. 1H-NMR spectra of poly(St) formed in the presence of 1 is consistent with the view that the polymers bear an oxirane at one terminal and an trimethylsilyloxy fragment at the other end. Moreover, peroxysilane 4 showed very low transfer properties by direct homolytic substitution (SH2). These findings indicate that the ethyl 2-[1-(substituted dimethylsilylperoxy)ethyl]-propenoates 1-3 undergo chain transfer reaction via a intramolecular homolytic substitution (SHi) following an addition process. Preparation of poly(styrene) up to high conversion in the presence of 3 yielded to the formation of the corresponding polymeric structures bearing hydrolysable C(SINGLE BOND)O(SINGLE BOND)Si(SINGLE BOND)O(SINGLE BOND)C bonds. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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