Recent advances in the polymerization of butadiene over the last decade

Document Type : Review

Authors

CNR - Istituto per lo Studio delle Macromolecole (ISMAC), via E. Bassini 15, I-20133 Milano (Italy)

Abstract

The stereospecific polymerization of conjugated dienes began in 1954 with the first catalysts obtained by combining TiCl4 or TiCl3 with aluminum-alkyls, i.e. the catalytic systems previously employed for ethylene and propylene polymerizations. Subsequently, many other catalytic systems were obtained and examined by a combination of transition metal or lanthanide compounds with appropriate alkylating agents. With the advent of MAO as alkylating agent, at the beginning of the 1980s, new catalytic systems were introduced, in some cases much more active and stereospecific than those based on common aluminum-alkyls. Starting from the 2000s, in the wake of what happened in the case of mono-olefins, a new generation of catalysts based on complexes of transition ,metals and lanthanides with various ligands containing donor atoms such as P, N, O (e.g., phosphines, imines imino-pyridines, cheto-imines) has been introduced. These systems have proved particularly active and able to (provide polymers with controlled microstructure (i.e., cis-1,4; 1,2; mixed cis-1,4/1,2 with a variable 1,2 content ,from several types of 1,3-dienes, permitting indeed to establish new correlations between the catalyst structure the monomer structure and the polymer microstructure, and to improve our knowledge on the polymerization mechanism of 1,3-dienes. This paper provides an exhaustive overview of the latest developments in the field of stereospecific polymerization of 1,3-butadiene.

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Main Subjects


  1. Porri L, Giarrusso A (1989) Conjugated diene polymerization. In: Eastmond G, Ledwith A, Russo S, Sigwalt P (eds) Comprehensive polymer science. Pergamon, Oxford, 53-108
  2. Thiele SKH, Wilson DR (2003) Alternate transition metal complex based diene polymerization. J Macromol Sci, Polym Rev C 43:581-628
  3. Osakada K, Takeuchi D (2004) Coordination polymerization of dienes, allenes, and methylenecycloalkanes. Adv Polym Sci 171:137-194
  4. Ricci G, Masi F, Boglia A, Sommazzi A, Ricci M (2007) In: Yamamoto K (ed) Advances in organometallic chemistry research. Nova Science, USA, 1-36
  5. Ricci G, Sommazzi A, Masi F, Ricci M, Boglia A, Leone G (2010) Well-defined transition metal complexes with phosphorus and nitrogen ligands for 1,3-dienes polymerization. Coord Chem Rev 254:661-676
  6. Friebe L, Nuyken O, Obrecht W (2006) Neodymium-based Ziegler/Natta catalysts and their application in diene polymerization. Adv Polym Sci 204:1-154
  7. Sinn H, Bliemeister J, Clausnitzer D, Winter L, Zarncke O (1998) In: Kaminsky W, Sinn H (eds) Transition metals and organometallics as catalysts for olefin polymerization. Springer-Verlag, Berlin Heidelberg, New York, 257-268
  8. Bliemeister J, Hagendorf W, Harder A, Heitmann B, Schimmel I, Schmedt E, Schnuchel W, Sinn H, Tikwe L, von Thiene N, Urlass K, Winter H, Zarncke O (1995) In: Fink G, Mülhaupt R, Brintzinger HH (eds) Ziegler catalysts. Springer- Verlag, Berlin Heidelberg, New York, 57-82
  9. Ricci G, Italia S, Comitani C, Porri L (1991) Polymerization of conjugated dialkenes with transition metal catalysts. Influence of methylaluminoxane on catalyst activity and stereospecificity. Polym Commun 32:514-517
  10. Ricci G, Italia S, Porri L (1994) Polymerization of 1,3-dienes with methylaluminoxane-triacetyl-acetonatovanadium. Macromol Chem Phys 195:1389-1397
  11. Ricci G, Porri L (1997) Polymerization of 4-methyl-1,3-pentadiene with MAO/Ti(OnBu)4. The influence of preparation/ageing temperature upon the stereospecificity of the catalyst. Polymer 38:4499-4503
