Dl-tert butyl peroxide

It was found when this monomer was treated with dl-tert-butyl peroxide at 130" and the reaction was stopped below 30% conversion, a soluble polymer was obtained having a structure of a polycarbonate with pendant methylene groups. The structure of the polymer was established by elemental analysis as well as Infrared and NMR spectroscopy. A very similar polymer could be attained by treatment of the monomer with boron trlfluorlde etherate at low conversions. The mechanism of the polymerization appeared to Involve a radical double ring-opening according to the following mechanslm (12) ... 

The resulting monomer was a crystalline solid with a melting point of 61-62°. When the polymerization was carried out in the presence of dl-tert-butyl peroxide and the reaction was stopped at low conversion, a linear polycarbonate containing pendant methylene groups was obtained. 

The polybutadiene used was Intene from I. S. Rubber [77] = 2.1 dl/g in cyclohexane at 30°C. Vinyl chloride and styrene monomers from Montedison were 99.99 and 99.5% pure respectively. Azobis(isobutyronitrile) (AIBN) from Fluka was 99% pure. Di-te/t-butyl peroxide was 95% pure. Tert-butyl peracetate was used at a 50% dilution with dimethyl phthalate. The n-butyl ester of 3,3- (di-te/t-butylperoxy)valerianic acid was 85% pure. Terf-dodecyl mercaptan, a commercial product of the Societe Nationale des Petroles d Aquitaine, was used as a modifier. The solvents used were commercial products purified by fractionation. 

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