Abstract
Binary (M1/M2) and ternary (M1/M2/M3) copolymer having aryl ketone and tertiary amine as pendant groups were prepared by radical polymerization, where M1 is 4-vinylbenzophenone (VBP) or 4-(2-naphthoyl)styrene (NSt), M2 is 2-N,N-dimethylaminoethyl methacrylate (DMAEMA) or 4-N,N-dimethylaminostyrene (DMASt), and M3 is methyl methacrylate. The polymer film was irradiated with a high-pressure mercury lamp (λ>300 nm), and photocrosslinking was followed by measuring the gel fraction. Crosslinking of the VBP(n,π*)-polymer was greatly accelerated by the amines, whereas that of the NSt(π,π*)-polymer could be induced only in their presence. The effects of the aliphatic amine (DMAEMA) were larger than those of the aromatic amine (DMASt). Absorption and emission spectra showed that the arylketones interact more strongly with aromatic amine than aliphatic amine. Laser photolysis experiments confirmed that the ketyl radicals were formed in the copolymers.
Similar content being viewed by others
Article PDF
References
S. G. Cohen, A. Parola, and G. H. Parsons, Jr., Chem. Rev., 73, 141 (1973).
S. Inbar, H. Linschitz, and S. G. Cohen, J. Am. Chem. Soc., 103, 1048 (1981).
S. Arimitsu, H. Masuhara, N. Mataga, and H. Tsubomura, J. Phys. Chem., 79, 1255 (1975).
J. Guillet, “Polymer Photophysics and Photochemistry,” Cambridge University Press, Cambridge, 1985, Chapter 10.
J. Hutchinson and A. Ledwith, Adv. Polym. Sci., 14, 49 (1974).
A. Ledwith, J. A. Bosley, and M. D. Purbrick, J. Oil Col. Chem. Assoc., 61, 95 (1978).
J. P. Fouassier, J. Chim. Phys., 80, 339 (1983).
G. Berner, R. Kirchmayr, and G. Rist, J. Oil Col. Chem. Assoc., 61, 105 (1978).
M. R. Sandner, C. L. Osborn, and D. J. Trecker, J. Polym. Sci., A-1, 10, 3173 (1972).
P. Ghosh and R. Ghosh, Eur. Polym. J., 17, 545 (1981).
P. Ghosh and R. Ghosh, Eur. Polym. J., 17, 817 (1981).
S. G. Cohen, G. A. Davis, and W. D. K. Clark, J. Am. Chem. Soc., 94, 869 (1972).
R. F. Bartholomew and R. S. Davidson, J. Chem. Soc. (C), 2342 (1971).
R. F. Bartholomew and R. S. Davidson, J. Chem. Soc. (C), 2347, (1971).
S. Tazuke, “Developments in Polymer Photochemistry-3,” N. S. Allen, Ed., Applied Science Publishers, London, 1982, p 62.
C. David, W. Demarteau, and G. Geuskens, Polymer, 10, 21 (1969).
G. Oster, G. K. Oster, and H. Moroson, J. Polym. Sci., 34, 671 (1959).
G. Sánchez, G. Weill, and R. Knoesel, Makromol. Chem., 176, 131 (1978).
G. J. Smets, Polym. J., 17, 135 (1985).
G. J. Smets, S. N. E. Hamouly, and T. J. Oh, Pure Appl. Chem., 56, 439 (1984).
K. Tsubakiyama, M. Yamamoto, and Y. Nishijima, J. Polym. Sci., A, Polym. Chem., 26, 1231 (1988).
C. S. Marvel, C. G. Overberger, R. E. Allen, and J. H. Saunders, J. Am. Chem. Soc., 68, 736 (1946).
A. Tsuchida, M. Yamamoto, and Y. Nishijima, J. Phys. Chem., 88, 5062 (1984).
A. Charlesby and S. H. Pinner, Proc. Ro. Soc., London, Ser. A, 249, 367 (1959).
H. H. G. Jellinek, J. Appl. Polym. Sci, Appl. Polym. Symp., No. 4, 41 (1967).
J. Chilton, L. Giring, and C. Steel, J. Am. Chem. Soc., 98, 1865 (1976).
C. Brauchle, D. M. Burland, and G. C. Bjorklund, J. Phys. Chem., 85, 123 (1981).
K. Horie, H. Ando, and I. Mita, Macromolecules, 20, 54 (1987).
K. Tsubakiyama, S. Ito, M. Yamamoto, and Y. Nishijima, Polym. Prepr. Jpn., 33, 289 (1984).
K. Tsubakiyama, S. Ito, M. Yamamoto, and Y. Nishijima, Polym. Prepr. Jpn., 33, 1475 (1984).
H. A. Hammond, J. C. Doty, T. M. Laakso, and J. L. R. Williams, Macromolecules, 6, 711 (1970).
R. Bensasson and E. J. Land, Trans. Faraday Soc., 67, 1904 (1971).
D. I. Schuster and M. D. Goldstein, Mol. Photochem., 7, 209 (1976).
K. Tsubakiyama, A. Tsuchida, M. Yamamoto, and Y. Nishijima, Preprints, The 51st Annual Meeting of the Chemical Society of Japan, Kanazawa, 1985, II, p 885.
C. G. Shaefer and K. S. Peters, J. Am. Chem. Soc., 102, 7566 (1980).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Tsubakiyama, K., Kuzuba, M., Yoshimura, K. et al. Photochemical Reaction of Polymers Having Arylketone and Tertiary Amine as Pendant Groups. Polym J 23, 781–788 (1991). https://doi.org/10.1295/polymj.23.781
Issue Date:
DOI: https://doi.org/10.1295/polymj.23.781
Keywords
This article is cited by
-
Transition-metal-free silylboronate-mediated cross-couplings of organic fluorides with amines
Nature Communications (2023)