  12. Ricci G, Zetta L, Alberti E, Motta T, Canetti M, Bertini F (2007) Butadiene–isoprene copolymerization with V(acac)3-MAO. Crystalline and amorphous trans-1,4 copolymers. J Polym Sci, Part A: Polym Chem 45:4635-4646
  13. Zambelli A, Ammendola P, Proto A (1989) Synthesis of syndiotactic poly-1,2-(4-methyl-1, 3-pentadiene). Macromolecules 22:2126-2128
  14. Oliva L, Longo P, Grassi A, Ammendola P, Pellecchia C (1990) Polymerization of 1, 3-alkadienes in the presence of Ni-and Ti-based catalytic systems containing methylalumoxane. Die Makromol Chem, Rapid Commun 11:519-524
  15. Venditto V, De Rosa C, Guerra G, Napolitano R (1992) X-Ray diffraction, conformational analysis and stereoregularity of a crystalline poly (3-methyl- 1,3-pentadiene). Polymer 33:3547-3551
  16. Ricci G, Italia S, Giarrusso A, Porri L (1993) Polymerization of 1,3-dienes with the soluble catalyst system methylaluminoxanes-[CpTiCl3]. Influence of monomer structure on polymerization stereospecificity. J Organomet Chem 451:67-72
  17. Ricci G, Panagia A, Porri L (1996) Polymerization of 1,3-dienes with catalysts based on mono- and bis-cyclopentadienyl derivatives of vanadium. Polymer 37:363-365
  18. Ricci G, Bosisio C, Porri L (1996) Polymerization of 1,3-butadiene, 4-methyl-1,3-pentadiene and styrene with catalyst systems based on biscyclopentadienyl derivatives of titanium. Macromol Chem, Rapid Commun 17:781-785
  19. Porri L, Ricci G, Giarrusso A (1999) In: Kaminsky W (ed) Metal organic catalysts for synthesis and polymerization. Springer-Verlag, Berlin, Heidelberg, 519-530
  20. Porri L, Giarrusso A, Ricci G (2000) In: Scheirs J, Kaminsky W (eds) Metallocene-based polyolefins. John Wiley, New York, 115-141
  21. Longo P, Oliva P, Proto A, Zambelli A (1996) Low-temperature polymerization of some conjugated diolefins in the presence of group 4 metal catalysts. Gazz Chim Ital 126:377-382
  22. Ricci G, Italia S, Porri L (1994) Polymerization of (Z)-1, 3-pentadiene with CpTiCl3/MAO. Effect of temperature on polymer structure and mechanistic implications. Macromolecules 27:868-869
  23. Ricci G, Alberti E, Zetta L, Motta T, Bertini F, Mendichi R, Arosio P, Famulari A, Meille SV (2005) Synthesis, characterization and molecular conformation of syndiotactic 1,2 polypentadiene: the cis polymer. Macromolecules 38:8353-8361
  24. Longo P, Guerra G, Grisi F, Pizzuti S, Zambelli A (1998) Chemoselective mechanism of (Z)- 1,3-pentadiene polymerization in the presence of cyclopentadienyltitaniumtrichloride and methylaluminoxane. Macromol Chem Phys 199:149-154
  25. Ricci G, Porri L (1997) Chemoselective mechan-ism of (Z)-1,3-pentadiene polymerization in the presence of cyclopentadienyltitaniumtrichloride and methylaluminoxane. Macromol Chem Phys 198:3647-3650
  26. Johnson LK, Killian CM, Brookhart M (1995) New Pd (II)-and Ni (II)-based catalysts for polymerization of ethylene and. alpha.-olefins. J Am Chem Soc 117:6414-6415
  27. Killian CM, Tempel DJ, Johnson LK, Brookhart M (1996) Living polymerization of α-olefins using niII-α-diiminecatalysts. Synthesis of new block polymers based on α-olefins. J Am Chem Soc 118:11664-11665
  28. Killian CM, Johnson LK, Brookhart M (1997) Preparation of linear α-olefins using cationic nickel (II) α-diimine catalysts. Organometallics 16:2005-2007
  29. Mecking S, Johnson LK, Wang L, Brookhart M (1998) Mechanistic studies of the palladium-catalyzed copolymerization of ethylene and α-olefins with methyl acrylate. J Am Chem Soc 120:888-899
  30. Svejda SA, Johnson LK, Brookhart M (1999) Low-temperature spectroscopic observation of chain growth and migratory insertion barriers in (α-Diimine) Ni (II) olefin polymerization catalysts. J Am Chem Soc 121:10634-10635
  31. Ittel SD, Johnson LK, Brookhart M (2000) Late-metal catalysts for ethylene homo- and copolymerization. Chem Rev 100:1169-1203
