Skip to main content
SpringerLink
Log in

Methylaluminoxane: Key Component for New Polymerization Catalysts

  • Chapter
  • First Online:
Polyolefins: 50 years after Ziegler and Natta II

Part of the book series: Advances in Polymer Science ((POLYMER,volume 258))

Abstract

The use of methylaluminoxane (MAO) as cocatalyst for the polymerization of olefins and some other vinyl compounds has widely increased the possibilities for more precisely controlling the polymer composition, polymer structure, tacticity, and special properties. Highly active catalysts are obtained by different transition metal complexes such as metallocenes, half-sandwich complexes, and bisimino complexes combined with MAO. These catalysts allow the synthesis of polyolefins with different tacticities and stereoregularities, new cycloolefins and other copolymers, and polyolefin composite materials of a purity that cannot be obtained by Ziegler–Natta catalysts. The single-site character of metallocene/MAO or other transition metal/MAO catalysts leads to a better understanding of the mechanism of olefin polymerization.

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 EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
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

Abbreviations

Ac:

Acetyl

Bu:

Butyl

CNF:

Carbon nanofiber

Cp:

Cyclopentadienyl

Cp*:

Pentamethyl cyclopentadienyl

En:

Ethylidene

Et:

Ethyl

Flu:

Fluorenyl

Ind:

Indenyl

IndH4 :

Tetrahydro indenyl

MAO:

Methylaluminoxan

Me:

Methyl

M w/M n :

Molecular weight distribution

MWCNT:

Multiwalled carbon nanotube

Naph:

Naphthyl

NmCp:

Neomenthyl cyclopentadienyl

NMR:

Nuclear magnetic resonance

PE:

Polyethylene

Ph:

Phenyl

PP:

Polypropylene

tBu:

Tertiary-butyl

TEM:

Transmission electron microscopy

TIBA:

Triisobuthyl aluminum

TMA:

Trimethylaluminum

References

  1. Ziegler K, Holzkamp E, Breil H, Martin H (1955) Angew Chem 67:541

    CAS  Google Scholar 

  2. Breslow DS, Newburg NR (1957) J Am Chem Soc 79:5072

    CAS  Google Scholar 

  3. Natta G, Pino P, Mazzanti G, Longi P (1957) Gazz Chim Ital 87:549

    CAS  Google Scholar 

  4. Patat F, Sinn H (1958) Angew Chem 70:496

    CAS  Google Scholar 

  5. Shilov AE (1960) Dok Akad Nauk SSS 132:599

    Google Scholar 

  6. Henrici-Olivé G, Olivé S (1969) J Organomet Chem 16:339

    Google Scholar 

  7. Reichert KH, Schoetter E (1968) Z Phys Chem 57:74

    CAS  Google Scholar 

  8. Fink G, Rottler R (1981) Angew Makromol Chem 94:2

    Google Scholar 

  9. Waters JA, Mortimer GA (1972) J Polym Sci A1 10:895–907

    Google Scholar 

  10. Chien JCW (1959) J Am Chem Soc 81:86

    CAS  Google Scholar 

  11. Fink G, Schnell D (1982) Angew Makromol Chem 105:39

    CAS  Google Scholar 

  12. Sinn H, Patat F (1963) Angew Chem 75:805

    Google Scholar 

  13. Sinn H, Hinck H, Bandermann F, Grützmacher HF (1968) Angew Chem 80:190

    Google Scholar 

  14. Kaminsky W, Sinn H (1975) Justus Liebigs Ann Chem 1975:424

    Google Scholar 

  15. Kaminsky W, Vollmer HJ, Heins E, Sinn H (1974) Makromol Chem 175:443

    CAS  Google Scholar 

  16. Sinn H, Kolk E (1966) J Organomet Chem 6:373

    CAS  Google Scholar 

  17. Kaminsky W, Kopf J, Sinn H, Vollmer HJ (1976) Angew Chem Int Ed Engl 15:629

    Google Scholar 

  18. Sinn H (1974) Chem Ing Technol 46:579

    CAS  Google Scholar 

  19. Sinn H, Kaminsky W, Janning J (1976) Angew Chem 88:737

    CAS  Google Scholar 

  20. Heins E, Hinck H, Kaminsky W, Oppermann G, Raulinat P, Sinn H (1970) Makromol Chem 134:125

    Google Scholar 

  21. Mottweiler R (1975) Thesis. University of Hamburg, Hamburg

    Google Scholar 

  22. Andresen A, Cordes HG, Herwig J, Kaminsky W, Merck A, Mottweiler R, Pein J, Sinn H, Vollmer HJ (1976) Angew Chem Int Ed Engl 15:630

