Development of half-titanocene catalysts for synthesis of cyclic olefin copolymers

Document Type : Mini Review

Author

Department of Chemistry, Tokyo Metropolitan University, Hachioji, Tokyo, 1920397, Japan

Abstract

Certain cyclic olefin copolymers (COCs) are known as promising amorphous materials with high transparency in the UV-vis region, thermal and humidity resistance, low dielectric constant, low water absorption, and dimensional stability. This short review focuses on the synthesis of (new) cyclic olefin copolymers by designed (nonbridged) half-titanocene catalysts, which enabled to proceed synthesis of the amorphous polymers by ethylene/ propylene copolymerization not only with norbornene (NBE), and tetracyclododecene (TCD), but also with so called low strained cyclic olefins (cyclopentene, cyclohexene, cycloheptene, and cyclooctene). Their thermal properties (glass transition temperature, Tg values) are affected by structure of the cyclic olefin employed and the contents, whereas linear relationships between Tg values and the contents were observed in all cases.

Keywords

Main Subjects

References

  1. Kaminsky W (1994) Olefinpolymerisation mittels metallocenkatalysatoren. Angew Makromol Chem 223: 101-120
  2. Kaminsky W (1996) New polymers by metallocene catalysis. Macromol Chem Phys 197: 3907-3945
  3. McKnight AL, Waymouth RM (1998) Group 4 ansa-cyclopentadienyl-amido catalysts for olefin polymerization. Chem Rev 98: 2587-2598
  4. Gibson VC, Spitzmesser SK (2003) Advances in non-metallocene olefin polymerization catalysis. Chem Rev 103: 283–316
  5. Nomura K, Liu J, Padmanabhan S, Kitiyanan B (2007) Nonbridged half-metallocenes containing anionic ancillary donor ligands: New promising candidates as catalysts for precise olefin polymerization. J Mol Catal-A 267: 1-29
  6. Nomura K (2009) Half-titanocenes containing anionic ancillary donor ligands as promising new catalysts for precise olefin polymerization. Dalton Trans 2009: 8811-8823
  7. Nomura K, Liu J (2011) Half-titanocenes for precise olefin polymerisation: Effects of ligand substituents and some mechanistic aspects. Dalton Trans 40: 7666-7682
  8. Redshaw C, Tang Y (2012) Tridentate ligands and beyond in group IV metal α-olefin homo-/ co-polymerization catalysis. Chem Soc Rev 41: 4484-4510
  9. Osakada K (2014) Organometallic Reactions and Polymerization, Springer-Verlag
  10. Hoff R, Mathers RT (2018) Handbook of Transition Metal Polymerization Catalysts, 2nd , Wiley.
  11. Stürzel M, Mihan S, Mülhaupt R (2016) From multisite polymerization catalysis to sustainable materials and all-polyolefin composites. Chem Rev 116: 1398-1433
  12. Baier MC, Zuideveld MA, Mecking S (2014) Post-metallocenes in the industrial production of polyolefins. Angew Chem Int Ed 53: 9722-9744
  13. van Doremaele G, van Duin M, Valla M, Berthoud A (2017) On the development of titanium κ1- amidinate complexes, commercialized as Keltan ACETM technology, enabling the production of an unprecedented large variety of EPDM polymer structures. J Polym Sci Pol Chem 55: 2877-2891
  14. Yuan S-F, Yan Y, Solan GA, Ma Y, Sun W-H (2020) Recent advancements in N-ligated group 4 molecular catalysts for the (co)polymerization of ethylene. Coord Chem Rev 411: 213254
  15. Nomura K (2023) Catalysis for a SustainableEnvironment: Reactions, Processes and Applied Technologies, Wiley, in press
  16. Suhm J, Schneider MJ, Mülhaupt R (1998) Influence of metallocene structures on ethene copolymerization with 1-butene and 1-octene. J Mol Catal-A 128: 215-227
  17. Suhm J, Schneider MJ, Mülhaupt R (1997) Temperature dependence of copolymerization parameters in ethene/1-octene copolymerization using homogeneous rac-Me2Si(2-MeBenz[e] Ind)2ZrCl2/MAO catalyst. J Polym Sci Pol Chem 35: 735-740
  18. Kakinuki K, Fujiki M, Nomura K (2009) Copolymerization of ethylene with α-olefins containing various substituents catalyzed by half-titanocenes: Factors affecting the monomer reactivities. Macromolecules 42: 4585-4595
  19. Li H, Marks TJ (2006) Nuclearity and cooperativity effects in binuclear catalysts and cocatalysts for olefin polymerization. Proc Nat Acad Sci USA 103: 15295-15302