  32. Gate DP, Svejda SA, Oñate E, Killian CM, Synthesis of branched polyethylene using (α-diimine) nickel (II) catalysts: influence of temperature, ethylene pressure, and ligand structure on polymer properties. Johnson LK, White PS, Brookhart M (2000) Macromolecules 33:2320-2324
  33. Tempel DJ, Johnson LK, Huff PS, Brookhart M (2000) Mechanistic studies of Pd (II)-α-diimine-catalyzed olefin polymerizations. J Am Chem Soc 122:6686-6700
  34. Shultz LH, Tempel DJ, Brookhart M (2001) Palladium (II) β-agostic alkyl cations and alkyl ethylene complexes:investigation of polymer chain isomerization mechanisms. J Am Chem Soc 123:11539-11555
  35. Shultz LH, Brookhart M (2001) Measurement of the barrier to β-hydride elimination in a β-agostic palladium−ethyl complex: a model for the energetics of chain-walking in (α-diimine)PdR+ olefin polymerization catalysts. Organometallics 20:3975-3982
  36. Leatherman MD, Svejda SA, Johnson LK, Brookhart M (2003) Mechanistic studies of nickel(II) alkyl agostic cations and alkyl ethylene complexes: investigations of chain propagation and isomerization in (α-diimine)Ni(II)-catalyzed ethylene polymerization. J Am Chem Soc 125:3068-3081
  37. Mecking S (2001) Olefin polymerization by late transition metal complexes—a root of Ziegler catalysts gains new ground. Angew Chem Int Ed 40:534-540
  38. Britovsek GJP, Gibson VC, Kimberley BS, Maddox PJ, McTavish SJ, Solan GA, White AJP, Williams DJ (1998) Novel olefin polymerization catalysts based on iron and cobalt. Chem Commun 7:849-850
  39. Small BL, Brookhart M, Bennett AMA (1998) Highly active iron and cobalt catalysts for the polymerization of ethylene. J Am Chem Soc 120:4049-4050
  40. Small BL, Brookhart M (1998) Iron-based catalysts with exceptionally high activities and selectivities for oligomerization of ethylene to linear α-olefins. J Am Chem Soc 120:7143-7144
  41. Bennet AMA (1999) Novel, highly active iron and cobalt catalysts for olefin polymerization. Chem tech 29:24-28
  42. Britovsek GJP, Bruce M, Gibson VC, Kimberley BS, Maddox PJ, Mastroianni S, McTavish SJ, Redshaw C, Solan GA, Stromberg S, White AJP, Williams DJ (1999) Iron and cobalt ethylene polymerization catalysts bearing 2,6- bis (imino) pyridyl ligands: synthesis, structures, and polymerization studies. J Am Chem Soc 121:8728-8740
  43. Britovsek GJP, Mastroianni S, Solan GA, Baugh SPD, Redshaw C, Gibson VC, White, AJP, Williams, AJP, Elsegood MRJ (2000) Oligomerisation of ethylene by bis (imino) pyridyliron and-cobalt complexes. Chem Eur J 6:2221-2231
  44. Ricci G, Battistella M, Porri L (2001) Chemoselectivity and stereospecificity of chromium (II) catalysts for 1,3-diene polymerization. Macromolecules 34:5766-5769
  45. Ricci G, Battistella M, Bertini F, Porri L (2002) 1,2 Syndiotactic polybutadiene of controlled crystallinity by butadiene-isoprene copolymerization with CrCl2(dmpe)2-MAO.Polym Bull 48:25-31
  46. Bazzini C, Giarrusso A, Porri L (2002) Diethylbis (2,2′-bipyridine) iron/MAO. A very active and stereospecific catalyst for 1,3-diene polymerization. Macromol Rapid Commun 23:922-927
  47. Ricci G, Morganti D, Sommazzi A, Santi R, Masi F (2003) Polymerization of 1,3-dienes with iron complexes based catalysts: influence of the ligand on catalyst activity and stereospecificity. J Mol Cat A: Chem 204/205:287-293
  48. Bazzini C, Giarrusso A, Porri L, Pirozzi B, Napolitano R (2004) Synthesis and characterization of syndiotactic 3,4-polyisoprene prepared with diethylbis (2,2′-bipyridine) iron– MAO. Polymer 45:2871-2875
  49. Pirozzi B, Napolitano R, Petraccone V, Esposito S (2004) Determination of the crystal structure of syndiotactic 3,4-poly(2-methyl-1,3-butadiene) by molecular mechanics and X-ray diffraction. Macromol Chem Phys 205:1343-1350
  50. Ricci G, Forni A, Boglia A, Sonzogni M (2004) New chromium (II) bidentate phosphine complexes: synthesis, characterization, and behavior in the polymerization of 1,3-butadiene. Organometallics 23:3727-3732
