Abstract
Radiation grafting is shown to be a method with considerable research and industrial potential for the insolubilization of a wide range of organic reagents on polymer surfaces. The principle of the method is outlined in detail and involves radiation-induced copolymerization of a monomer containing an appropriate functional group to a polymer, then attachment of the reagent by subsequent chemical reactions. The relative merits of the two relevant grafting methods for this purpose, namely pre-irradiation and the mutual technique, are evaluated. Typical experimental procedures for each method are discussed. The mutual technique is shown to be more satisfactory for insolubilization reactions because of the lower radiation doses needed to achieve a particular percentage graft, resulting in less radiation damage to the backbone polymer. Variables influencing the efficiency of the mutual grafting method are reviewed, including solvent, dose rate, and dose. Additives for optimizing the grafting yield and properties are considered, including mineral acid and polyfunctional monomers. Methods for reducing competing homopolymerization are summarized. Three examples of the application of the mutual radiation grafting technique for insolubilization reactions are discussed in detail. These include immobilization of enzymes, heterogenization of catalytically active homogeneous metal complexes, and the anchoring of analytical reagents to form ion exchange resins.
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References
G. R. Marshall and R. B. Merrifield, in: Biochemical Aspects of Reactions on Solid Supports (G. R. Stark, ed.), pp. 111–169, Academic Press, New York (1971).
K. G. Allum, R. D. Hancock, I. V. Howell, R. C. Pitkethly, and P. J. Robinson, Supported transition metal complexes. IV. Rhodium catalysts for the liquid phase hydroformylation of hexene-1,J. Catal. 43, 322–330 (1976).
K. G. Allum, R. D. Hancock, I. V. Howell, R. C. Pitkethly, and P. J. Robinson, Supported transition metal complexes. V. Liquid phase catalytic hydrogenation of hexene-1,J. Catal 43, 331–338 (1976).
Y. Kawabata, M. Tanaka, and I. Ogata, Asymmetric hydrogenation by a rhodium catalyst complexed with a phosphinite derived from cellulose, Chem. Lett.1976, 1213–1214.
T. J. Pinnavaia and P. K. Welty, Catalytic hydrogenation of 1-hexene by rhodium complexes in the intracrystal space of a swelling layer lattice silicate, J. Am. Chem. Soc. 97, 3819–3820 (1976).
M. Capka and V. Kavan, Catalytic activity of rhodium (I) complexes containing poly(siloxy)alkyl diphenyl phosphines, Collect. Czech. Chem. Commun. 45, 2100–2107 (1980).
J. L. Garnett, R. S. Kenyon, and M. J. Liddy, Enzyme immobilization by covalent attachment to novel polymer matrices prepared by a radiation grafting technique,J. Chem. Soc. Chem. Commun.1974, 735–736.
I. Kaetsu, M. Kumakura, M. Yoshida, M. Asano, M. Himei, M. Tamura, K. Hayashi, Immobilization of enzymes by radiation, Rad. Phys. Chem. 14, 595–602 (1979).
A. Charlesby, Atomic Radiation and Polymers, Pergamon Press, Oxford (1960).
A. Chapiro, Radiation Chemistry of Polymeric Systems, Interscience, New York and London (1962).
J. L. Garnett, Grafting, Rad. Phys. Chem. 14, 79–99 (1979).
J. L. Garnett and N. T. Yen, Acid effects in the radiation grafting of monomers to polymers, particularly polyethylene, ACS Symp. Ser. 121, 243–261 (1980).
S. Dilli and J. L. Garnett, Radiation-induced reactions with cellulose. IX. Copolymeriza-tion with styrene using a pre-irradiation procedure and the effect of additives on the grafting reaction, Aust. J. Chem. 24, 981–987 (1971).
G. M. Kline, Analytical Chemistry of Polymers Part1, 3rd Edition, Interscience, New York (1966).
A. Ekstrom and J. L. Garnett, Radiolysis of binary mixtures. Part IV. The effect of polycyclic aromatic additives in methanol, J. Chem. Soc. A1968, 2416–2418.
A. Chapiro, A. M. Jendrychowska-Bonamour, and G. Lelievre, Molecular products in the radiolysis of vinyl monomers, Faraday Discuss Chem. Soc. 63, 134–140 (1977).
S. Dilli and J. L. Garnett, Radiation-induced reactions with cellulose. III. Kinetics of styrene copolymerization in methanol, J. Appl. Polym. Sci. 11, 859–870 (1967).
J. L. Garnett, Grafting to cellulose using UV and gamma radiation as initiators, ACS Symp. Ser. 48, 334–360 (1977).
R. B. Phillips, J. Quere, G. Guiroy, and V. T. Stannett, Modification of pulp and paper by graft copolymerization, Tappi 55, 858–867 (1972).
R. J. Demint, J. C. Arthur Jr., A. R. Markezich, and W. F. McSherry, Radiation-induced interactions of styrene with cotton, Text. Res. J. 32, 918 (1962).
A. Hebeish and J. T. Guthrie, The Chemistry and Technology of Cellulosic Copolymers, Springer-Verlag, Berlin and Heidelberg (1981).
G. Odian, T. Acker, and M. Sobel, Accelerated effects in radiation induced graft polymerization, J. Appl. Polym. Sci. 7, 245–250 (1963).
