Polymeric composites, viii

Reaction 22 has an RC>2H/Fe2+ mole ratio of 160 but has about the same yield as an uncontaminated reaction, 17 and 21. Reaction 19 has an RC>2H/Fe2+ mole ratio of 13.3 but again shows no change in yield from that of an uncontaminated reaction. Sample 20 has a 1.35 mole ratio of RO2H to Fe2+ and shows a sharp decrease in reaction yield and grafting. Here, the approximately 1 1 mole ratio of peroxide to iron should produce a high concentration of hydroxide radicals and extensive polymerization if these radicals are part of the polymerization process. Instead of a high yield, however, the reaction yield was less than one third of that obtained in the absence of iron. Therefore, a Fenton s initiation mechanism for this reaction is inconsistent with the data and probably does not occur. Elemental analysis data of Table VIII showed that product composition is proximate to, but not equal to, reaction mixture composition. 

The N values in Table VIII are highly constrained because of the use of Seed 1. As made, Seed 1 had 100% surfactant surface coverage and N =. 96. By adding additional surfactant, S could be varied upward, but relatively low values for N could not be achieved without producing extraordinarily high S values. To allow a wider range of N values, the monomer fed seed composition was developed and replicate Seeds 2 and 3 were prepared and used. These seeds had low S values and did allow relatively low N values to be obtained in the second stage polymerizations. Four S,... 

It should be noted that VIII gives neither polymer nor oligomer under the conditions described, and the yield is smaller with VII than with VI. Moreover, the percentage composition of the polymers does not correspond to that of the monomers about one atom of chlorine per molecule of monomer is lost when polymerization occurs. The polymer does not possess the characteristics of the cyclopropanes. It therefore appears that opening of the cyclopropane ring, dehydrochlorination, and polymerization occur simultaneously. 

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