  51. Ricci G, Forni A, Boglia A, Motta T (2005) Synthesis, structure, and butadiene polymerization behavior of alkylphosphine cobalt (II) complexes. J Mol Cat A: Chem 226:235-241
  52. Ricci G, Forni A, Boglia A, Motta T, Zannoni G, Canetti M, Bertini F (2005) Synthesis and X-ray structure of CoCl2(PiPrPh2)2. A new highly active and stereospecific catalyst for 1,2 polymerization of conjugated dienes when used in association with MAO. Macromolecules 38:1064-1070
  53. Ricci G, Forni A, Boglia A, Sommazzi A, Masi F (2005) Synthesis, structure and butadiene polymerization behavior of CoCl2(PRxPh3−x)2 (R = methyl, ethyl, propyl, allyl, isopropyl, cyclohexyl; x = 1, 2). Influence of the phosphorous ligand on polymerization stereoselectivity. J Organomet Chem 690:1845-1854
  54. Ricci G, Boglia A, Motta T (2007) Synthesis of new Cr(II) complexes with bidentate phosphine ligands and their behavior in the polymerization of butadiene: Influence of the phosphine bite angle on catalyst activity and stereoselectivity. J Mol Cat A: Chem 267:102-107
  55. Ricci G, Boglia A, Boccia AC, Zetta L (2007) Chromium catalysts for butadiene and norbornene polymerization. Macromol Symp 260:172-178
  56. Ricci G, Motta T, Boglia A, Alberti E, Zetta L, Bertini F, Arosio P, Famulari A, Meille SV (2005) Synthesis, characterization, and crystalline structure of syndiotactic 1,2-polypentadiene: the trans polymer. Macromolecules 38:8345-8352
  57. Ricci G, Boglia A, Motta T, Bertini F, Boccia A.C, Zetta L, Alberti E, Famulari A, Arosio P, Meille SV (2007) Synthesis and structural characterization of syndiotactic trans-1,2 and cis- 1,2-polyhexadienes. J Polym Sci, Part A: Polym Chem 45:5339-5353
  58. Ricci G, Bertini F, Boccia AC, Zetta L, Alberti E, Pirozzi B, Giarrusso A, Porri L (2007) Synthesis and characterization of syndiotactic 1,2-poly (3-methyl-1,3-pentadiene). Macromolecules, 40:7238-7243
  59. Pirozzi B, Napolitano R, Giusto G, Esposito S, Ricci G (2007) Determination of the crystal structure of syndiotactic 1,2-poly(E-3-methyl-1, 3-pentadiene) by X-ray diffraction and molecular mechanics. Macromolecules 40:8962-8968
  60. Ricci G, Leone G, Boglia A, Bertini F, Boccia AC, Zetta L (2009) Synthesis and characterization of isotactic 1,2-poly(E-3-methyl-1,3-pentadiene). Some remarks about the influence of monomer structure on polymerization stereoselectivity. Macromolecules 48:3048-3056
  61. Ricci G, Sommazzi A, Leone G, Boglia A, Masi F (2012) In: Ming Y C, Da-Xia Y (eds) Phosphorus: Properties, Health effects and the Environment. Nova Science, USA, 53-94
  62. Leone G, Boccia A C, Ricci G, Giarrusso A, Porri L (2013) Polymerization of (E)-1,3- pentadiene and (E)-2-methyl-1,3-pentadiene with neodymium catalysts. Examination of the factors that affect the stereoselectivity. J Polym Sci Part A: Polym Chem 51:3227-3232
  63. Porri L (1981) In: Ciardelli F, Giusti P (eds) Structural order in polymers. Pergamon, Oxford, 51-62
  64. Porri L, Giarrusso A, Ricci G (1991) Recent views on the mechanism of diolefin polymerization with transition metal initiator systems. Prog Polym Sci 16:405-441
  65. Porri L, Giarrusso A, Ricci G (1991) The polymerization of conjugated dialkenes to isotactic and syndiotactic polymers. Effect of ligands on the stereospecificity. Makromol Chem, Macromol Symp 48/49:239-243
  66. Porri L, Giarrusso A, Ricci G (1994) Mechanism of the steoreospecific polymerization of conjugated dienes: new insights and open questions. Polym Sci. 36:1421-1432
  67. Porri L, Giarrusso A, Ricci G (2002) On the mechanism of formation of isotactic and syndiotactic polydiolefins. Macromol Symp 178:55-68
  68. Lopez-Sanchez JA, Lamberti M, Pappalardo D, Pellecchia C (2003) Polymerization of conjugated dienes promoted by bis (phenoxyimino) titanium catalysts. Macromolecules 36:9260-9263
