Head-to-head polymers. XXIV. Synthesis of head-to-head polyisobutylene by Grignard coupling reaction

Head-to-head polyisobutylene of molecular weight 3000 to 10,000 was prepared in about 30% yield by Grignard coupling polymerization of 2,2,3,3-tetramethyl-1,4-dibromobutane with copper(I) tris(triphenylphosphino)bromide as the catalyst. Head-to-head polyisobutylene is crystalline, with a T_m of 187°C and a T_g of 87°C and still has bromine end groups left. The polymers have been characterized by their infrared, ¹H-, and ¹³C-NMR spectra and compared to the corresponding head-to-tail polymers of similar molecular weight. A substantial portion of the reaction product of the Grignard coupling polymerization is not polymeric but was identified as cyclized product, 1,1,2,2-tetramethylcyclobutane.