Preparation of Photo-Crosslinkable Polymers Having Coumarin Side Groups and Their Properties

Chung JS; Kim HS; Chae KH

Korea Polymer Journal, Vol.3, No.1, 12-18, April, 1995

Photocrosslinkable polymers containing coumarin side groups were prepared by copolymerizing 7-methacryloyloxycoumarin(MAC) and methyl methacrylate. Photochemical reaction of the copolymers was investigated by UV, IR and GPC analysis in film as well as in solution state. Upon irradiation of 350nm UV light to the polymer films in the presence of sensitizer, the rate of double bond disappearence increased in the order of acetophenone>benzophenone>naphthalene>anthraquinone>no sensitizer. The disappearence rate also increased with the content of MAC units in the copolymer and the amount of sensitizer. The reaction was photoreversible similar to that of 7-acetoxycoumarin, a model compound of the copolymer. 7-acetoxycoumarin photodimer and 7-hydroxycoumarin was produced upon irradiation with 350nm to 7-acetoxycoumarin. The photodimer was photosplitted into 7-acetoxycoumarin upon irradiation with 254 nm. GPC resu-Its show that molecular weight distribution of the copolymer on irradiation of 350 nm light became broader, i.e the content of both low and high molecular weight fraction increased which suggest that photocycloaddition and photodecomposition of coumarin moiety take place simultaneously.

[References]

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[2] Dilling WL, Chem. Rev., 83, 1 (1983)

[3] Minsk LM, Smith JG, Deusen WPN, Wricht JF, J. Appl. Polym. Sci., 2, 302 (1959)

[4] Robertson EM, Deusen WPV, Minsk LM, J. Appl. Polym. Sci., 2, 308 (1959)

[5] Lewis FD, Barancyk SV, J. Am. Chem. Soc., 111, 8653 (1989)

[6] Hoffman R, Wells P, Morrison H, J. Org. Chem., 36, 102 (1971)

[7] Muthuramu K, Raamamurthy V, J. Org. Chem., 47, 3976 (1982)

[8] Delzene GA, Adv. Photochem., 11 (1979)

[9] Delzene GA, Laridon U, Deeters SH, Eur. Polym. J., 21, 781 (1985)

[10] Hasegawa M, Saigo K, "Photochemistry and Photophysics," Vol. II, Chap. 2, p. 27, J.F. Rabek ed., CRC Press Inc., Boca Raton, Florida (1989)

[11] Chujo Y, Sada K, Saegusa T, Macromolecules, 23, 2693 (1990)

[12] Moghaddam MJ, Matsuda T, J. Polym. Sci. A: Polym. Chem., 31, 1589 (1993)

[13] Chae KH, Oh YJ, J. Photopolym. Sci. Tech., 7, 183 (1994)

[14] Chae KH, Cho DW, Choi MH, Kim JM, Oh S, Polym.(Korea), 18(3), 330 (1994)

[15] Chae KH, Park JS, Chung JS, Bull. Korean Chem. Soc., 14, 655 (1993)

[16] Chae KH, Park IJ, Choi MH, Bull. Korean Chem. Soc., 14, 614 (1993)

[17] Hammond GS, Stout CA, Lamola AA, J. Am. Chem. Soc., 86, 3103 (1964)