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Polymerization by Metalloporphyrin and Related Complexes

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Polymer Synthesis/Polymer-Polymer Complexation

Part of the book series: Advances in Polymer Science ((POLYMER,volume 146))

Abstract

This review describes the recent development of the living and immortal polymerizations of various monomers controlled by using as excellent initiators the metalloporphyrins of aluminum, zinc, manganese, and tin. Aluminum porphyrin initiates the living polymerizations of methacrylic esters, acrylic esters, and methacrylonitirile, and the living and immortal polymerizations of epxides, and lactones, affording polymers of very narrow molecular-weight distribution, where the rates of polymerization are much accelerated by the presence of an appropriate Lewis acid as an electrophilic monomer activator. Zinc N-alkyl-porphyrin brings about the living and immortal polymerizations of epoxides and episulfides. Manganese porphyrin also gives polyethers of a fairly narrow molecular-weight distribution by the living and immortal polymerization of epoxides. Tin porphyrin produces poly(methyl methacrylate) via a radical mechanism.

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References and Notes

  1. Smith KM (ed) (1975) Porphyrins and metalloporphyrins. Elsevier, New York

    Google Scholar 

  2. Dolphin D (ed) The porphyrins. Academic Press, New York

    Google Scholar 

  3. Ortiz de Montellano PR (ed) (1986) Cytochrome P-450, structure, mechanism and biochemistry. Plenum Press, New York

    Google Scholar 

  4. Mansuy D (1987) Pure Appl Chem 59:759

    Article  CAS  Google Scholar 

  5. Osa T (ed) (1982) Porufirin no Kagaku. Kyoritsushuppan, Tokyo

    Google Scholar 

  6. Rix CJ (1982) J Chem Educ 59:389

    Article  CAS  Google Scholar 

  7. Poulos TL (1988) Heme Proteins. In: Eichhorn GL, Marzill LG (eds) Adv Inorg Biochem 7:1–36

    Google Scholar 

  8. White RE, Coon MJ (1980) Annu Rev Biochem 49:315

    Article  CAS  Google Scholar 

  9. Deisenhofer J, Epp O, Miki K, Huber R, Michael H (1985) Nature 318:618

    Article  Google Scholar 

  10. Allen JP, Feher, G, Yrates TO, Komiya H, Rees DC (1987) Proc Natl Acad USA 84:5730

    Article  CAS  Google Scholar 

  11. Woodward RB (1973) Pure Appl Chem 33:145

    Article  CAS  Google Scholar 

  12. Collman JP, Gagne RR, Halbert TR, Marchon J-C (1973) J Am Chem Soc 95:7868

    Article  CAS  Google Scholar 

  13. Alworg A, Baldwin JE, Huff J (1975) J Am Chem Soc 97:27

    Article  Google Scholar 

  14. Ogoshi H, Sugimoto H, Yoshida Z (1976) Tetrahedron Lett 4477

    Google Scholar 

  15. Baldwin JE, Klose T, Peters M (1976) J Chem Soc Chem. Commun 881

    Google Scholar 

  16. Collman JP, Brauman JI, Doxsee KM, Halbert TR, Bunnenberg E, Linder RE, Lamar GN, Gaudio JD, Lang G, Spartalian KJ (1980) Am Chem Soc 102:4182

