Solid phase modification of poly(propylene). The role of the polymer texture in the peroxide distribution

Zsuzsa László-Hedvig, Enikö Dobai, László Korecz, Péter Nagy, Achim Hesse, Manfred Rätzsch, Ferenc Tüdös

Research output: Contribution to journalArticle

1 Citation (Scopus)


Different poly(propylene)s were reacted with tert-butyl peroxybenzoate (TBPB) in solid phase and the time dependence of the concentration of tertiary polymer radicals ([A*]) formed was measured by ESR spectroscopy at 145°C. The distribution (or solubility) of peroxide was found uneven (or limited), the segregation of solid dilauroyl peroxide (DLPO) was proved by DSC. It was found that not the crystalline/amorphous ratio was the decisive factor in poly(propylene)/peroxide solid phase reactions, but much more the crystallite size of the polymer texture. The latter was determined by X-ray measurements. Poly- (propylene)s with average crystallite diameters of about 250 Å showed a characteristic dependence on peroxide concentration in the solid phase reaction of tertiary carbon radical forming. The log [A*] vs. time curves show a good linearity, the relationships correspond to a unimolecular overall kinetics. When the crystallite diameters were 17-40% less than 250 Å, the polymer radical concentration ([A*]) did not show a characteristic dependence on TBPB concentration. Our findings are interpretable in terms of capillary condensation of peroxides.

Original languageEnglish
Pages (from-to)2696-2701
Number of pages6
JournalMacromolecular Chemistry and Physics
Issue number13
Publication statusPublished - Sep 18 2001

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

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