Effects of complex formation and cyclization in radical copolymerization of allyl(metha)acrylates with maleic anhydride

✍ Scribed by Zakir M. O. Rzaev; Güneri Akovali; Ülviye Salamova

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 197 KB
• Volume: 36
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19980730)36:10<1501::aid-pola2>3.0.co;2-t

✦ Synopsis

Radical copolymerization of allyl acrylate (AA) and allyl methacrylate (AMA) as bifunctional monomers of donor (allyl) -acceptor (acryl) type with maleic anhydride (MA) as an acceptor monomer were carried out in metrhyl ethyl ketone (MEK) at 50-70ЊC in the presence of 2,2-azoisobutyronitrile (AIBN) as initiator. Constants of complex formation (K c ), cyclization (k cl ), and copolymerization (r 1 , r 2 , r 1c , r 1c 1 , and r 1c 2 ) as well as energies of activation for cyclization ( E ac ) and copolymerization reactions ( E a ), and orders for the monomer ( m) and initiator ( n) concentrations were determined. The following values were found, for AA and AMA, respectively: K c Å 0.038 and 0.11 L/mol in deutered acetone at 35 { 0.1ЊC, k cl Å 6.45 and 6.53, r 1 Å 0.083 { 0.005 and 0.028 { 0.002, r 2 Å 0.027 { 0.002 and 0.063 { 0.003 (by the Kelen-Tu ¨do ¨s method), r 1c Å 0.04 and 0.025, r 1c 1 Å 0.128 and 0.176, r 1c 2 Å 0.127 and 0.177 (by the Seiner-Litt equation), E ac Å 28.9 and 28.7 kJ/mol, E a Å 67.0 and 87.9 kJ/mol, m Å 1.53 and 1.45, and n Å 0.50 and 0.52. The presence of cyclic, unsaturated, and anhydride fragments in the macromolecules was confirmed with FTIR data and chemical (iodometrical and potentiometric titrations) analysis. It was established that complex formation in the monomer systems studied is the main factor for alternating cyclocopolymerization leading to formation of copolymers containing lactone and linearunsaturated fragments in the macromolecular chain.