  20. Delferro M, Marks TJ (2011) Multinuclear olefin polymerization catalysts. Chem Rev 111: 2450- 2485
  21. McInnis JP, Delferro M, Marks TJ (2014) Multinuclear group 4 catalysis: Olefin polymerization pathways modified by strong metal–metal cooperative effects. Acc Chem Res 47: 2545-2557
  22. Nomura K, Naga N, Miki M, Yanagi K, Imai, A (1998) Synthesis of various non-bridged Cp-aryloxy titanium(IV) complexes of the type CpTi(OAr)X2, and the catalytic alkene polymerization. – Important role of substituents on both aryloxy and cyclopentadienyl groups. Organometallics 17: 2152-2154
  23. Nomura K, Naga N, Miki M, Yanagi K (1998) Olefin polymerization by (cyclopentadienyl) (aryloxy)titanium(IV) complexes−cocatalyst systems. Macromolecules 31: 7588-7597
  24. Nomura K, Oya K, Komatsu T, Imanishi Y (2000) Effect of cyclopentadienyl fragment on monomer reactivities and monomer sequence distributions in ethylene/a-olefin copolymerization by nonbridged (cyclopentadienyl)(aryloxy) titanium(IV) complexes – MAO catalyst systems. Macromolecules 33: 3187-3189
  25. Nomura K, Okumura H, Komatsu T, Naga N (2002) Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy) titanium(IV) complexes - MAO catalyst systems. Macromolecules 35: 5388-5395
  26. Nomura K, Itagaki K, Fujiki M (2005) Efficient incorporation of 2-methyl-1-pentene in copolymerization of ethylene with 2-methyl- 1-pentene catalyzed by nonbridged half-titanocenes. Macromolecules 38: 2053-2055
  27. Nomura K, Itagaki K (2005) Efficient incorporation of vinylcylohexane in ethylene/ vinylcyclohexane copolymerization catalyzed by nonbridged half-titanocenes. Macromolecules 38: 8121-8123
  28. Nomura K, Liu J, Fujiki M, Takemoto A (2007) Facile, efficient functionalization of polyolefins via controlled incorporation of terminal olefins by repeated 1,7-octadiene insertion. J Am Chem Soc 129: 14170-14171
  29. Liu J, Nomura K (2008) Efficient functional group introduction into polyolefins by copolymerization of ethylene with allyltrialkylsilane using nonbridged half-titanocenes. Macromolecules 41: 1070-1072
  30. Itagaki K, Nomura K (2009) Efficient synthesis of functionalized polyolefin by incorporation of 4-vinylcyclohexene in ethylene copolymerization using half-titanocene catalysts. Macromolecules 42: 5097-5103
  31. Kitphaitun S, Yan Q, Nomura K (2020) Effect of SiMe3, SiEt3 para-substituents for exhibiting high activity, introduction of hydroxy group in ethylene copolymerization catalyzed by phenoxide-modified half-titanocenes. Angew Chem Int Ed 59: 23072-23076
  32. Aoki H, Nomura K (2021) Synthesis of amorphous ethylene copolymers with 2-vinylnaphthalene, 4-vinylbiphenyl and 1-(4-vinylphenyl) naphthalene. Macromolecules 54: 83-93
  33. Kawamura K, Nomura K (2021) Ethylene copolymerization with limonene, β-pinene: New bio-based polyolefins prepared by coordination polymerization. Macromolecules 54: 4693-4703
  34. Kitphaitun S, Chaimongkolkunasin S, Manit J, Makino R, Kadota J, Hirano H, Nomura K (2021) Ethylene/myrcene copolymer as new bio-based elastomers prepared by coordination polymerization using titanium catalysts. Macromolecules 54: 10049-10058
  35. Kitphaitun S, Takeshita H, Nomura K (2022) Analysis of ethylene copolymers with long chain α-olefins (1-dodecene, 1-tetradecene, 1-hexadecene): A transition between main chain crystallization and side chain crystallization. ACS Omega 7: 6900-6910
  36. Kitphaitun S, Fujimoto T, Ochi Y, Nomura K (2022) Effect of borate cocatalysts toward activity and comonomer incorporation in ethylene copolymerization by half-titanocene catalysts in methylcyclohexane. ACS Org Inorg Au 2: 386-391
  37. Okabe M, Nomura K (2023) Propylene cyclic olefin copolymers with cyclopentene, cyclohexene, cyclooctene, tricyclo[6.2.1.0(2,7)] undeca-4-ene, and with tetracyclododecene: The synthesis and effect of cyclic structure on thermal properties. Macromolecules 56: 81-91
  38. Guo L, Makino R, Shimoyama D, Kadota J, Hirano H, Nomura K (2023) Synthesis of ethylene/ isoprene copolymers containing cyclopentane/ cyclohexane units as unique elastomers by half-titanocene catalysts. Macromolecules: 10.1021/ acs.macromol.2c02399
