SYNTHESIS AND POLYMERIZATION OF SUBSTITUTED ARYL VINYL SULFOXIDES - ONLINE MONITORING AND KINETICS OF THE THERMAL-DEGRADATION OF POLYMERIC SULFOXIDES INTO TRANSPOLYACETYLENE
A. Bader et Jr. Wunsch, SYNTHESIS AND POLYMERIZATION OF SUBSTITUTED ARYL VINYL SULFOXIDES - ONLINE MONITORING AND KINETICS OF THE THERMAL-DEGRADATION OF POLYMERIC SULFOXIDES INTO TRANSPOLYACETYLENE, Macromolecules, 28(11), 1995, pp. 3794-3800
The substituted aryl vinyl sulfoxides p-[RC(6)H(4)S(O)CH=CH2] (8a-c, R
= F, Cl, OMe) were prepared and polymerized in the presence of(3-meth
yl-1,1-diphenylpentyl)lithium (MDPPLi, 1) as anionic initiator to give
the corresponding poly(aryl vinyl sulfoxides) 9a-c. Upon thermolysis
of compounds 9 between 70 and 120 degrees C, the arenesulfenic acids (
10) were eliminated via an Ei mechanism generating all-trans-polyacety
lene (PA, 11). The formation of all-trans-PA was monitored on-line by
means of near-infrared-excited Fourier-transform (FT)-Raman spectrosco
py. The kinetics of the reaction were found to be first-order at conve
rsions above approximately 10%. On the basis of the rate constants det
ermined for the thermolysis of 9a-c at 70, 80, 90, 100, and 120 degree
s C, the relative reactivities of 9a-c, and thus the influence of the
substituents R on the rate of the PA formation, could be quantitativel
y estimated, and the following ratios were found: 9a (R = F):9b (R = C
l):9c (R = OMe) = 1.0 +/- 0.1:2.2 +/- 0.3:0.8 +/- 0.1.