  69. Annunziata L, Pragliola S, Pappalardo D, Tedesco C, Pellecchia C (2011) New (anilidomethyl) pyridine titanium (IV) and zirconium (IV) catalyst precursors for the highly chemo-and stereoselective cis-1, 4-polymerization of 1, 3-Butadiene. Macromolecules 44:1934-1941
  70. Milione S, Cuomo C, Capacchione C, Zannoni C, Grassi A, Proto A (2007) Stereoselective polymerization of conjugated dienes and styrene-butadiene copolymerization promoted by octahedral titanium catalyst. Macromolecules 40:5638-5643
  71. Natta G, Porri L, Corradini P, Morero D (1958) Polimerizzazioni stereospecifiche di diolefine coniugate. Nota I. Sintesi e struttura di polidiolefine a concatenamento 1,4-trans. Chim Ind 40: 362-371
  72. Natta G, Porri L, Mazzei A (1959) Polimerizzazioni stereospecifiche di diolefine coniugate. Nota II Polimerizzazioni del butadiene con catalizzatori preparati da alluminio alchili e cloruri solubili di vanadio. Chim Ind 41:116122
  73. Natta G, Porri L, Carbonaro A (1961) Stereospecificità di catalizzatori omogenei preparati da VCl3 nella polimerizzazione di diolefine coniugate. Atti Accad Naz Lincei, Rend Cl Sci Fis Mat Nat 31(5):189-197
  74. Porri L, Carbonaro A, Ciampelli F (1963) Copolymerization of 1,3-butadiene and 1,3-pentadiene with homogeneous Al(C2H5)2Cl-vanadium compounds catalyst systems. I. Preparation and properties of the copolymers. Makromol Chem 61:90-103
  75. Colamarco E, Milione S, Cuomo C, Grassi A (2004) Homo- and copolymerization of butadiene catalyzed by an bis(imino)pyridyl vanadium complex. Macromol Rapid Commun 25:450-454
  76. Natta G, Porri L, Zanini G, Palvarini A (1959) Polimerizzazioni stereospecifiche di diolefine coniugate. Nota V. Preparazione e proprietà del polibutadiene 1,2 isotattico
  77. Ricci G, Leone G, Masi F, Sommazzi A (2011) In: Salden MP (ed) Chromium: environmental, medical and material studies. Nova Science, USA, 121-140
  78. Cariou R, Chirinos J, Gibson VC Jacobsen G, Tomov AK, Elsegood MRJ (2009) 1,3-Butadiene polymerization by bis(benzimidazolyl)amine metal complexes: remarkable microstructural control and a protocol for in-reactor blending of trans-1,4-, cis-1,4-, and cis-1,4-co-1,2-vinylpolybutadiene. Macromolecules 42:1443-1444
  79. Yamamoto A, Shimizu T, Ikeda SM (1970) Polymerization of vinyl monomers by alkyl-iron and alkyl-cobalt complexes. Makromol Chem 136:297-302
  80. Zhang ZY, Zhang HJ, Ma HM, Wu Y (1982) A novel iron catalyst for the polymerization of butadiene. J Mol Catal 17:65-76
  81. Ricci G, Leone G, Masi F, Sommazzi A (2011) In: Phillips ES (ed) Ferrocenes: compounds, properties and applications. Nova Science, USA, 273-313
  82. Gong D, Dong W, Hu J, Zhang X, Jiang L (2009) Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphate. Polymer 50:2826-2829
  83. Gong D, Jia X, Wang B, Zhang X, Jiang L (2012) Synthesis, characterization, and butadiene polymerization of iron(III), iron(II) and cobalt(II) chlorides bearing 2,6-bis(2-benzimidazolyl) pyridyl or 2,6-bis(pyrazol)pyridine ligand. J Organomet Chem 702:10-18
  84. Nobbs JD, Tomov Ak, Cariou R, Gibson VC, White AJP, Britovsek GJP (2012) Thio-pybox and thio-pheboxcomplexes of chromium, iron, cobalt and nickel and their application in ethylene and butadiene polymerisation catalysis. Dalton Trans 41:5949-5964
  85. Ricci G, Leone G, Boglia A, Masi F, Sommazzi A (2011) Cobalt: Characteristics, compounds, and applications. Vidmar LJ (ed) Nova Science, USA, 39-81
  86. Racanelli P, Porri L (1970) Cis-1,4-polybutadiene by cobalt catalysts. Some features of the catalysts prepared from alkyl aluminium compounds containing Al-O-Al Bonds. Eur Polym J 6:751-761
  87. Cooper W, Eaves DE, Vaughan G (1966) Electron donors in diene polymerization. Adv Chem Ser 52:46-66