    Article  CAS  Google Scholar 

  17. Chang, CK (1977) J Am Chem Soc 99:2819

    Article  CAS  Google Scholar 

  18. Chang CK,T raylor TG (1973) Proc Natl Acad Sci USA 50:951

    Google Scholar 

  19. Collman JP, Suslick KS (1978) Pure Appl Chem 50:951

    Article  CAS  Google Scholar 

  20. Traylor TG Acc Chem Rev 1981, 14, 102

    Article  CAS  Google Scholar 

  21. Yoshida Z (1984) Heterocycles 21:331

    Article  CAS  Google Scholar 

  22. Tsuchida E, Nishide H (1986) Top Curr Chem 132:63

    Article  CAS  Google Scholar 

  23. Tabushi I (1988) Coord Chem Rev 86:1

    Article  CAS  Google Scholar 

  24. Aida T, Mizuta R, Yoshida Y, Inoue S (1981) Makromol Chem 182:1073

    Article  CAS  Google Scholar 

  25. Yasuda T, Aida T, Inoue S (1982) Makromol Chem Rapid Commun 3:585

    Article  CAS  Google Scholar 

  26. Yasuda T, Aida T, Inoue S (1984) Macromolecules 17:2217

    Article  CAS  Google Scholar 

  27. Endo M, Aida T, Inoue S (1987) Macromolecules 20:2982

    Article  CAS  Google Scholar 

  28. Shimasaki K, Aida T, Inoue S (1987) Macromolecules 20:3076

    Article  CAS  Google Scholar 

  29. Trofimoff LR, Aida T, Inoue S (1987) Chem Lett 991

    Google Scholar 

  30. Sugimoto H, Aida T, Inoue S (1990) Macromolecules 23:2869

    Article  CAS  Google Scholar 

  31. Kuroki M, Aida T, Inoue S (1987) J Am Chem Soc 109:4737

    Article  CAS  Google Scholar 

  32. Hosokawa Y, Kuroki M, Aida T, Inoue S (1991) Macromolecules 24:824

    Article  CAS  Google Scholar 

  33. Kuroki M, Watanabe T, Aida T, Inoue S (1991) J Am Chem Soc 113:5903

    Article  CAS  Google Scholar 

  34. Sugimoto H, Kuroki M, Watanabe T, Kawamura C, Aida T, Inoue S (1993) Macromolecules 26:3403

    Article  CAS  Google Scholar 

  35. Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:4751

    Article  CAS  Google Scholar 

  36. For brief reviews: (a) Sugimoto H, Aida T, Inoue S (1995) Bull Chem Soc Jpn 68:1239

    Article  Google Scholar 

  37. Sugimoto H, Inoue S (1998) Polymer News, in press

    Google Scholar 

  38. The assignment was made according to: Maruoka K, Araki Y, Yamamoto HJ (1988) J Am Chem Soc 110:2650 (Supplementary material)

    Article  Google Scholar 

  39. A small shoulder was observed on the higher-molecular-weight side of the main peak in GPC

    Google Scholar 

  40. Sugimoto H, Aida T, Inoue S (1994) Macromolecules 27:3672

    Article  CAS  Google Scholar 

  41. Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:4751

    Article  CAS  Google Scholar 

  42. From the relative intensity of the OCH3 signals of MMA (δ 3.75 ppm) to the polymer (δ 3.65)

    Google Scholar 

  43. The green color is typically observed for the axial ligand-exchange reaction of (TPP)AlCl with KF (unpublished results)

    Google Scholar 

  44. Sugimoto H, Kuroki M, Watanabe T, Kawamura C, Aida T, Inoue S (1998) Macromolecules in press

    Google Scholar 

  45. Kuroki M, Watanabe T, Aida T, Inoue S (1991) J Am Chem Soc 113:5903

    Article  CAS  Google Scholar 

  46. Adachi T, Sugimoto H, Aida T, Inoue S (1992) Macromolecules 25:2280

    Article  CAS  Google Scholar 

  47. Adachi T, Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:1238

    Article  CAS  Google Scholar 

  48. Guilard R, Zrineh A, Tabard A, Endo A, Hau BC, Lecomte C, Souhassou M, Habbou A, Ferhat M, Kadish KM (1990) Inorg Chem 29:4476. 1H NMR in C6D6 [C6H6 (δ 7.40) as internal standard: δ 9.34 (pyrrole-β-H, 8H, s), 8.27 (Ph-o-H, 8H, d), 7.68 (Ph-m, p-H, 12H, m), 6.08 (Al-Ph-p-H, 1H, t), 5.83 (Al-Ph-m-H, 2H, t), and 2.73 (Al-Ph-o-H, 2H, t)

    Article  CAS  Google Scholar 

  49. Adachi T, Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:1238

    Article  CAS  Google Scholar 

  50. 1c also initiates the living polymerization of tert-butyl acrylate even in the dark:Hosokawa Y, Kuroki M, Aida T, Inoue S (1992) Macromolecules 25:824

    Google Scholar 

  51. Adachi T, Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:1238

    Article  CAS  Google Scholar 

  52. Ute K, Nishimura T, Hatada K (1989) Polymer J 21:1027

    Article  CAS  Google Scholar 

  53. The selection of the wavelength for UV detection was based on the λmax of thioanisole in THF

    Google Scholar 

  54. Even when PMMA prepared with 1a was mixed with benzenethiol prior to GPC analysis, no UV response was observed for the polymer fraction, where benzenethiol eluted very late and the peak was perfectly separated from that of the polymer