    Google Scholar 

  23. Sinn H, Kaminsky W (1980) Ziegler–Natta catalysis. Adv Organomet Chem 18:99

    CAS  Google Scholar 

  24. Kaminsky W (2004) J Polym Sci A Polym Chem 42:3911

    CAS  Google Scholar 

  25. Kaminsky W (2012) Macromolecules 45:3289

    CAS  Google Scholar 

  26. Reichert KH, Meyer KR (1973) Makromol Chem 169:163

    CAS  Google Scholar 

  27. Long WP, Breslow DS (1975) Justus Liebigs Ann Chem 1975:463

    Google Scholar 

  28. Lehmkuhl H, Ziegler K (1970) In: Houben J, Weyl T (eds) Methoden der organische Chemie (Houben-Weyl) vol XIII, part 4. Thieme, Stuttgart, p 76

    Google Scholar 

  29. Storr A, Jones K, Laubengayer AW (1968) J Am Chem Soc 90:3173

    CAS  Google Scholar 

  30. Bähr G (1946) Fiat review of German Science. Inorganic chemistry, Part II, p 161

    Google Scholar 

  31. Herwig J, Kaminsky W (1983) Polym Bull 9:464

    CAS  Google Scholar 

  32. Sinn H, Bliemeister J, Clausnitzer D, Tikwe L, Winter H, Zarncke O (1988) In: Kaminsky W, Sinn H (eds) Transition metals and organometallics as catalysts for olefin polymerization. Springer, Berlin, p 257

    Google Scholar 

  33. Bliemeister J, Hagendorf W, Harder A, Heitmann B, Schimmel I, Schmedt E, Schnuchel W, Sinn H, Tikwe L, vThienen N, Urlass K, Winter H, Zarncke O (1995) In: Fink G, Mülhaupt P, Brintzinger HH (eds) Ziegler catalysts. Springer, Berlin, p 57

    Google Scholar 

  34. Sinn H, Schimmel I, Ott M, vThienen N, Harder A, Hagendorf W, Heitmann B, Haupt E (1999) In: Kaminsky W (ed) Metalorganic catalysts for synthesis and polymerization. Springer, Berlin, p 105

    Google Scholar 

  35. Sinn H, Namyslo J (2012) Colloquium at Chemistry Department, University Hamburg, 30 May 2012

    Google Scholar 

  36. Smith GM, Palmaka SW, Rogers JS, Malpass DB, Monfiston DJ (1998) US Patent 5,831,109 to Akzo Nobel

    Google Scholar 

  37. Malpass DB, Palmaka SW, Smith GM, Rogers JS (1997) Int Patent Appl WO 9,723,288, A1 19,970,703 to Akzo Nobel

    Google Scholar 

  38. Sinn H (1995) Macromol Symp 97:27

    CAS  Google Scholar 

  39. Eilertsen JL, Rytter E, Ystenes (1999) In: Kaminsky W (ed) Metalorganic catalysts for synthesis and polymerization. Springer, Berlin, p 136

    Google Scholar 

  40. Mason MR, Smith JM, Bott SG, Barron R (1993) J Am Chem Soc 115:4971

    CAS  Google Scholar 

  41. Koide Y, Bott SG, Barron AR (1996) Organometallics 15:2213

    CAS  Google Scholar 

  42. Kaminsky W, Miri M, Sinn H, Woldt R (1983) Makromol Chem Rapid Commun 4:417

    CAS  Google Scholar 

  43. Sinn H, Kaminsky W, Vollmer HJ, Woldt R (1980) DE Patent 3,007,725

    Google Scholar 

  44. Dyachkovskii FS, Shilova AK, Shilov AE (1967) Polym Sci C 16:2333

    Google Scholar 

  45. Eisch JJ, Pombrick SI, Zheng GX (1993) Organometallics 12:3856

    CAS  Google Scholar 

  46. Jordon RF, Dasher WE, Echols SF (1968) J Am Chem Soc 108:1718

    Google Scholar 

  47. Bochmann M, Wilson LM (1986) J Chem Soc Chem Commun 1610

    Google Scholar 

  48. Yang X, Stern CL, Marks TJ (1991) Organometallics 10:840

    CAS  Google Scholar 

  49. Sishta C, Hathorn RM, Marks TJ (1992) J Am Chem Soc 114:1112

    CAS  Google Scholar 

  50. Hlatky GG, Turner HW, Eckmann RR (1989) J Am Chem Soc 111:2728

    CAS  Google Scholar 

  51. Chien JCW, Tsai WM, Rausch MD (1991) J Am Chem Soc 113:8570

    CAS  Google Scholar 

  52. Bochmann M, Lancaster SJ (1993) Organometallics 12:633

    CAS  Google Scholar 

  53. Zambelli A, Longo P, Grassi A (1989) Macromolecules 22:2186

    CAS  Google Scholar 

  54. Shiono T (2013) Trialkylaluminum-free modified methylaluminoxane as a cocatalyst for living polymerization of olefins. Adv Polym Sci. doi:10.1007/12_2013_211

