La. Novokshonova et al., STUDY OF ENERGY-DISTRIBUTION OF ACTIVE-SITES IN HETEROGENEOUS ZIEGLER-NATTA CATALYSTS, Polymer bulletin, 39(1), 1997, pp. 59-65
New method of investigation of active sites non-uniformity was develop
ed. The method is based on mass-spectrometric study of temperature pro
grammed desorption (TPD) products from the catalyst surface at initial
stages of olefin gasphase polymerization. The conditions of polymeriz
ation allowed to obtain the short macrochains on catalyst surface. Two
well-resolved intense maxima in the temperature ranges of 180-210 deg
rees C and 280-320 degrees C on the TPD curves from SiO2/TiCl4/AlEt2Cl
catalyst surface after polymerization were observed in a result of th
ermal destruction of active TI-C bonds and the evolution of hydrocarbo
n molecules of different length (up to 14 monomer units in chain). One
may conclude that in this catalyst there are at least two types of ac
tive sites varying in the activation energy of thermal destruction of
Ti-C bonds. The distribution of active sites over activation energy of
Ti-C bond thermal destruction was calculated.