Skip to main content
SpringerLink
Log in

Organo Rare Earth Metal Catalysis for the Living Polymerizations of Polar and Nonpolar Monomers

  • Chapter
  • First Online:
Lanthanides: Chemistry and Use in Organic Synthesis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 2))

Abstract

This article deals with the rare earth metal initiated polymerization of polar and nonpolar monomers in a living fashion. For example, [SmH(C5Me5)2]2 or LnMe(C5Me5)2(THF) (Ln= Sm, Y and Lu) conducted the polymerization of methyl methacrylate(MMA) to give high molecular weight syndiotactic polymers (M n>500,000, syndiotacticity>95%) quantitatively at low temperature (-95 °C). The initiation mechanism was discussed on the basis of X-ray analysis of the 1:2 adduct of [SmH(C5Me5)2]2 with MMA. Synthesis of high molecular weight isotactic poly(MMA) with very narrow molecular weight distribution was for the first time realized by the efficient catalytic function of Yb[C(SiMe3)3]2. Living polymerizations of alkyl acrylates (methyl acrylate, ethyl acrylate, and butyl acrylate) were also possible by the excellent catalysis of LnMe(C5Me5)2(THF) (Ln=Sm, Y). By taking advantages of the living polymerization ability, we attempted ABA triblock copolymerization of MMA/butyl acrylate/MMA to obtain rubber-like elastic polymers. Organo rare earth metal complexes such as LnOR(C5R5)2 or LnR(C5R5)2 conducted the living polymerizations of various lactones such as β-propiolactone, δ-valerolactone and ε-caprolactone, and also conducted the block copolymerizations of MMA with various lactones. Lanthanum alkoxide(III) has good catalytic activity for the polymerization of alkyl isocyanates. Monodisperse polymerizations of lactide and various oxiranes were also achieved by the use of rare earth metal complexes. C 1 symmetric bulky organolanthanide(III) complexes such as SiMe2[2(3),4-(SiMe)2C5H2]2LnCH(SiMe3)2 (Ln=La, Sm, and Y) show high catalytic activity towards linear polymerization of ethylene.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 259.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 329.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 329.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Klein JW, Lamps JP, Gnaonou Y, Remp P (1991) Polymer 32:2278

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. Sogah DY, Hertler WR, Webster OW, GM Cohen (1987) Macromolecules 20:1473

    Article  CAS  Google Scholar 

  4. Yasuda H, Yamamoto H, Yokota K, Miyake S, Nakamura A (1992) J Am Chem Soc 114:4908

    Article  CAS  Google Scholar 

  5. Yasuda H, Yamamoto H, Takemoto Y, Yamashita M, Yokota K, Miyake S, Nakamura A (1993) Makromol Chem Macromol Symp 67:187