    Google Scholar 

  55. Brintzinger HH, Fischer D, Mülhaupt R, Rieger B, Waymouth R (1995) Angew Chem 107:1255, Angew Chem Int Ed Engl 34:1143

    Google Scholar 

  56. Scheirs J, Kaminsky W (eds) (2000) Metallocene-based polyolefins: preparation, properties, and technology, vols 1 and 2. Wiley, Chichester

    Google Scholar 

  57. Coates GW (2000) Chem Rev 100:1223

    CAS  Google Scholar 

  58. Rieger B, Baugh LS, Kacker S, Striegler S (eds) (2003) Late transition metal polymerization catalysis. Wiley-VCH, Weinheim

    Google Scholar 

  59. Keii T (2004) Heterogeneous kinetics: theory of Ziegler–Natta–Kaminsky polymerization, vol 77, Springer series in chemical physics. Springer, Berlin

    Google Scholar 

  60. Razavi A, Thewalt U (2006) Coord Chem Rev 250:155

    CAS  Google Scholar 

  61. Kaminsky W (ed) (2005) Olefin polymerization. Macromol Symp 236

    Google Scholar 

  62. Chum PS, Swogger KW (2008) Prog Polym Sci 33:797

    CAS  Google Scholar 

  63. Baugh LS, Canich JAM (eds) (2008) Stereoselective polymerization with single-site catalysts. CRC, Boca Raton

    Google Scholar 

  64. Busico V (2009) Dalton Trans 41:8794

    Google Scholar 

  65. Severn J, Robert L (2010) In: Hoff R, Mathers RT (eds) Handbook of transition metal polymerization catalysts. Wiley, New York, p 157

    Google Scholar 

  66. Nomura K, Liu KJ (2011) Dalton Trans 40:7666

    CAS  Google Scholar 

  67. Heurtefen B, Bouilhac C, Cloutet E, Taton D, Deffieux A, Cramail H (2011) Prog Polym Sci 36:89

    Google Scholar 

  68. Delferro M, Marks TJ (2011) Chem Rev 111:2450

    CAS  Google Scholar 

  69. Tait P (1988) In: Kaminsky W, Sinn H (eds) Transition metals and organometallics as catalysts for olefin polymerization. Springer, Berlin, p 309

    Google Scholar 

  70. Chien JCW, Wang BP (1989) J Polym Sci A 27:139

    Google Scholar 

  71. Kaminsky W, Engehausen R, Zoumis K, Spaleck W, Rohrmann J (1992) Makromol Chem 193:1643

    CAS  Google Scholar 

  72. Kaminsky W (1996) Macromol Chem Phys 197:3907

    CAS  Google Scholar 

  73. Alt GH, Milius W, Palackal SJ (1994) J Organomet Chem 472:113

    CAS  Google Scholar 

  74. Kaminsky W, Lüker H (1989) Makromol Chem Rapid Commun 5:225

    Google Scholar 

  75. Erker JKG, Fröhlich R (1997) J Am Chem Soc 119:11165

    Google Scholar 

  76. Kawai K, Fujita T (2009) Top Organomet Chem 26:3–41

    Google Scholar 

  77. Shiono T (2011) Polym J 43:331

    CAS  Google Scholar 

  78. Stevens (1993) Proceedings worldwide metallocene conference, MetCon 93, Houston, 26–28 May 1993. Catalyst Consultants, Houston, p 157

    Google Scholar 

  79. Hlatky GG (2000) Chem Rev 100:1347

    CAS  Google Scholar 

  80. Pino P, Mühlhaupt R (1980) Angew Chem 92:869

    CAS  Google Scholar 

  81. Wild FR, Zsolnai L, Huttner G, Brintzinger HH (1982) J Organomet Chem 232:233

    CAS  Google Scholar 

  82. Kaminsky W, Külper K, Brintzinger HH, Wild FR (1985) Angew Chem Int Ed Engl 24:507

    Google Scholar 

  83. Ewen JA (1984) J Am Chem Soc 106:6355

    CAS  Google Scholar 

  84. Spaleck W, Aulbach M, Bachmann B, Kueber F, Winter A (1995) Macromol Symp 89:237

    CAS  Google Scholar 

  85. Ewen JA, Jones RL, Razavi A, Ferrara JP (1988) J Am Chem Soc 110:6255

    CAS  Google Scholar 

  86. Kaminsky W, Buschermöhle M (1987) In: Fontanille M, Guyot A (eds) Recent advances in mechanistic and synthetic aspects of polymerization. Reidel, Dordrecht, p 503