  39. http://www.topas.com/products/topas-coc-polymers (TOPAS®)
  40. https://jp.mitsuichemicals.com/en/special/apel/ index.htm (APEL®)
  41. Cherdron H, Brekner M-J, Osan F (1994) Cycloolefin copolymer: A new class of transparent thermoplastics. Angew Makromol Chem 223: 121-133
  42. Kaminsky W, Beulich I, Arndt-Rosenau M (2001) Copolymerization of ethene with cyclic and other sterically hindered olefins. Macromol Symp 173: 211-226
  43. Dragutan V, Streck R (2000) Catalytic polymerization of cycloolefins: Ionic, Ziegler-Natta and ring-opening metathesis polymerization, Elsevier
  44. Tritto I, Boggioni L, Ferro DR (2006) Metallocene catalyzed ethene- and propene co-norbornene polymerization: Mechanisms from a detailed microstructural analysis. Coord Chem Rev 250: 212-241
  45. Nomura K (2008) Nonbridged half-titanocenes containing anionic ancillary donor ligands: promising new catalysts for precise synthesis of cyclic olefin copolymers (COCs). Chin J Polym Sci 26: 513-523
  46. Li X, Hou Z (2008) Organometallic catalysts for copolymerization of cyclic olefins. Coord Chem Rev 252: 1842-1869
  47. Zhao W, Nomura K (2016) Design of efficient molecular catalysts for synthesis of cyclic olefin copolymers (COC) by copolymerization of ethylene and α-olefins with norbornene or tetracyclododecene. Catalysts 6: 175
  48. Boggioni L, Tritto I (2017) State of the art of cyclic olefin polymers. MRS Bull 38: 245-251
  49. Nomura K, Tsubota M, Fujiki M (2003) Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)titanium(IV) complexes− MAO catalyst system. Macromolecules 36: 3797-3799
  50. Hasan T, Ikeda T, Shiono T (2004) Ethene−norbornene copolymer with high norbornene content produced by ansa-fluorenylamidodimethyltitanium complex using a suitable activator. Macromolecules 37: 8503- 8 5 0 9
  51. Nomura K, Wang W, Fujiki M, Liu J (2006) Notable norbornene (NBE) incorporation in ethylene–NBE copolymerization catalysed by nonbridged half-titanocenes: better correlation between NBE incorporation and coordination energy. Chem Commun 2659-2661
  52. Hasan T, Nishii K, Shiono T, Ikeda T (2002) Living polymerization of norbornene via vinyl addition with ansa-fluorenylamidodimethyltitanium complex. Macromolecules 35: 8933-8935
  53. Cai Z, Nakayama Y, Shiono, T (2006) Living random copolymerization of propylene and norbornene with ansa-fluorenylamidodimethyltitanium complex: Synthesis of novel syndiotactic polypropylene-b-poly(propylene-ran-norbornene). Macromolecules 39: 2031-2033
  54. Shiono T, Sugimoto M, Hasan T, Cai Z, Ikeda T (2008) Random copolymerization of norbornene with higher 1-alkene with ansa-fluorenylamidodimethyltitanium catalyst. Macromolecules 41: 8292-8294
  55. Cai Z, Harada R, Nakayama Y, Shiono T (2010) Highly active living random copolymerization of norbornene and 1-alkene with ansa-fluorenylamidodimethyltitanium derivative: Substituent effects on fluorenyl ligand. Macromolecules 43: 4527-4531
  56. Yuan H, Kida T, Kim H, Tanaka R, Cai Z, Nakayama Y, Shiono T (2020) Synthesis and properties of gradient copolymers composed of norbornene and higher α-olefins using an ansa-fluorenylamidodimethyltitanium-[Ph3C] [B(C6F5)4] catalyst system. Macromolecules 53: 4323-4329
  57. Zhao W, Nomura K (2016) Copolymerizations of norbornene, tetracyclododecene with α-olefins by half-titanocene catalysts: Efficient synthesis of highly transparent, thermal resistance polymers. Macromolecules 49: 59-70
  58. Apisuk W, Trambitas A G, Kitiyanan B, Tamm M, Nomura K (2013) Efficient ethylene/norbornene copolymerization by half-titanocenes containing imidazolin-2-iminato ligands and MAO catalyst systems. J Polym Sci Pol Chem 51: 2575-2580
  59. Mitsui Chemicals Co., Synthesis of ethylene/ TCD copolymers by vanadium catalyst systems [VOCl3, VO(OEt)Cl2 – EtAlCl2Et2AlCl etc.] in the presence of halogenated Al alkyl cocatalyst, JP2001-106730; JP2006-22266; JP2008-248171
  60. Kaminsky W, Bark A (1992) Copolymerization of ethene and dimethanooctahydro-naphthalene with aluminoxane containing catalysts. Polym Int 28: 251-253
