Zmo. Rzaev et al., COMPLEX-RADICAL CYCLO-COPOLYMERIZATION OF ALLYL A-(N-MALEIMIDO)ACETATE WITH STYRENE AND MALEIC-ANHYDRIDE, Macromolecular chemistry and physics, 198(8), 1997, pp. 2475-2487
Radical copolymerizations of allyl alpha-(N-maleimido)acetate (AMI) wi
th styrene (D, electron-donor) or maleic anhydride (A, electron-accept
or) were carried out in benzene and/or methyl ethyl ketone (MEK) at 50
-70 degrees C in the presence of 2,2'-azoisobutyronitrile (AIBN) as in
itiator. The structure and properties of copolymers synthesized were d
erived from IR, chemical, DTA and TGA analyses. Side-chain unsaturatio
n of macromolecules was also proved by the crosslinking effect observe
d. Kinetic parameters of copolymerization such as complex-formation (K
-c), cyclization (k(cyc)), and copolymerization constants and ratios o
f chain growth rates for the participation of monomer charge transfer
complexes (CTC) and free monomers for both systems were obtained: K-c
= 0,20 +/- 0,01 and 0,05 +/- 0,005 L/mol in CH3COOH-d(4) at 35 +/- 0,1
degrees C (H-1 NMR method) for D...AMI and AMI... A complexes, respec
tively; k(cyc) . 10(5) = 1.71 and 0,66 L/(mol . s), r(1) = 0,13 +/- 0,
01 and 0,037 +/- 0,002, r(2) = 0,048 +/- 0.002 and 0,052 +/- 0,002 (by
Kelen-Tudos method), k(12)/ k(21) = 0,20 and 0,62, k(1c)/k(12) = 0,6
and 29,8, k(2c)/k(21) = 4,8 and 9,1 for the D-AMI and AMI- A systems,
respectively. The results show that alternating cyclocopolymerization
reactions are realized which are carried out via a ''mixed'' mechanism
in the D-AMI system and via a ''complex'' mechanism in the AMI-A syst
em, with formation of cyclolinear macromolecules containing side-chain
unsaturated fragments of ''allyl'' (D-AMI copolymer) and ''imide' (AM
I-A copolymer) types. The synthesized copolymers easily undergo crossl
inking by thermotreatment (105 degrees C, 30 min) and/or by UV-irradia
tion (25 degrees C, 15 min), which was confirmed by DTA and TGA analys
es.