    Google Scholar 

  87. Brintzinger HH, Fischer D (2013) Development of ansa-metallocenes for isotactic olefin polymerization. Adv Polym Sci. doi:10.1007/12_2013_215

    Google Scholar 

  88. Razavi A (2013) Syndiotactic polypropene: discovery, development, and industrialization via bridged metallocene catalysts. Adv Polym Sci. doi:10.1007/12_2013_220

    Google Scholar 

  89. Kaminsky W, Spiehl R (1989) Makromol Chem 190:515

    CAS  Google Scholar 

  90. Collins S, Kelly WM (1992) Macromolecules 25:233

    CAS  Google Scholar 

  91. Tritto I, Boggioni L, Ferro DR (2006) Coord Chem Rev 250:212

    CAS  Google Scholar 

  92. Schäfer A, Karl E, Zsolnai L, Huttner G, Brintzinger HH (1987) J Organomet Chem 328:87

    Google Scholar 

  93. Kaminsky W, Ahlers A, Möller-Lindenhof N (1989) Angew Chem Int Ed Engl 28:1216

    Google Scholar 

  94. Kaminsky W, Ahlers A, Rabe O, König W (1992) In: Enders D, Gais H-J, Keim W (eds) Organic synthesis via organometallics. Vieweg, Braunschweig, p 151

    Google Scholar 

  95. Kaminsky W, Miri M (1985) J Polym Sci A Polym Chem 23:2151

    CAS  Google Scholar 

  96. Kaminsky W, Schlobohm M (1986) Makromol Chem Rapid Symp 4:103

    CAS  Google Scholar 

  97. Kaminsky W (1994) Catal Today 20:257

    CAS  Google Scholar 

  98. Jüngling S, Mülhaupt R, Fischer D, Langhauser F (1995) Angew Makromol Chem 229:93

    Google Scholar 

  99. Kaminsky W (2000) Catal Today 62:23

    CAS  Google Scholar 

  100. Frediani M, Bianchini C, Kaminsky W (2006) Kinet Catal 47:207

    CAS  Google Scholar 

  101. Arikan B, Stadler FJ, Kaschta J, Münstedt H, Kaminsky W (2007) Macromol Rapid Commun 28:1472

    CAS  Google Scholar 

  102. Stadler FJ, Arikan-Conley B, Kaschta J, Kaminsky W, Münstedt H (2011) Macromolecules 44:5053

    CAS  Google Scholar 

  103. Kaminsky W, Boggioni L, Tritto I (2012) In: Matyjaszewski K, Möller M (eds) Polymer science: a comprehensive reference, vol 3. Elsevier, Amsterdam, p 843

    Google Scholar 

  104. Kaminsky W, Bark A, Arndt M (1991) Makromol Chem Macromol Symp 47:83

    CAS  Google Scholar 

  105. Cherdron H, Brekner MJ, Osan F (1994) Angew Makromol Chem 223:121

    CAS  Google Scholar 

  106. Boggioni L, Tritto I (2013) Polyolefins with cyclic comonomers. Adv Polym Sci. doi:10.1007/12_2013_217

    Google Scholar 

  107. Dong M, Wang L, Jiang G, Sun T, Zhao Y, Yu H, Chen T (2006) J Appl Polym Sci 101:1291

    CAS  Google Scholar 

  108. Alexandre M, Martin E, Dubois P, Garcia-Marti M, Jerome R (2000) Macromol Rapid Commun 21:931

    CAS  Google Scholar 

  109. Xalter R, Halbach TS, Muelhaupt R (2006) Macromol Symp 236:145

    CAS  Google Scholar 

  110. Funck A, Kaminsky W (2007) Compos A Technol 67:906

    CAS  Google Scholar 

  111. Guo N, Benedetto SA, Tewari P, Lanagan MT, Ratner MA, Marks TJ (2010) Chem Mater 22:1567

    CAS  Google Scholar 

  112. Xalter R, Mülhaupt R (2010) Macromol Reaction Eng 4:25

    CAS  Google Scholar 

  113. Etcheverry M, Ferreira ML, Capiati NJ, Pegoretti A, Barbosa SE (2008) Compos A Appl Sci 39:1915

    Google Scholar 

  114. Stürzel M, Kurek A, Anselm M, Halbach T, Mülhaupt R (2013) Polyolefin nanocomposites and hybrid catalysts. Adv Polym Sci. doi:10.1007/12_2013_219