  88. Deb Nath DC, Shiono T, Ikeda T (2002) Effects of halogen ligands on 1,3-butadiene polymerization with cobalt dihalides and methylaluminoxane. Macromol Chem Phys 203:1171-1177
  89. Deb Nath DC, Shiono T, Ikeda T (2003) Polymerization of 1,3-butadiene by cobalt dichlo-ride activated with various methylaluminoxanes. Appl Catal A-Gen 238:193-199
  90. Takeushi M, Shiono T, Soga K (1992) Polymerization of 1,3-butadiene with the catalyst system composed of a cobalt compound and methylaluminoxane. Polym Int 29:209-212
  91. Takeushi M, Shiono T, Soga K (1995) Polymerization of 1,3-butadiene with MgCl2- supported cobalt catalysts activated by ordinary alkylaluminums. Polym Int 36:41-45
  92. Takeushi M, Shiono T, Soga K (1995) Characterization of polybutadiene produced with CoBr2(PPh3)2-based catalysts. Macromol Rapid Commun 16:373-378
  93. Nath DCD, Shiono T, Ikeda T (2003) Additive effect of triphenylphosphine on the living polymerization of 1,3-butadiene with a cobalt dichloride-methylaluminoxane catalytic system. Macromol Chem Phys 204:2017-2022
  94. Cai Z, Shinzawa M, Nakayama Y, Shiono T (2009) Synthesis of regioblock polybutadiene with CoCl2-based catalyst via reversible coordination of lewis base. Macromolecules 42:7642-7643
  95. Furukawa J, Haga K, Kobayashi E, Iseda Y, Yoshimoto T, Sakamoto K (1971) Cis-vinyl-1:1 Polymer of butadiene. Polym J 2:371-378
  96. Ashitaka H, Isikawa H, Ueno H (1983) Syndiotactic 1,2-polybutadiene with Co-CS2 catalyst system. I. Preparation, properties, and application of highly crystalline syndiotactic 1,2-polybutadiene. J Polym Sci, Part A: Polym Chem 21:1853-1860
  97. Ashitaka H, Jinda K, Ueno H (1983) Syndiotactic 1,2-polybutadiene with Co-CS2 catalyst system. II. Catalysts for stereospecific polymerization of butadiene to syndiotactic 1,2-polybutadiene. J Polym Sci, Part A: Polym Chem 21:1951-1972
  98. Ashitaka H, Inaishi K, Ueno H (1983) Syndiotactic 1,2-polybutadiene with Co-CS2catalyst system. III.1H- and 13C-NMR study of highly syndiotactic 1,2-polybutadiene. J Polym Sci, Part A: Polym Chem 21:1973-1988
  99. Ashitaka H, Jinda K, Ueno H (1983) Syndiotactic 1,2-polybutadiene with Co-CS2 catalyst system. IV. Mechanism of syndiotactic polymerization of butadiene with cobalt compounds– organoaluminum–CS2. J Polym Sci, Part A: Polym Chem 21:1989-1995
  100. Ricci G, Boglia A, Santi R, Sommazzi A, Masi F (2003) Procedimento per la preparazione di polibutadiene a contenuto variabile cis-1,4/1,2, Italian Patent MI03A 001807
  101. Ricci G, Boglia A, Forni A, Santi R, Sommazzi A, Masi F (2003) Complessi fosfinici di cobalto e procedimento per la loro preparazione, Italian Patent MI 03A 001808
  102. Ricci G, Boglia A, Santi R, Sommazzi A, Masi F (2003) Procedimento per la preparazione di polibutadiene ad alto contenuto in unità 1,2, Italian Patent MI03A 001809
  103. Dierkes P, van Leeuwen PWNM (1999) The bite angle makes the difference: a practical ligand parameter for diphosphine ligands. J Chem Soc, Dalton Trans 1519-1530
  104. van Leeuwen PWNM, Kamer CJ, Reek JNH, Dierkes P (2000) Ligand bite angle effects in metal-catalyzed C-C bond formation. Chem Rev 100:2741-2770
  105. Freixa Z, van Leeuwen PWNM (2003) Bite angle effects in diphosphinemetal catalysts: steric or electronic? Dalton Trans 10:1890-1901
  106. Tolman C (1977) Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis. Chem Rev 77:313-348
  107. Kim JS, Ha CS, Kim II (2006) Highly stereospecific polymerization of 1,3-butadiene with cobalt(II) pyridylbis(imine) complexes. e-Polymer 27
  108. Endo K, Kitagawa T, Nakatani K (2006) Effect of an alkyl substituted in salen ligands on 1,4- cis selectivity and molecular weight control in the polymerization of 1,3-butadiene with (salen) Co(II) complexes in combination with methylaluminoxane. J Polym Sci, Part A: Polym Chem 44:4088-4094
