Abstract
The present study is an extension of our preceding work on gelation behavior. We observed no substantial difference in the actual gel points among three isomeric diallyl phthalates: diallyl phthalate, diallyl isophthalate and diallyl terephthalate. The resulting network polymer precursors (NPPs) were characterized by size-exclusion chromatography with both multiangle laser light scattering and viscometry. It is of note that the structure of NPP, consisting of oligomeric primary polymer chains, becomes core-shell type dendritic or nanogel-like with the progress of polymerization. The nanogel-like NPPs can then collide with one another to form cross-links, eventually leading to gelation. Although the concentration of NPP should be high at the conversion close to the gel point, the dilution of NPP by adding monomer could prevent the cross-link formation among NPPs, and consequently lead to the successive growth of high-molecular-weight NPP from a nanogel to a microgel. The further growth of the microgel as an inhomogeneous NPP with high cross-link density could eventually reach an extremely inhomogeneous network polymer. These processes were pursued as typical examples using the bulk polymerization of DAT.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Matsumoto, A., Yokoyama, S., Khono, T. & Oiwa, M. Studies of the polymerization of diallyl compounds. XXV. Gel point in the polymerization of diallyl esters of aromatic dicarboxylic acids. J. Polym. Sci. Polym. Phys. Ed. 15, 127–136 (1977).
Gordon, M. Network theory of the gel point and the ‘incestuous’ polymerization of diallyl phthalate. J. Chem. Phys. 22, 610–613 (1954).
Matsumoto, A., Ogasawara, Y., Nishikawa, S., Aso, T. & Oiwa, M. Studies of the polymerization of diallyl compounds. XLI. Discussion of substantially identical gel points among three isomeric diallyl phthalates. J. Polym. Sci.: Part A: Polym. Chem. 27, 839–845 (1989).
Matsumoto, A., Sasaki, H. & Oiwa, M. Polymerization of diallyl compounds. XVI. Copolymerizations of diallyl esters of aromatic dicarboxylic acids with methylallyl benzoate. Makromol. Chem. 166, 179–188 (1973).
Matsumoto, A., Hamamoto, H., Miwa, Y., Aota, H., Inoue, S., Yokoyama, K., Matoba, Y. & Shibano, M. Discussion of substantially identical gel points among multiallyl monomers based on characterization of resultant network polymer precursors consisting of oligomeric primary polymer chains. J. Polym. Sci.: Part A: Polym. Chem. 47, 2871–2881 (2009).
Altschul, P. D. Polymerization of allyl compounds. II. Preliminary kinetic study of the peroxide-induced polymerization of allyl acetate. J. Am. Chem. Soc. 67, 816–822 (1945).
Matsumoto, A. Free-radical crosslinking polymerization and copolymerization of multivinyl compounds. Adv. Polym. Sci. 123, 41–80 (1955).
Matsumoto, A. Polymerization of multiallyl monomers. Prog. Polym. Sci. 26, 189–257 (2001).
Horie, K., Otagawa, A., Muraoka, M. & Mita, I. Calorimetric investigation of polymerization reactions. V. Crosslinked copolymerization of methyl methacrylate with ethylene dimethacrylate. J. Polym. Sci. Polym. Chem. Ed. 13, 445–454 (1975).
Galina, H., Dusek, K., Tuzar, Z., Bohdanecky, M. & Sokr, J. The structure of low conversion polymers of ethylene dimethacrylate. Eur. Polym. J. 16, 1043–1046 (1980).
Spevacek, J. & Dusek, K. Manifestation of microgel-like particles of styrene ethylene dimethacrylate copolymers in solution in proton and carbon-13 NMR spectra. J. Polym. Sci. Polym. Phys. Ed. 18, 2027–2035 (1980).
Shah, A. C., Parsons, I. W. & Haward, R. N. Dilute gelling systems: copolymers of styrene and glycol dimethacrylates. Polymer 21, 825–828 (1980).
Leicht, R. & Furrmann, J. Network formation during styrene-divinylbenzene copolymerization investigated by the fluorescence polarization method. Polym. Bull. 4, 141–148 (1981).
Matsumoto, A., Nakajima, H. & Oiwa, M. Polymerization of diallyl compounds. XLIV. Three-dimensional network formation of diallyl phthalate: microheterogenization of gel during polymerization beyond gel point. Netsukokasei. Jushi. (J. Thermoset. Plast. Jpn.) 9, 141–148 (1988).
Erath, E. H. & Robinson, M. Colloidal particles in thermosetting resins. J. Polym. Sci. C3, 65–76 (1963).
Stockmayer, W. H. Theory of molecular size distribution and gel formation in branched-chain polymers. J. Chem. Phys. 11, 45–55 (1943).
Stockmayer, W. H. Theory of molecular size distribution and gel formation in branched polymers. II. General cross-linking. J. Chem. Phys. 12, 125–131 (1944).
Odian, G . Principles of Polymerization, 4th edn, 263–264 (Wiley, New York, 2004).
Schildknecht, C. E. Allyl Compounds and Their Polymers (Wiley, New York, 1973).
Laible, R. C. Allyl polymerizations. Chem. Rev. 58, 807–843 (1958).
Volodina, V. I., Tarasov, A. I. & Spasskii, S. Polymerization of allyl compounds. Russ. Chem. Rev. 39, 140–155 (1970).
Walling, C. Gel formation in addition polymerization. J. Am. Chem. Soc. 67, 441–447 (1945).
Dusek, K. & Duskova-Smrckova, M. Network structure formation during crosslinking of organic coating systems. Prog. Polym. Sci. 25, 1215–1260 (2000).
Flory, P. J. Molecular size distribution in three-dimensional polymers. I. Gelation. J. Am. Chem. Soc. 63, 3083–3090 (1941).
Matsumoto, A., Yokoyama, S., Khono, T. & Oiwa, M. Studies of the polymerization of diallyl compounds. XXV. Gel point in the polymerization of diallyl esters of aromatic dicarboxylic acids. J. Polym. Sci. Polym. Phys. Ed. 15, 127–136 (1977).
Trommsdorff, E., Kohle, H. & Lagally, P. Polymerization of methyl methacrylate. Makromol. Chem. 1, 169–198 (1948).
Zimm, B. H. & Stockmayer, W. H. The dimensions of chain molecules containing branches and rings. J. Chem. Phys. 17, 1301–1314 (1949).
Acknowledgements
This research was financially supported by the ‘High-Tech Research Center’ Project for Private Universities: a matching fund subsidy from the Ministry of Education, Culture, Sports, Science and Technology, 2005–2009.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hamamoto, H., Himei, K., Inoue, S. et al. Microgel-like network polymer precursor formation in free-radical cross-linking multiallyl polymerization. Polym J 42, 923–927 (2010). https://doi.org/10.1038/pj.2010.96
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2010.96