synopsis 100-MHz NMR spectra are reported for solutions of the 1 : 1 copolymers of sulfur dioxide with hex-1-ene, cis-and trans-butrknes, cyclohexene, cyclopentene, and norbornene, including the deuterated polymers made from hex-l-ene-%d,, cis-and trambutrhne-2,3-d*, and cyclohexene-3,3,6,6-d,. The resolution of the spectrum of poly-(hex-1-ene sulfone) was very poor in CCL as solvent but good in polar solvents. The main-chain CHe protons are nonequivalent, and their chemical shifts show sensitivity to dyad structure; the a-CH2 protons are also non-equivalent. The spectra of most of the other polymers are discussed in terms of possible preferential modes of addition as well as tacticity effects.
The reactivities of isoprene, piperylene,2,3‐dimethylbutadiene, hex‐1‐yne, and phenylacetylene, at −20°C, relative to that of cyclohexene, have been determined for the radical‐initiated copolymerization with sulfur dioxide to form 1:1 polysulfones. The unsaturated hydrocarbons were copolymerized with sulfur dioxide in pairs and the composition of the terpolymers determined from the 100 MHz NMR spectra. The dienes react 11–15 times as fast as hex‐1‐ene, while hex‐1‐yne reacts 16 times more slowly. Phenylacetylene reacts 21 times as fast as hex‐1‐yne. The relative reactivities are interpreted mainly in terms of the effect of electron delocalization on the stability of the product radical.
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