SYNTHESIS OF POLYMERS CONTAINING PSEUDOHALIDE GROUPS BY CATIONIC POLYMERIZATION .13. LIVING POLYMERIZATION OF 2-METHYLPROPENE INITIATED BY THE SYSTEM 1,4-BIS(1-AZIDO-1-METHYLETHYL)BENZENE/BCL3/DIMETHYLSULFOXIDE

Polymerizations of 2-methylpropene (MP) initiated by the system 1,4-bis(1-azido-1-methylethyl)benzene (DAMEB)/BCl3 in the presence of DMSO were carried out by ''all monomer in'' (AMI) technique at -70 degrees C in CH2CI2 solution. FT-IR, H-1 NMR and SEC analyses of polymers (PMP) showed that the (M) over bar(n), versus weight of PMP plot is a straight line without intercept and azide F-N, and aromatic ring F-Phi functionalities are close to the theoretical values of 2 and 1, respectively. A polymerization of MP initiated by the system alpha,omega-diazido-PMP/BCl3/DMSO led to a final poly(2-methylpropene) (PMP) with an increase of (M) over bar(n) corresponding to the amount of MP introduced and presenting the same functionalities F-N and F-Phi as the starting PMP. These results indicate that the polymerization system MP/DAMEB/BCl3/DMSO is a ''living'' one, because in an acceptably large range of molecular weight ((M) over bar(n) < 50000) the Mayo plot 1/<(DP)over bar> versus 1/<(DP)over bar>(0) is a straight line. The intercept gives k(trM)/k(p) = 4.10(-5), showing the transfer reaction proceeds at very low rate.