Premium
Ring‐opening polymerization of the cyclobutane adduct of tetracyanoethylene and ethyl vinyl ether by the initiating system vinyl ether‐acetic acid adduct/zinc iodide. Synthesis of a molecular weight‐controlled alternating copolymer of the two olefins
Author(s) -
Yokozawa Tsutomu,
Fujino Tooru,
Morita Izumi,
Toyoizumi Takashi
Publication year - 1998
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19980601)199:6<997::aid-macp997>3.0.co;2-r
Subject(s) - chemistry , tetracyanoethylene , polymer chemistry , polymerization , monomer , vinyl ether , ether , acetic acid , organic chemistry , polymer
Ring‐opening polymerization of the cyclobutane adduct ( 1 ) of tetracyanoethylene (TCNE) and ethyl vinyl ether (EVE) was carried out with protonic acid/Lewis acid or EVE‐acetic acid adduct ( 2 )/ZnI 2 as initiating systems in CH 3 NO 2 at ambient temperature. Poly 1 s with narrow molecular weight distribution (MWD) were obtained with the systems acetic acid(AcOH)/ZnI 2 or 2 /ZnI 2 . In the polymerization with 2 /ZnI 2 , the number‐average molecular weight (M̄ n ) of the polymers decreases with increasing amount of 2 /ZnI 2 , and increases in direct proportion to the monomer conversion. Furthermore, M̄ n increases on addition of a fresh feed of monomer at the end of the first‐stage polymerization. The MWD remains narrow throughout the reaction. On the basis of the reaction of 1 with an equimolar amount of 2 in the presence of ZnI 2 and the diene 5 as a by‐product formed by elimination of hydrogen cyanide from 1 in the polymerization, it was proposed that ZnI 2 activates both the CH‐OAc terminal groups of the growing polymer chain and monomer 1 .