    Google Scholar 

  115. Tarte NH, Cui L, Woo S (2013) Polyolefin/layered silicate nanocomposites prepared by in-situ polymerization. Adv Polym Sci. doi:10.1007/12_2013_228

    Google Scholar 

  116. Meyer RSA, Luinstra GA (2013) Iron catalyst in the preparation of polyolefin composites. Adv Polym Sci. doi:10.1007/12_2013_223

    Google Scholar 

  117. Kaminsky W (2008) Macromol Chem Phys 209:459

    CAS  Google Scholar 

  118. Kaminsky W, Funck A, Klinke C (2008) Top Catal 48:84

    CAS  Google Scholar 

  119. Klapper M, Jang YJ, Bieber K, Nemnich T, Nenov N, Müllen K (2004) Macromol Symp 213:131

    CAS  Google Scholar 

  120. Busico V, Cipullo R, Corradini P (1993) Macromol Chem Rapid Commun 117:195

    Google Scholar 

  121. Stadler FJ, Arikan B, Kaschta J, Kaminsky W (2010) Macromol Chem Phys 211:1472

    CAS  Google Scholar 

  122. Malmberg A, Kokko E, Lehmus P, Löfgren B, Seppälä JV (1998) Macromolecules 31:8448

    CAS  Google Scholar 

  123. Ittel SD, Johnson LK, Brookhart M (2000) Chem Rev 100:1169

    CAS  Google Scholar 

  124. Mecking S (2007) Colloid Polym Sci 285:605

    CAS  Google Scholar 

  125. Möller HM, Baier MC, Mecking S, Talsi EP, Bryliakov KP (2012) Chem A Eur J 18:848

    Google Scholar 

  126. Zhang D, Guironnet D, Goettker-Schnetmann I, Mecking S (2009) Organometallics 28:4072

    CAS  Google Scholar 

  127. Kaminsky W (2009) J Chem Soc Dalton Trans 2009:8003

    Google Scholar 

  128. Heinemann J, Muelhaupt R, Brinkmann P, Luinstra GA (1999) Macromol Chem Phys 200:384

    CAS  Google Scholar 

  129. Lipponen S, Seppälä J (2011) Organometallics 30:528

    CAS  Google Scholar 

  130. Seppälä J, Kokko E, Lehmus P, Pakkanen A, Hakala K, Lipponen S, Löfgren B (2013) Functional polyolefins through polymerizations by using bis(indenyl)zirconium catalysts. Adv Polym Sci. doi:10.1007/12_2013_210

    Google Scholar 

  131. Chung TCM (2013) Functional polyolefins: synthesis and energy storage applications. Adv Polym Sci. doi:10.1007/12_2013_209

    Google Scholar 

  132. Saito J, Mitani M, Matsui S, Kashiwa T, Fujita T (2000) Macromol Rapid Commun 21:1333

    CAS  Google Scholar 

  133. Arriola DJ, Carnahan EM, Hustad PD, Kuhlman RL, Wenzel TT (2006) Science 312:714

    CAS  Google Scholar 

  134. Kaminsky W (1986) In: Seymour RB, Cheng T (eds) History of polyolefins. Reidel, New York, p 257

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute for Technical and Macromolecular Chemistry, University of Hamburg, Bundesstraase 45, 20146, Hamburg, Germany

    Walter Kaminsky

  2. Guest at the Technical University Clausthal, Institute for Technical and Macromolecular Chemistry, University of Hamburg, Bundesstraase 45, 20146, Hamburg, Germany

    Hansjörg Sinn

Authors
  1. Walter Kaminsky
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hansjörg Sinn
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Walter Kaminsky .

Editor information

Editors and Affiliations

  1. Dept. of Chemistry Inst. for Techn. and Macromol. Chemistry, University of Hamburg, Hamburg, Germany

    Walter Kaminsky

Rights and permissions

Reprints and permissions

Copyright information

© 2013 Springer-Verlag Berlin Heidelberg

About this chapter

Cite this chapter

Kaminsky, W., Sinn, H. (2013). Methylaluminoxane: Key Component for New Polymerization Catalysts. In: Kaminsky, W. (eds) Polyolefins: 50 years after Ziegler and Natta II. Advances in Polymer Science, vol 258. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2013_226

Download citation

Publish with us

Policies and ethics

Search

Navigation