S. Machi, I. Kamel, and J. Silverman, Effect of swelling on radiation-induced grafting of styrene to polyethylene,J. Polym. Sci. A-1 8, 3329–3337 (1970).
C. H. Ang, J. L. Garnett, and R. Levot, Use of polyfunctional monomers as additives in accelerating the radiation grafting of styrene to polyolefins, Proceedings of the American Chemical Society, 183rd National Meeting, Las Vegas, Nevada (March 1982).
S. Dilli and J. L. Garnett, A charge-transfer theory for the interpretation and radiation-induced grafting of monomers to cellulose, J. Polym. Sci. A-1 4,2323–2324 (1966).
A. Ekstrom and J. L. Garnett, Radiolysis of binary mixtures. I. Liquid phase studies with benzene-methanol,J. Phys. Chem. 70, 324–330 (1966).
D. F. Sangster and A. Davison, Pulse radiolysis of styrene and acrylate monomers, J. Polym. Sci. Symp. Polym. 49, 191–210 (1975).
J. L. Garnett and J. D. Leeder, Recent developments in grafting of monomers to wool keratin using U.V. and γ-radiation, ACS Symp. Ser. 49, 197–220 (1977).
H. Barker, J. L. Garnett, R. Levot, and M. A. Long, Use of additives to enhance radiation grafting of monomers to poly(vinyl chloride) and application of these PVC copolymers to immobilization of enzymes and heterogenization of homogeneous metal complexes, J. Macromol Sci., Chem. A12(2), 261–273 (1978).
J. H. Baxendale and F. W. Mellows, The gamma radiolysis of methanol and methanol solution, J. Am. Chem. Soc. 83, 4720–4726 (1961).
W. J. Chappas and J. Silverman, The effect of acid on the radiation-induced grafting of styrene to polyethylene, Rad. Phys. Chem. 14, 847–852 (1979).
J. L. Garnett, S. V. Jankiewicz, and D. F. Sangster, Effect of mineral acid on polymer produced during radiation-induced grafting of styrene monomer, J. Polym. Sci., Polym. Lett. Ed. 20, 171–175 (1982).
G..Fletcher and J. L. Garnett (unpublished work).
C. H. Ang, J. L. Garnett, R. Levot, and M. A. Long, Polyfunctional monomers as additives for enhancing the radiation copolymerization of styrene to polyethylene, polypropylene and PVC, J. Appl. Polym. Sci. 27, 4893–4897 (1982).
C. H. Ang, J. L. Garnett, R. Levot, and M. A. Long, Accelerated radiation-induced grafting of styrene to polyolefins in the presence of acid and polyfunctional monomers, J. Polym. Sci., Polym. Lett. Ed. 21, 257–261 (1983).
C. H. Ang, J. L. Garnett, R. Levot, and M. A. Long, Novel additives for accelerating radiation grafting of monomers to polymers in acid media, Proceedings of the Fourth International Meetings on Radiation Proceeding, Yugoslavia, 1982 (in press).
M. B. Huglin and B. L. Johnson, Role of cations in radiation grafting and homopolymerization, J. Polym. Sci. A-1, 7, 1379–1384 (1969).
J. L. Garnett and R. S. Kenyon, Acid effects in the styrene comonomer technique for radiation grafting to wool, J. Polym. Sco., Polym. Lett. Ed. 15, 421–425 (1977).
M. J. Liddy, J. L. Garnett, and R. S. Kenyon, The insolubilization of trypsin by attachment to radiation graft copolymers of polypropylene, J. Polym. Sci., Symp. Polym. 49, 109–116 (1975).
R. H. Grubbs and E. M. Sweet, Polymer attached catalysts. A comparison between polystyrene attached and homogeneous Rh(I) hydrogenation catalysts, J. Mol. Catal. 3, 259–270 (1977/8).
R. V. Davies, J. Kennedy, E. S. Lane, and J. L. Williams, Synthesis of metal complexing polymers, IV. Polymers containing miscellaneous functional groups, J. Appl. Chem. 9, 368–371 (1959).
J. R. Parrish and R. Stevenson, Chelating resins from 8-hydroxyquinoline, Anal. Chim. Acta 70, 189–198 (1974).
F. Vernon and H. Eccles, Chelating ion-exchangers containing 8-hydroxyquinoline as the functional group, Anal. Chim. Acta 63, 403–414 (1973).
F. Vernon and H. Eccles, Chelating ion-exchangers containing salicyclic acid, Anal. Chim. Acta 72, 331–338(1974).
C. H. Ang and J. L. Garnett (unpublished work).
N. P. Davis, J. L. Garnett, and R. G. Urquhart, Comparison of photosensitized and γ-ray-induced graft copolymerization of monomers to cellulose, J. Polym. Sci., Symp. Polym. 55, 287–301 (1976).
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© 1985 Plenum Press, New York
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Ang, C.H., Garnett, J.L., Levot, R.G., Long, M.A. (1985). Application of Radiation Grafting in Reagent Insolubilization. In: Gebelein, C.G., Carraher, C.E. (eds) Bioactive Polymeric Systems. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-0405-1_10
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DOI: https://doi.org/10.1007/978-1-4757-0405-1_10
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