    CAS  Google Scholar 

  6. Yasuda H, Yamamoto H, Yamashita M, Yokota K, Nakamura A, Miyake S, Kai Y, Kanehisa N (1993) Macromolecules 22:7134

    Article  Google Scholar 

  7. Yasuda H, Tamai H (1993) Prog Polym Sci 18:1097

    Article  CAS  Google Scholar 

  8. Yasuda H, Ihara E (1997) Adv Polym Sci 133:53

    Article  CAS  Google Scholar 

  9. Ihara E, Morimoto M, Yasuda H (1995) Macromolecules 28:7886

    Article  CAS  Google Scholar 

  10. Yamashita M, Takemoto Y, Ihara E, Yasuda H (1996) Macromolecules 29:1798

    Article  CAS  Google Scholar 

  11. Tanaka K, Ihara E, Yasuda H (1996) (unpublished results)

    Google Scholar 

  12. Szwarc M (1983) Adv Polym Sci 49:1

    Article  Google Scholar 

  13. Nakahama S, Hirao A (1990) Prog Polym Sci (1990) 13:299

    Article  Google Scholar 

  14. Inoue S (1988) Macromolecules 21:1195

    Article  Google Scholar 

  15. Sawamoto M, Okamoto O, Higashimura T (1987) Macromolecules 20:2693

    Article  CAS  Google Scholar 

  16. Ko-jima K, Sawamoto M, Higashimura T (1988) Macromolecules 21:1552

    Google Scholar 

  17. Gillon LR, Grubbs RH (1986) J Am Chem Soc (1986) 108:733

    Article  Google Scholar 

  18. Grubbs RH, Tumas W (1989) Science 243:907

    Article  CAS  Google Scholar 

  19. Schrock RR, Feldman J, Canizzo LF, Grubbs RH (1989) Macromolecules 20:1169

    Article  Google Scholar 

  20. Cao ZK, Okamoto Y, Hatada K ( 1986) Kobunshi Ronbunshu 43:857

    CAS  Google Scholar 

  21. Joh Y, Kotake Y (1976) Macromolecules 3:337

    Article  Google Scholar 

  22. Hatada K, Nakanishi H, Ute K, Kitayama T (1986) Polym J 18:581

    Article  CAS  Google Scholar 

  23. Abe H, Imai K, Matsumoto M (1968) J Polym Sci C23:469

    Google Scholar 

  24. Nakano N, Ute K, Okamoto Y, Matsuura Y, Hatada K (1989) Polym J 21:935

    Article  CAS  Google Scholar 

  25. Bawn CEH, Ledwith A (1962) Quart Rev Chem Soc 16:361

    Article  CAS  Google Scholar 

  26. Cram DJ, Kopecky KR (1959) J Am Chem Soc 81:2748

    Article  CAS  Google Scholar 

  27. Hatada K, Ute K, Tanaka Y, Kitayama T, Okamoto (1986) Polym J 18:1037

    Article  CAS  Google Scholar 

  28. Nitto Y, Hayakawa T, Ihara E, Yasuda H (1998) (unpublished result)

    Google Scholar 

  29. Yamamoto Y, Giardello MA, Brard L, Marks TJ (1995) J Am Chem Soc 117:3726

    Google Scholar 

  30. Boffa LS, Novak BM (1994) Macromolecules 27:6993

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  32. Aida T, Inoue S (1996) Acc Chem Res 29:39