    Google Scholar 

  55. Adachi T, Sugimoto H, Aida, T, Inoue S (1992) Macromolecules 25:2280

    Article  CAS  Google Scholar 

  56. Adachi T, Sugimoto H, Aida T, Inoue S (1992) Macromolecules 25:2280

    Article  CAS  Google Scholar 

  57. Sugimoto H, Saika M, Hosokawa,Y, Aida,T, Inoue S (1996) Macromolecules 29:3359

    Article  CAS  Google Scholar 

  58. Feit B-A, Heller E, Zilkha A (1966) J Polym Sci Part A-1 4:1151

    Google Scholar 

  59. Beaman RC (1948) J Am Chem Soc 70:3115

    Article  CAS  Google Scholar 

  60. Rempp P, Blumstein A (1961) Bull Soc Chim Fr 1018

    Google Scholar 

  61. Overberger CG, Yuki H, Urakawa N (1960) J Polym Sci 45:127

    Article  CAS  Google Scholar 

  62. Feit B-A, Mirelman D, Zilkha A (1964) J Polym Sci Part A-1 2:4743

    Google Scholar 

  63. Overberger CG, Pearce EM, Mayes N (1958) J Polym Sci 31:217

    Article  Google Scholar 

  64. Zilkha A, Feit B-A, Frankel M (1961) J Polym Sci 49:231

    Article  CAS  Google Scholar 

  65. Feit B-A, Direlman D, Zilkha A (1965) J Appl Polym Sci 9:2459

    Article  CAS  Google Scholar 

  66. Webster OW, Hertler WR, Sogah DY, Farnham WB, RajanBabu TV (1983) J Am Chem Soc 105:5706

    Article  CAS  Google Scholar 

  67. Sugimoto H, Aida T, Inoue S (1995) Bull Chem Soc Jpn 68:1239

    Article  CAS  Google Scholar 

  68. Kuroki M, Watanabe T, Aida T, Inoue S (1991) J Am Chem Soc 113:5903

    Article  CAS  Google Scholar 

  69. Sugimoto H, Kuroki M, Watanabe T, Kawamura C, Aida T, Inoue S (1993) Macromolecules 26:3403

    Article  CAS  Google Scholar 

  70. Adachi T, Sugimoto H, Aida T, Inoue S (1992) Macromolecules 25:2280

    Article  CAS  Google Scholar 

  71. Adachi T, Sugimoto H, Aida T, Inoue S (1993) Macromolecules 26:1238

    Article  CAS  Google Scholar 

  72. Takeda N, Inoue S (1977) Bull Chem Soc Jpn 50:984

    Article  Google Scholar 

  73. Aida T, Inoue S (1983) J Am Chem Soc 105:1304

    Article  CAS  Google Scholar 

  74. Hirai Y, Aida T, Inoue S (1989) J Am Chem Soc 111:3062

    Article  CAS  Google Scholar 

  75. Bovey FA, Tiers GVD (1960) J Polym Sci 44:173

    Article  CAS  Google Scholar 

  76. Yuki H, Hatada K, Nimori T, Kikuchi Y (1970) Polym J 1:36

    Article  CAS  Google Scholar 

  77. The effect of visible light on the propagating step was also observed for the polymerization of MMA [12]; however, the acceleration effect for the polymerization of MAN was much more remarkable