  109. Cariou R, Chirinos JJ, Gibson VC, Jacobsen G, Tomov AK, Britovsek GJP, White AJP (2010) The effect of the central donor in bis(benzimidazole)- based cobalt catalysts for the selective cis-1,4 polymerisation of butadiene. Dalton Trans 39:9039-9045
  110. Appukuttan V, Zhang L, Ha CS, Kim II (2009) Highly active and stereospecific polymerizations of 1,3-butadiene by using bis(benzimidazolyl) amine ligands derived Co(II) complexes in combination with ethylaluminumsesquichloride. Polymer 50:1150-1158
  111. Gong D, Wang B, Bai C, Bi J, Wang F, Dong W, Zhang X, Jiang L (2009) Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl) ethyl]pyridine. Polymer 50:6259-6264
  112. Appukuttan V, Zhang L, Ha JY, Chandran D, Bahuleyan BK, Ha CS, Kim II (2010) Stereospecific polymerizations of 1,3-butadiene catalyzed by Co(II) complexes ligated by 2,6-bis(benzimidazolyl)pyridines. J Mol Cat A: Chem 325:84-90
  113. Gong D, Wang B, Cai H, Zhang X, Jiang L (2011) Synthesis, characterization and butadiene polymerization studies of cobalt(II) complexes bearing bisiminopyridine ligand. J Organomet Chem 696:1584-1590
  114. Sato H, Yagi Y (1992) Studies on nickel-containing Ziegler-type catalysts. I. New catalysts for high-cis-1,4 polybutadiene. Bull Chem Soc Jpn 65:1299-1302
  115. Longo P, Grisi F, Proto A, Zambelli A (1998) New Ni(II) based catalysts active in the polymerization of olefins. Macromol Rapid Commun 19:31-34
  116. Throckmorton MC, Saltman WM (1971), German Patent 2113527, (ChemAbstr 79, 67631, 1973)
  117. Taube R, Gehrke J, Bohme P, Kottnitz J (1990) Komplexkatalyse XXXIV. Darstellung und charakterisierungkationischer η3,η2-Octa-2(E),7- dien-1-yl(ligand) nickel(II)-komplexe [Ni(C8H13)L] X (X = PF6, BF4; L = PIII-Ligand) alskatalysatoren der stereospezifischenbutadien polymerisation. J Organomet Chem 395:341-358
  118. Sato H, Yasui S (1992) Studies on nickel-containing Ziegler-type catalysts. II. Low molecular weight (liquid) poly(diene)s with 1,4-microstructure. Bull Chem Soc Jpn 65:1307- 1311
  119. Sieler J, Kempe R, Wache S, Taube R (1993) Komplexkatalyse: XLI. Die Kristallstruktur des η3,η2-Octa-2(E),7-dien-1-yl-(triphenylphosphin) nickel(II)-tetrafluoroborats, ein beitragzur Klärung der Koordinationsverhältnisse in der kelkomplexkatalysierten butadien polymerisation. J Organomet Chem 455:241-246
  120. Taube R, Maiwald S, Sommer C (2002) Highly active single-site catalysts for the 1,4-cis polymerization of butadiene from allylneodymium(III) chlorides and trialkylaluminiums – a contribution to the activation of tri(allyl)neodymium(III) and the further elucidation of the structure-activity relationship. Macromol Chem Phys 203:1029-1039
  121. Kim JS, Chadran D, Park DW, Ha CS, Kim I (2007) Polymerization of 1,3-butadiene with nickel(II) alpha-diiminecomplexes combined with ethylaluminumsesquischloride. Stud Surf Sci Catal 172:525-526
  122. Campora J, Ortiz de la Tabla L, Palma P, Alvarez E, Lahoz F, Mereiter K (2006) Synthesis and catalytic activity of cationic allylcomplexes of nickel stabilized by a single N-heterocyclic carbene ligand. Organometallics 25:3314-3316
  123. Gerbase AE, de Souza RF, de Souza Vichi EJ, Vieira da Cunha F (1996) Stereoselective polymerization of butadiene by a new dicationic nickel complex. Angew Makromol Chem 239:33- 41
  124. Yamamoto A, Morifuji K, Ikeda S, Saito T, Uchida Y, Misono A (1965) Butadiene polymerization catalysts. Diethylbis(dipyridyl) iron and diethyldipyridyl nickel. J Am Chem Soc 87:4652-4653
  125. Ai P, Chen L, Guo Y, Jie S, Li B (2012) Polymerization of 1,3-butadiene catalyzed by cobalt(II) and nickel(II) complexes bearing imino- or amino-pyridylalcohol ligands in combination with ethylaluminumsesquichloride. J Organomet Chem 705:51-58
  126. Cabassi F, Italia S, Ricci G, Porri L (1988) In: Quirk RP(ed) Transition metal catalyzed polymerizations. Cambridge Univ, MA, USA 655-670