    Article  CAS  Google Scholar 

  33. Sun J, Wang G, Shen Z (1993)Yingyong Huaxue 10:1

    CAS  Google Scholar 

  34. Collins S, Ward DG, Suddaby KH (1994) Macromolecules 27:7222

    Article  CAS  Google Scholar 

  35. Soga K, Deng H, Yano T, Shiono T (1994) Macromolecules 27:7938

    Article  CAS  Google Scholar 

  36. Hosokawa Y, Kuroki M, Aida T, Inoue S (1991) Macromolecules 24:8243

    Article  Google Scholar 

  37. Ihara E, Morimoto M, Yasuda H (1996) Proc Japan Acad 71:126

    Article  Google Scholar 

  38. Ihara E, Mori-moto M, Yasuda H (1995) Macromolecules 28:7886

    Article  CAS  Google Scholar 

  39. Suchoparek M, Spvacek J (1993) Macromolecules 26:102

    Article  CAS  Google Scholar 

  40. Madruga EL, Roman JS, Rodriguez MJ (1983) J Polym Sci Polym Chem Ed 21: 2739

    Article  CAS  Google Scholar 

  41. Kakehi T, Yasuda H (1997) (unpublished result)

    Google Scholar 

  42. Patten TE, Novak BM (1991) J Am Chem Soc 113:5065

    Article  CAS  Google Scholar 

  43. Patten TE, Novak BM (1993) Makromol Chem Macromol Symp 67:203

    CAS  Google Scholar 

  44. Fukuwatari N, Sugimoto H, Inoue S (1996) Macromol Rapid Commun 17:1

    Article  CAS  Google Scholar 

  45. Tanaka K, Ihara E, Yasuda H (1998) (unpublished result)

    Google Scholar 

  46. Hofman A, Szymanski R, Skomkowski S, Penczek S (1980) Makromol Chem 185:655

    Article  Google Scholar 

  47. Agostini DE, Lado JB, Sheeton JR (1971) J Polym Sci A1:2775

    Google Scholar 

  48. Cherdran H, Ohse H, Korte F (1962) Makromol Chem 56:187

    Article  Google Scholar 

  49. Evans JE, Shreeve JL, Doedens RJ (1993) Inorg Chem 32:245

    Article  CAS  Google Scholar 

  50. Zhang Y, Chen X, Shen Z (1989) Inorg Chim Acta 155:263

    Article  CAS  Google Scholar 

  51. Wu J, Shen Z (1990) J Polym Sci Polym Chem Ed 28:1995

    Article  CAS  Google Scholar 

  52. Itoh H, Shirahama H, Yasuda H (1998) (unpublished results)

    Google Scholar 

  53. Shen Z, Wu J, Wang G (1990) J Polym Sci Polym Chem Ed 28:1965

    Article  CAS  Google Scholar 

  54. Wu J, Shen Z (1990) Polymer J 22:326

    Article  CAS  Google Scholar 

  55. Inoue S, Tsuruta T (1969) J Polym Sci Polym Lett Ed 7:287

    CAS  Google Scholar 

  56. Kobayashi M., Inoue S, Tsurtuta T ( 1973) J Polym Sci Polym Chem Ed 11:2383

    Article  CAS  Google Scholar 

  57. Shen X, Zhang Y, Shen Z (1994) Chinese J Polym Sci 12:28

    Google Scholar 

  58. Shen Z, Chen X, Zhang Y (1994) Macromol Chem Phys 195:2003

    Article  CAS  Google Scholar 

  59. Machoon JP, Sigwalt P (1965) Compt Rend 260:549

    Google Scholar 

  60. Belonovskaja GP (1979) Europ Polym J 15:185

    Article  Google Scholar 

  61. Dumas P, Spassky N, Sigwalt P (1972) Makromol Chem 156:65

    Article  CAS  Google Scholar 

  62. Guerin PB, Sigwalt P (1974) Eur Polym J 10:13

    Article  CAS  Google Scholar 

  63. Shen Z, Zhang Y, Pebg J, Ling L (1990) Sci China 33:553

    CAS  Google Scholar 

  64. Shen Z, Sun J, Wu Li, Wu L (1990) Acta Chim Sinica 48:686

    CAS  Google Scholar 

  65. Yao Y, Shen Q (private communication)

    Google Scholar 

  66. Stevels WM, Ankone JK, Dijkstra PJ, Feijen J (1996) Macromolecules 29:3332

    Article  CAS  Google Scholar 

  67. Shen Y, Zhang F, Zhang Y, Shen Z (1995) Acta Polym Sinica 5:222

    Google Scholar 

  68. Yasuda H, Ihara E (1993) J Synth Org Chem Jpn 51:931

    CAS  Google Scholar 

  69. Yasuda H, Ihara E, Yosh-ioka S, Nodono M, Morimoto M, Yamashita M ( 1994) Catalyst design for tailor-made polyolefins. Kodansha-Elsevierp, p237