    Google Scholar 

  78. Aida T, Mizuta R, Yoshida Y, Inoue S (1981) Makromol Chem 182:1073

    Article  CAS  Google Scholar 

  79. Yasuda T, Aida T, Inoue S (1982) Makromol Chem Rapid Commun 3:585

    Article  CAS  Google Scholar 

  80. Yasuda T, Aida T, Inoue S (1984) Macromolecules 17:2217

    Article  CAS  Google Scholar 

  81. Endo M, Aida T, Inoue S (1987) Macromolecules 20:2982

    Article  CAS  Google Scholar 

  82. Shimasaki K, Aida T, Inoue S (1987) Macromolecules 20:3076

    Article  CAS  Google Scholar 

  83. Trofimoff LR, Aida T, Inoue S (1987) Chem Lett 991

    Google Scholar 

  84. Sugimoto H, Aida T, Inoue S (1990) Macromolecules 23:2869

    Article  CAS  Google Scholar 

  85. Kuroki M, Aida T, Inoue S (1987) J Am Chem Soc 109:4737

    Article  CAS  Google Scholar 

  86. Hosokawa Y, Kuroki M, Aida T, Inoue S (1991) Macromolecules 24:824

    Article  CAS  Google Scholar 

  87. Kuroki M, Watanabe T, Aida T, Inoue S (1991) J Am Chem Soc 113:5903

    Article  CAS  Google Scholar 

  88. Sugimoto H, Kuroki M, Watanabe T, Kawamura C (1993) Macromolecules 26:3403

    Article  CAS  Google Scholar 

  89. Sugimoto H, Kuroki M, Kawamura C, Aida T, Inoue S (1994) Macromolecules 27:2013

    Article  CAS  Google Scholar 

  90. Vincens V, Le Borgne A, Spassky N (1989) Makromol Chem Rapid Commun 10:623

    Article  CAS  Google Scholar 

  91. Vincens V, Le Borgne A, Spassky N (1992) In: Vandenberg EJ, Salamone JC (eds) Catalysis in polymer synthesis. ACS Symp Ser No. 496, chap 16, p 205

    Google Scholar 

  92. Le Borgne A, Vincens V, Jouglard M, Spassky N (1993) Makromol Chem Macromol Symp 73:37

    Google Scholar 

  93. Akatsuka M, Aida T, Inoue S (1994) Macromolecules 27:2820

    Article  CAS  Google Scholar 

  94. For immortal polymerizations: (a) Asano S, Aida T, Inoue S (1985) J Chem Soc Chem Commun 1148

    Google Scholar 

  95. Aida T, Maekawa Y, Asano S, Inoue S (1988) Macromolecules 21:1195

    Article  CAS  Google Scholar 

  96. Endo M, Aida T, Inoue S (1987) Macromolecules 20:2982

    Article  CAS  Google Scholar 

  97. Thanabal V, de Ropp JS, La Mar GN (1987) J Am Chem Soc 109:265

    Article  CAS  Google Scholar 

  98. Arai T, Inoue S (1990) Tetrahedron 46:749

    Article  CAS  Google Scholar 

  99. Takeuchi D, Watanabe Y, Aida T, Inoue S (1995) Maclomolecules 28:651

    Article  CAS  Google Scholar 

  100. Recent reviews: (a) Aida T (1994) Prog Polym Sci 19:469

    Article  Google Scholar 

  101. Inoue S, Aida T (1998) Controlled polymer synthesis with metalloporphyrins. In: Vogl O, Hatada K (eds) Molecular design of polymeric materials. Dekker, New York, in press

    Google Scholar 

  102. Kuroki M, Watanabe T, Aida T, Inoue S (1991) J Am Chem Soc 113:5903

    Article  CAS  Google Scholar 

  103. Sugimoto H, Kuroki M, Watanabe T, Kawamura C, Aida T, Inoue S (1993) Macromolecules 26:3403

    Article  CAS  Google Scholar 

  104. Sugimoto H, Aida T, Inoue S (1994) Macromolecules 27:3672

    Article  CAS  Google Scholar 

  105. Sugimoto H, Kawamura C, Kuroki M, Aida T, Inoue S (1994) Macromolecules 27:2013

    Article  CAS  Google Scholar 

  106. Akatsuka M, Aida T, Inoue S (1994) Macromolecules 27:2820

    Article  CAS  Google Scholar 

  107. Inoue, S, Aida T (1994) Chemtech 24:28

    CAS  Google Scholar 

  108. A part of the present work was presented at the 43rd Annual Meeting of the Society of Polymer Science, Japan (May 1994, Nagoya): Polymer Prepr. Jpn. 1994, 43, 171. Concurrently, Amass et al. reported the polymerization of oxetane with (TPP)AlCl (1) alone at 55 °C: Amass AJ, Perry MC, Riat DS, Tighe BJ, Colclough E, Steward M (1994) J Eur Polym J 30(5):641

