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/dimethyl sulfoxide

✍ Scribed by Berhooz Rajabalitabar; Hung Anh Nguyen; Hervé Cheradame

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 344 KB
• Volume: 196
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.1995.021961113

✦ Synopsis

Abstract

Polymerizations of 2‐methylpropene (MP) initiated by the system 1,4‐bis(1‐azido‐1‐methylethyl)benzene (DAMEB)/BCl~3~ in the presence of DMSO were carried out by “all monomer in” (AMI) technique at −70°C in CH~2~Cl~2~ solution. FT‐IR, ^1^H NMR and SEC analyses of polymers (PMP) showed that the M~n~ versus weight of PMP plot is a straight line without intercept and azide F~n3~ and aromatic ring F~ϕ~ functionalities are close to the theoretical values of 2 and 1, respectively. A polymerization of MP initiated by the system α,ω‐diazido‐PMP/BCl~3~/DMSO led to a final poly(2‐methylpropene) (PMP) with an increase of M~n~ corresponding to the amount of MP introduced and presenting the same functionalities F~N3~ and F~ϕ~ as the starting PMP. These results indicate that the polymerization system MP/DAMEB/BCl~3~/DMSO is a “living” one, because in an acceptably large range of molecular weight (M~n~ < 50000) the Mayo plot 1/DP versus 1/DP~0~ is a straight line. The intercept gives k~trM~/k~p~ = 4 · 10^−5^, showing the transfer reaction proceeds at very low rate.