    Google Scholar 

  70. Nodono M, Ihara E, Yasuda H (unpublished result)

    Google Scholar 

  71. Fu P, Marks TJ (1995) J Am Chem Soc 117:10,747

    Article  CAS  Google Scholar 

  72. Ihara E, Nodono M, Yasuda H, Kanehisa N, Kai Y (1996) Macromol Chem Phys 197:1909

    Article  CAS  Google Scholar 

  73. Evans WJ, Ulibbari TA, Ziller JW ( 1988) J Am Chem Soc 110:6877

    Article  CAS  Google Scholar 

  74. Evans WJ, Ulibbari TA, Ziller JW ( 1990) J Am Chem Soc 112:219

    Article  CAS  Google Scholar 

  75. Lang DP, Bianconi PA (1996) J Am Chem Soc 118:52,453

    Google Scholar 

  76. Yasuda H, Furo M, Yamamoto H, Nakamra A, Miyake S, Kibino N (1992) Macromolecules 25:5115

    Article  CAS  Google Scholar 

  77. Yang Y, Seyam AM, Fuad PF Marks TJ (1994) Macromolecules 27:4625

    Article  CAS  Google Scholar 

  78. Yang M, Chan C, Shen Z (1990) Polym J 22:919

    Article  CAS  Google Scholar 

  79. Kobayashi E, Aida S, Aoshima S, Furukawa J (1994) J Polym Sci Polym Chem Ed 32:1195

    Article  CAS  Google Scholar 

  80. Hayakawa T, Ihara E, Yasuda H (1995) 69th National Meeting of Chem Soc Jpn 2B530

    Google Scholar 

  81. Cheng XC, Shen Q ( 1993) Chinese Chem Lett 4:743

    CAS  Google Scholar 

  82. Hu J, Shen Q (1993) Cuihua Xuebao 11:16

    Google Scholar 

  83. Tanaka K, Yasuda H (1997) (unpublished result)

    Google Scholar 

  84. Ishihara N, Seimiya T, Kuramoto M, Uoi M (1986) Macromolecules 19:2464

    Article  CAS  Google Scholar 

  85. Ishihara N, Kuramoto M, Uoi M (1988) Macromolecules 21: 3356

    Article  CAS  Google Scholar 

  86. Yu G, Chen W, Wang Y (1981) Kexue Tongabo 29:412

    Google Scholar 

  87. Ji X, Png S, Li Y, Ouyang J (1986) Scientia Sinica 29:8

    CAS  Google Scholar 

  88. Jin S, Guan J, Liang H, Shen Q (1993) J Catalysis (Cuihua Xuebao) 159:14

    Google Scholar 

  89. Hu J, Liang H, Shen Q (1993) J Rare Earths 11:304

    Google Scholar 

  90. Jin Y, Li F, Pei F, Wang F, Sun Y (1994) Macromolecules 27:4397

    Article  CAS  Google Scholar 

  91. Li F, Jin Y, Pei K, Wang F (1994) J Macromol Sci Pure Appl Chem A31:273

    CAS  Google Scholar 

  92. Jin Y, Li X, Sun Y, Ouyang J (1982) Kexue Tongbai] 27:1189

    Google Scholar 

  93. Jin Y, Li X, Lin Y, Jin S, Shi E, Wang M (1989) Chinese Sci Bull 34:390

    CAS  Google Scholar 

  94. Ricci G, Boffa G, Porri L ( 1986) Makromol Chem Rapid Commun 7:355

    Article  CAS  Google Scholar 

  95. Natta G, Polli L (1966) Adv Chem Ser 52:24

    Article  Google Scholar 

  96. Wong F (1994) J Macromol Sci Pure Appl Chem A31:273

    Google Scholar 

  97. Li X, Sun Y, Jin Y ( 1986) Acta Chim Sinica 44:1163

    CAS  Google Scholar 

  98. Hu Y, Ze L, Shen Q (1993) J Rare Earths 11:304

    Google Scholar 

  99. Lee DH, Wang JK, Ahn TO (1987) J Polym Sci Polym Chem Ed 25:1407

    Google Scholar 

  100. Lee DH, Ahn TO (1988) Polymer 29:71

    Google Scholar 

  101. Wang P, Jin Y, Pei F, Jing F, Sun Y (1994) Acta Polym Sinica 4:392

    Google Scholar 

  102. Ito T, Shirakawa H, Ikeda S (1974) J Polym Sci Polym Chem Ed 12:11

    Article  CAS  Google Scholar 

  103. Luttinger LB (1962) J Org Chem 27:159

    Google Scholar 

  104. Shen Z, Wang Z, Can Y (1985) Inorg Chim Acta 110:55

    Article  CAS  Google Scholar 

  105. Shen Z, Yang M, Shi M, Cai Y (1982) J Polym Sci Polym Chem Ed 20:411

    CAS  Google Scholar 

  106. Shen Z, Yu L, Yang M (1984) Inorg Chim Acta 109: 55

    Google Scholar 

  107. Hu X, Wang F, Zhao X, Yan D (1987) Chin J Polym Sci 5: 221

    Google Scholar 

  108. Zhao J, Yang M, Yuan Y, Shen Z (1988) Zhonggono Xitu Xuebao 6:17

    CAS  Google Scholar 

  109. Shen Z, Farona MF (1984) J Polym Sci Polym Chem Ed 22:1009

    Article  CAS  Google Scholar 

  110. Shen Z, Farona MF (1983) Polym Bull 10:298

    Article  CAS  Google Scholar 

  111. Mullagaliev IR, Mudarisova RK (1988) Izv Akad Nai]k SSSR Ser Khim 7:1687

    Google Scholar 

  112. HeersH J, Teuben JH (1991) Organometallics 10:1980

    Article  Google Scholar 

  113. Akita M, Yasuda H, Nakamura A (1984) Bull Chem Soc Jpn 57:480

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, Higashi-Hiroshima, 739-8527, Japan

    Hajime Yasuda

Authors
  1. Hajime Yasuda
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan

    Shū Kobayashi

Rights and permissions

Reprints and permissions

Copyright information

© 1999 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Yasuda, H. (1999). Organo Rare Earth Metal Catalysis for the Living Polymerizations of Polar and Nonpolar Monomers. In: Kobayashi, S. (eds) Lanthanides: Chemistry and Use in Organic Synthesis. Topics in Organometallic Chemistry, vol 2. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-69801-9_7

Download citation

  • DOI: https://doi.org/10.1007/3-540-69801-9_7

  • Published:

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-64526-9

  • Online ISBN: 978-3-540-69801-2

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation