Complex-radical cyclocopolymerization of allyl a-(N-maleimido)acetate with styrene and maleic anhydride

Date

1997-08-01

Author

Rzaev, ZMO
Salamova, UU
Altindal, S

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Radical copolymerizations of allyl alpha-(N-maleimido)acetate (AMI) with styrene (D, electron-donor) or maleic anhydride (A, electron-acceptor) 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 initiator. The structure and properties of copolymers synthesized were derived from IR, chemical, DTA and TGA analyses. Side-chain unsaturation of macromolecules was also proved by the crosslinking effect observed. Kinetic parameters of copolymerization such as complex-formation (K-c), cyclization (k(cyc)), and copolymerization constants and ratios of 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, respectively; 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 system, with formation of cyclolinear macromolecules containing side-chain unsaturated fragments of ''allyl'' (D-AMI copolymer) and ''imide' (AMI-A copolymer) types. The synthesized copolymers easily undergo crosslinking by thermotreatment (105 degrees C, 30 min) and/or by UV-irradiation (25 degrees C, 15 min), which was confirmed by DTA and TGA analyses.

Subject Keywords

Physical and Theoretical Chemistry, Organic Chemistry, Materials Chemistry, Polymers and Plastics, Condensed Matter Physics

URI

https://hdl.handle.net/11511/67192

Journal

MACROMOLECULAR CHEMISTRY AND PHYSICS

DOI

https://doi.org/10.1002/macp.1997.021980809

Collections

Graduate School of Natural and Applied Sciences, Article

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Citation Formats

Z. Rzaev, U. Salamova, and S. Altindal, “Complex-radical cyclocopolymerization of allyl a-(N-maleimido)acetate with styrene and maleic anhydride,” MACROMOLECULAR CHEMISTRY AND PHYSICS, pp. 2475–2487, 1997, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/67192.