  61. Kaminsky W, Engehausen R, Kopf J (1995) A tailor-made metallocene for the copolymerization of ethene with bulky cycloalkenes. Angew Chem Int Ed Engl 34: 2273-2275
  62. Goodall BL, McIntosh LH, Rhodes LF (1995) New catalysts for the polymerization of cyclic olefins. Macromol Symp 89: 421-432
  63. Kaminsky W, Beulich I, Arndt-Rosenau M (2001) Copolymerization of ethene with cyclic and other sterically hindered olefins. Macromol Symp 173: 211-226
  64. Donner M, Fernandes M, Kaminsky W (2006) Synthesis of copolymers with sterically hindered and polar monomers. Macromol Symp 236: 193- 202
  65. Apisuk W, Ito H, Nomura K (2016) Efficient synthesis of cyclic olefin copolymers with high glass transition temperatures by ethylene copolymerization with tetracyclododecene (TCD) using (tert-BuC5H4)TiCl2(N=CtBu2) – MAO catalyst. J Polym Sci Pol Chem 54: 2662- 2667
  66. Hong M, Cui L, Liu S, Li Y (2012) Synthesis of novel cyclic olefin copolymer (COC) with high performance via effective copolymerization of ethylene with bulky cyclic olefin. Macromolecules 45: 5397-5402
  67. Wang W, Fujiki M, Nomura K (2005) Copolymerization of ethylene with cyclohexene (CHE) catalyzed by nonbridged half-titanocenes containing aryloxo ligand: Notable effect of both cyclopentadienyl and anionic donor ligand for efficient CHE incorporation. J Am Chem Soc 127: 4582-4583
  68. Lavoie AR, Waymouth RM (2004) Catalytic syntheses of alternating, stereoregular ethylene/ cycloolefin copolymers. Tetrahedron 60: 7147- 7155
  69. Naga N (2005) Copolymerization of ethylene with cycloolefins or cyclodiolefins by a constrained-geometry catalyst. J Polym Sci Pol Chem 43: 1285-1291
  70. Harakawa H, Okabe M, Nomura K (2020) Synthesis of cyclic olefin copolymers (COCs) by ethylene copolymerisations with cyclooctene, cycloheptene, and with tricyclo[6.2.1.0(2,7)] undeca-4-ene: Effect of cyclic monomer structures on thermal properties. Polym Chem 11: 5590-5600
  71. Buchmeiser MR, Camadanli S, Wang D, Zou Y, Decker U, Kühnel C, Reinhardt I (2011) A catalyst for the simultaneous ring-opening metathesis polymerization/vinyl insertion polymerization. Angew Chem Int Ed 50: 3566-3571
  72. Kaminsky W, Spiehl R (1989) Copolymerization of cycloalkenes with ethylene in presence of chiral zirconocene catalysts. Makromol Chem 190: 515-526
  73. Naga N, Imanishi Y (2002) Copolymerization of ethylene and cyclopentene with zirconocene catalysts: Effect of ligand structure of zirconocenes. Macromol Chem Phys 203: 159- 165
  74. Lavoie AR, Ho MH, Waymouth RM (2003) Alternating stereospecific copolymerization of cyclopentene and ethylene with constrained geometry catalysts. Chem Commun 864-865
  75. Fujita M, Coates GW (2002) Synthesis and characterization of alternating and multiblock copolymers from ethylene and cyclopentene. Macromolecules 35: 9640-9647
  76. Liu J, Nomura K (2007) Highly efficient ethylene/cyclopentene copolymerization with exclusive 1,2-cyclopentene incorporation by (cyclopentadienyl)(ketimide)titanium(IV) complex - MAO catalysts. Adv Synth Catal 349 : 2235-2240
  77. Harakawa H, Patamma S, Boccia AC, Boggioni L, Ferro DR, Losio S, Nomura K, Tritto I (2018) Ethylene copolymerization with 4-methylcyclohexene, 1-methylcyclopentene by half-titanocene catalysts: Effect of ligands and microstructural analysis of the copolymers. Macromolecules 51: 853-863
  78. Nomura K (2019) Solution X-ray absorption spectroscopy (XAS) for analysis of catalytically active species in reactions with ethylene by homogeneous (imido)vanadium(V) complexes – Al cocatalyst systems. Catalysts 9: 1016
  79. Yi J, Nakatani N, Nomura K (2020) Solution XANES and EXAFS analysis of active species of titanium, vanadium complex catalysts in ethylene polymerisation/dimerisation and syndiospecific styrene polymerization. Dalton Tran 49: 8008- 8028

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  • Receive Date: 14 January 2023
  • Accept Date: 27 January 2023
  • First Publish Date: 30 January 2023

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