Addition Polymerization of Aliphatic Dlthlols with Diene Monomers

The photoinitiated free radical polymerization of triethylene-glycoldithiol and hydrochinonebisallylether or ethyleneglycoldivi-nylether leads to poly (the ethers) having anti-Markovnikov structure M n: 14,000, 12,000 (VPO), respectively. The chain propagation is limited by a cyclic product (nearly 4%). Telechelics may be obtained by the use of nonequivalent molar ratio of the thioVenemonomers. They are useful in preparation of block copol-ymers and networks, respectively. By means of ESR-spectroscopic investigations, it is shown that in dithiole/diene mixtures, which are free of daylight and oxygen, radicals are formed spontaneously. Using the spin-trapping technique, the existence of sulfur and carbon radicals could be proved unambiguously.