    Article  Google Scholar 

  109. Isoda M, Sugimoto H, Aida T, Inoue S (1997) Macromolecules 30:57

    Article  CAS  Google Scholar 

  110. Yasuda T, Aida T, Inoue S (1982) Makromol Chem Rapid Commun 3:585

    Article  CAS  Google Scholar 

  111. Yasuda T, Aida T, Inoue S (1986) Bull Chem Soc Jpn 59:3931

    Article  CAS  Google Scholar 

  112. Sugimoto H, Aida T, Inoue S (1990) Macromolecules 23:2869

    Article  CAS  Google Scholar 

  113. Endo M, Aida T, Inoue S (1987) Macromolecules 20:2982

    Article  CAS  Google Scholar 

  114. Shimasaki K, Aida T, Inoue S (1987) Macromolecules 20:3076

    Article  CAS  Google Scholar 

  115. For transesterification of polylactone, see: (a) Nobutoki K, Sumitomo H (1967) Bull Chem Soc Jpn 40:1741

    Article  Google Scholar 

  116. Perret R, Skoulious A (1972) Makromol Chem 152:291

    Article  CAS  Google Scholar 

  117. Kricheldorf HR, Mang T, Jont JM (1984) Macromolecules 17:2173

    Article  CAS  Google Scholar 

  118. Kricheldorf HR, Berl M, Scharnagl N (1988) Macromolecules 21:286

    Article  CAS  Google Scholar 

  119. Kricheldorf HR, Kreiser I (1987) J Macromol Sci Chem A24(11):1345

    Article  CAS  Google Scholar 

  120. Kricheldorf HR, Kreiser I, Scharnagl N (1990) Makromol Chem Macromol Symp 32:285

    CAS  Google Scholar 

  121. Aida T, Kawaguchi K, Inoue S (1990) Macromolecules 23:3887

    Article  CAS  Google Scholar 

  122. Watanebe Y, Aida T, Inoue S (1990) Macromolecules 23:2612

    Article  Google Scholar 

  123. The distributions of isotactic (I) and syndiotactic (s) diad together with isotactic (I), heterotactic (H) and syndiotactic (S) triad sequences were determined from the resonances due to methylene and methine carbons: Oguni N, Lee K, Tani H (1972) Macromolecules 5:819

    Article  Google Scholar 

  124. Asano S, Aida T, Inoue S (1985) J Chem Soc Chem Commun 1148

    Google Scholar 

  125. Aida T, Maekawa Y, Asano, S, Inoue S (1988) Macromolecules 21:1195

    Article  CAS  Google Scholar 

  126. Inoue, S, Aida T (1986) Makromol Chem Macromol Symp 6:217

    CAS  Google Scholar 

  127. Watanebe Y, Aida T, Inoue S (1991) Macromolecules 24:3970

    Article  Google Scholar 

  128. Sigwalt P, Spassky N (1984) In: Ivin KJ, Saegusa T (eds) Ring-opening polymerization, vol 2. Elsevier, London, p 685

    Google Scholar 

  129. Kuznetsov, Yu P, Glumova TD, Polotskaya GA, Belonovskaya GP (1981) Vysokomol. Soedin Ser A 23:2217

    Google Scholar 

  130. Watanabe Y, Aida T, Inoue S (1990) Macromolecules 23:2612

    Article  CAS  Google Scholar 

  131. Aida T, Kawaguchi K, Inoue S (1990) Macromolecules 23:3887

    Article  CAS  Google Scholar 

  132. Kuroki M, Aida T, Inoue S (1988) Makromol Chem 189:1305

    Article  CAS  Google Scholar 

  133. Yamaguchi C, Sugimoto H, Inoue S unpublished results

    Google Scholar 

  134. Wayland BB, Poszmik G, Mukerjee SL, Fryd MJ (1994) J Am Chem Soc 116:7493

    Article  Google Scholar 

  135. Dawson DY, Sangalang JC, Arnold J (1996) J Am Chem Soc 118:6082

    Article  CAS  Google Scholar 

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  1. Department of Industrial Chemistry, Faculty of Engineering, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo, 162-8601, Japan

    Hiroshi Sugimoto & Shohei Inoue

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  1. Hiroshi Sugimoto
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  2. Shohei Inoue
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S. Inoue S. Jacob M. Jiang J. P. Kennedy M. Li H. Sugimoto M. Xiang H. Zhou

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Sugimoto, H., Inoue, S. (1999). Polymerization by Metalloporphyrin and Related Complexes. In: Inoue, S., et al. Polymer Synthesis/Polymer-Polymer Complexation. Advances in Polymer Science, vol 146. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-49424-3_2

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  • DOI: https://doi.org/10.1007/3-540-49424-3_2

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