  127. Ricci G, Italia S, Cabassi F, Porri L (1987) Neodymium catalysts for 1,3-diene polymerization: influence of the preparation conditions on activity. Polym Commun 28:223-226
  128. Wilson DJ, Jenkins DK (1992) Butadiene polymerisation using ternary neodymium-based catalyst systems. Polym Bull 27:407-411
  129. Porri L, Ricci G, Shubin N (1998) Polymerization of 1,3-dienes with neodymium catalysts. Macromol Symp 128:53-61
  130. Porri L, Ricci G, Giarrusso A, Shubin N, Lu Z (2000) In: Arjunan P, McGrath JC, Hanlon T (eds) ACS Symposium Series 749 - Olefin polymerization: emerging frontiers. Oxford University, USA, 15-30
  131. Robert D, Spaniol TP, Okuda J (2008) Neutral and monocationic half-sandwich methyl rare-earth metal complexes: synthesis, structure, and 1,3-butadiene polymerization catalysis. Eur J Inorg Chem 2008:2801-2809
  132. Wang D, Li S, Liu X, Gao W, Cui D (2008) Thiophene-NPN ligand supported rare-earth metal bis(alkyl) complexes. Synthesis and catalysis toward highly trans-1,4 selective polymerization of butadiene. Organometallics 27:6531-6538
  133. Sugiyama H, Gambarotta S, Yap GPA, Wilson DR, Thiele SKH (2004) Preparation of an active neodymium catalyst for regioselective butadiene cis-polymerization supported by a dianionic modification of the 2,6-diiminopyridine ligand. Organometallics 23:5054-5061
  134. Zhang L, Suzuki T, Luo Y, Nishiura M, Hou Z (2007) Cationic alkyl rare-earth metal complexes bearing an ancillary bis(phosphinophenyl) amidoligand: a catalytic system for living cis-1,4- polymerization and copolymerization of isoprene and butadiene. Angew Chem Int Ed 46:1909-1913
  135. Gao W, Cui D (2008) Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichloride precursors. J Am Chem Soc 130:4984-4991
  136. Liu D, Cui D (2011) Highly trans-1,4 selective (co-)polymerization of butadiene and isoprene with quinolylanilido rare earth metal bis(alkyl) precursors. Dalton Trans 40:7755-7761
  137. Pirozzi B, Napolitano R, Petraccone V, Esposito S (2004) Determination of the crystal structure of syndiotactic 3,4-poly(2-methyl-1,3-butadiene) by molecular mechanics and X-ray diffraction. Macromol Chem Phys 205:1343-1350
  138. Zhang L, Luo Y, Hou Z (2005) Unprecedented isospecific 3,4-polymerization of isoprene by cationic rare earth metal alkyl species resulting from a binuclear precursor. J Am Chem Soc 127:14562-14563
  139. Nakajima Y, Hou Z (2009) Rare-earth-metal/ platinum heterobinuclear complexes containing reactive Ln-alkyl groups (Ln = Y, Lu): synthesis, structural characterization, and reactivity. Organometallics 28:6861-6870
  140. Ricci G, Leone G, Boglia A, Boccia AC, Zetta L (2009) Cis-1,4-alt-3,4 polyisoprene: synthesis and characterization. Macromolecules 42:9263-9267
  141. Ricci G, Motta T, Boglia A, Alberti E, Zetta L, Bertini F, Arosio P, Famulari A, Meille SV (2005) Synthesis, characterization, and crystalline structure of syndiotactic 1,2-polypentadiene: the trans polymer. Macromolecules 38:8345-8352
  142. Ricci G, Boglia A, Motta T, Bertini F, Boccia AC, Zetta L, Alberti E, Famulari A, Arosio P, Meille SV (2007) Synthesis and structural characterization of syndiotactic trans-1,2 and cis- 1,2 polyhexadienes. J Polym Sci, Part A: Polym Chem 45:5339-5353
  143. Ricci G, Bertini F, Boccia AC, Zetta L, Alberti E, Pirozzi B, Giarrusso A, Porri L (2007) Synthesis and characterization of syndiotactic 1,2-poly(3- methyl-1,3-pentadiene).Macromolecules 40:7238-7243
  144. Pirozzi B, Napolitano R, Giusto G, Esposito S, Ricci G (2007) Determination of the crystal structure of syndiotactic 1,2-poly(E-3-methyl- 1,3-pentadiene) by X-ray diffraction and molecular mechanics. Macromolecules 40:8962- 8968
  145. Boccia AC, Leone G, Boglia A, Ricci G (2013) Novel stereoregular cis-1,4 and trans-1,2 poly(diene)s: synthesis, characterization, and mechanistic considerations. Polymer 54:3492- 3503