We have presented the first example of the synthesis of macromonomers by mechanochemical reaction of polymethylmethacrylate (PMMA) and maleic anhydride (MA). The mechanochemical reaction of PMMA and MA was carried out by vibratory ball milling under anaerobic condition. The ESR spectrum of the fractured sample of PMMA and MA showed a broad singlet, which was apparently different from the spectrum of PMMA mechanoradical. Therefore, PMMA mechanoradical would react with MA. We underwent the UV-labeling of the fractured samples of PMMA and MA to confirm the formation of macromonomers. The gel permeation chromatograms of UV-labeled compounds derived from this fractured sample showed a broad peak in a polymer region with refractive index detector and UV detector, which indicates that macromonomers bounding MA would be produced. This method seems to be applicable for a wide variety of polymers to synthesize macromonomers possessing MA.
Yokoyama M, Miyauchi M, Yamada N, Okano T, Kataoka K, Inoue S. et al. Polymer micelles as novel drug carrier: adriamycin-conjugated poly(ethylene glycol)-poly(aspartic acid) block copolymer. J Control Rel 1990; 11: 269–78.
Kohori F, Sakai K, Aoyagi T, Yokoyama M, Sakurai Y, Okano T. Preparation and characterization of thermally responsive block copolymer micelles comprising poly (N-isopropylacrylamide-b-DL- lactide). J Control Rel 1998; 55: 87–98.
Yasugi K, Nagasaki Y, Kato M, Kataoka K. Preparation and characterization of polymer micelles from poly(ethylene glycol)-poly(D,L-lactide) block copolymers as potential drug carrier. J Control Rel 1999; 62: 89–100.
Akiyoshi K, Kang E.-C, Kurumada S, Sunamoto J, Principi T, Winnik FM. Controlled association of amphiphilic polymers in water: thermosensitive nanoparticles formed by self-assembly of hydrophobically modified pullulans and poly(N-isopropylacrylamides). Macromolecules 2000; 33: 3244–9.
Katayama Y., Sonoda T., Maeda M. A polymer micelle responding to the protein kinase a signal. Macromolecules 2001; 34: 8569–73.
Kataoka K, Harada A, Nagasaki Y. Block copolymer micelles for drug delivery: design, characterization and biological significance. Adv Drug Deliv Rev 2001; 47: 113–31 and references cited therein.
Savic R, Luo L, Eisenberg A, Maysinger D. Micellar nanocontainers distribute to defined cytoplasmic organelles. Science 2003; 300: 615–8.
Francis M. F., Cristea M., Winnik F. M. Polymeric micelles for oral drug delivery : Why and how. Pure Appl. Chem. 2004; 76: 1321–35, and references cited therein.
Djordjevic J., Barch M., Uhrich K. E. Polymeric micelles based on amphiphilic scorpion-like macromolecules: novel carriers for water-insoluble drugs Pharm Res 2005; 22: 24–32.
Bae Y, Nishiyama N, Fukushima S, Koyama H, Yasuhiro M, Kataoka K. Preparation and biological characterization of polymeric micelle drug carriers with intracellular pH-triggered drug release property: tumor permeability, controlled subcellular drug distribution, and enhanced in vivo antitumor efficacy. Bioconjugate Chem 2005; 16: 122–130.
Ito K. Polymeric design by macromonomer technique . Prog Polym Sci 1998; 23: 581–620.
Ito K, Kawaguchi S. Poly(macromonomers): homo- and copolymerization . Adv Polym Sci 1999; 142: 129–78.
Maniruzzaman M, Kawaguchi S, Ito K. Micellar copolymerization of styrene with poly(ethylene oxide) macromonomer in water: approach to unimolecular nanoparticles via pseudo-liming radical polymerization. Macromolecules 2000; 33: 1583–92.
Kondo S., Kuzuya M. Advances in mechanochemical solid-state polymerization: mechanochemical polymeric prodrug syntheses. Curr. Trends Polym. Sci. 1998; 3: 1–23, and references cited therein.
Kondo S, Hosaka S, Hatakeyama I, Kuzuya M. Mechanochemical solid-State polymerization. IX. theoretical analysis of rate of drug release from powdered polymeric prodrugs in a heterogeneous system. Chem Pharm Bull 1998; 46: 1918–23.
Kondo S, Hatakeyama I, Hosaka S, Kuzuya M. Mechanochemical solid-state polymerization (X) : the influence of copolymer structure in copolymeric prodrugs on the nature of drug release. Chem Pharm Bull 2000; 48: 1882–5.
Kondo S, Sasai Y, Kuzuya M, Furukawa S. Synthesis of water-soluble polymeric prodrugs possessing 4-methylcatechol derivatives by mechanochemical solid-state copolymerization and nature of drug release. Chem Pharm Bull 2002; 50: 1434–8.
Kondo S, Sasai Y, Hosaka S, Ishikawa T, Kuzuya M. Kinetic analysis of the mechanolysis of polymethylmethacrylate in the course of vibratory ball milling at various mechanical energy. J Polym Sci Part A Polym Chem 2004; 42: 4161–7.
Kondo S, Shichijyou D, Sasai Y, Yamauchi Y, Kuzuya M. Synthesis of DNA conjugate by mechanochemical solid-State polymerization and its affinity separation of oligonucleotides having single-base difference by capillary electrophoresis. Chem Pharm Bull 2005; 53: 863–5.
Kondo S, Mori H, Sasai Y, Yamauchi Y, Kuzuya M. Conventional synthesis of amphiphilic block copolymer utilized for polymeric micelle by mechanochemical solid-state polymerization. Chem Pharm Bull 2007; 55: 389–92.
Kondo S, Yamamoto K, Sawama Y, Sasai Y, Yamauchi Y, Kuzuya M. Characterization of novel pH-sensitive polymeric micelles prepared by the self-assembly of amphiphilic block copolymer with poly-4-vinylpyridine block synthesized by mechanochemical solid-state polymerization. Chem Pharm Bull 2011; 59: 1200–2.
Shoma J, Sakaguchi M. ESR studies on polymer radicals produced by mechanical destruction and their reactivity. Adv Polym Sci 1976; 20: 109–58, and references cited therein.
Pilar J, Ulbert K. An ESR study of PMMA mechanoradicals and of their interaction with oxygen. J Polym Sci, Polym Phys Ed 1978; 16: 1973–82.
Sohma J. Mechanochemistry of polymers. J. Prog. Polym. Sci. 1989; 14: 451–596, and references cited therein.
Kuzuya M., Kondo S., Noguchi A., Noda N. Mechanistic Study on Mechanochemical Polymerization of Acrylamide. J Polym Sci, Part A: Polym Chem 1991; 29: 489–94. http://dx.doi.org/10.1002/pola.1991.080290405
Tatar L, Kaptan HY. Computer-simulation analysis of the ESR spectra of mechanoradicals in PMMA. J Polym Sci, Part B: Polym Phys 1997; 35: 2195–200.
Fukaya M, Muto H, Toriyama K, Iwasaki M. Electron spin resonance study of radiation-induced radicals from maleic anhydride in irradiated frozen solutions. J Phys Chem 1976; 80: 728–32.
Tino J., Placek, Pavlinec J. ESR study of mechanically destructed methyl methacrylate-maleic anhydride copolymer. Europ Polym J 1974; 10: 291–4.
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
Copyright (c) 2011 Shin-ichi Kondo , Masashi Tsukamoto , Yasushi Sasai , Yukinori Yamauchi , Masayuki Kuzuya