Skip to main content
SpringerLink
Log in

Synthetic rubbers prepared by lanthanide coordination catalysts

  • Published:
Science in China Series B: Chemistry Aims and scope Submit manuscript

Abstract

China is rich in rare earth resources. Rare earth elements, also named lanthanides, are number 58 to number 81 elements in the elemental periodic table. They have unique electronic structures and may form various coordination compounds. In the early 1960s, researchers at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences (CIAC) found the catalytic activities of lanthanide compounds in stereospecific polymerization of conjugated dienes, and published the first paper on this topic in 1964. On the basis of this finding, CIAC launched extensive research activities on lanthanide compounds as diene polymerization catalysts, from a series of fundamental research to the efforts of industrializing the rare earth catalyzed cis-1,4-polybutatine rubber and cis-1,4-polyisoprene rubber. This review aims to summarize the progress in this field in the past half century.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Ouyang J. Lanthanide Catalysts and Polymerization (in Chinese). Changchun: Jilin Science Technology Publishing House, 1991. 1–3

    Google Scholar 

  2. Shen Z Q, Gong Z Y, Zhong C Q, Ouyang J. Catalytic activities of lanthanide compounds in stereospecific polymerization. Chin Sci Bull, 1964, (4): 335–336

  3. Shen Z Q, Gong Z Y, Zhong C Q, Ouyang J. Catalytic activities of lanthanide compounds in stereospecific polymerization II: Activity of lanthanide chelate compounds and aluminum alkyl-composed homogeneous catalyst systems for butadiene polymerization (in Chinese). Polym Commun, 1985, 7(3): 193–200

    Google Scholar 

  4. Wang F S, Pang D R, Shen Z Q, Shen Q, Chen Q R, Song X Y, Yang G J, Zheng Y L, Shan X Z. Ce(naph)3-Ali-Bu3-Al2Et3Cl3 catalytic system: isoprene mold-continuous polymerization. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 83–89

    Google Scholar 

  5. Li B, Dong W M, Shi L Y, Jiang L S, Zhang X Q. Industrial development of rare earth butadiene rubber in China (in Chinese). Chin Synth Rubber Indus, 2008, 31(1): 1–4

    Google Scholar 

  6. Yang J H, Hu J Y, Pang S F, Pan E L, Xie D M, Zhong C Q, Ouyang J. Higher activity of lanthanide chloride catalysts for conjugation diene polymerization. Scientia Sinica Ser B, 1980, 23(2): 127–135

    Google Scholar 

  7. Ren C Y, Li G L, Dong W M, Jiang L S, Zhang X Q, Wang F S. Soluble neodymium chloride 2-ethylhexanol complex as a highly active catalyst for controlled isoprene polymerization. Polymer, 2007, 48: 2470–2474

    Article  CAS  Google Scholar 

  8. Li Z X, Wang S L, Wang F S. Study on electronic structure and complex activation of neodymium chloride complex with isopropanol (in Chinese). Acta Phys Chim Sin, 1985, 1(5): 420–423

    CAS  Google Scholar 

  9. Yang J H. Tsutui M, Chen Z, Bergreiter D E, New binary lanthanide catalysts for stereospecific diene polymerization. Macromolecules, 1982, 15(2): 230–233

    Article  CAS  Google Scholar 

  10. Chen W Q, Jin Z S, Xing Y, Fan Y G, Yang G D. Crystal structure of NdCl3-4THF and it’s catalytic activity of diene polymerization. Org Chim Acta, 1987, 130: 125

    CAS  Google Scholar 

  11. Li B, Zhang Z Q, Liu F, Dong W M, Shi L Y, Jiang L S, Zhang X Q. Synthesis of high cis-1,4-polybutadiene with narrow relative molecular mass distribution by homogeneous neodymium-based catalyst (in Chinese). Chin Synth Rubber Indus, 2008, 31(5): 358–361

    Google Scholar 

  12. Wang F S, Shen Z Q, Chen W Q, Zhao H R. Preparation of lanthanide naphthenate with direct extraction method. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 381–387

    Google Scholar 

  13. Wang F S (Changchun Institute of Applied Chemistry Chinese Academy of Sciences Fourth Laboratory Third Group). Stereospecific polymerization of cis-1,4-polyisoprene with lanthanide catalyst. Scientia Sinica Ser B, 1974, 17(5):486–491; (Changchun Institute of Applied Chemistry Chinese Academy of Sciences Fourth Laboratory), Study on stereospecific polymerization with lanthanide coordination catalyst (in Chinese). J Cata, 1980:1(1): 15–25

    Google Scholar 

  14. Liao Y Z, Zhang S X, Liu X C. Butadiene polymerization with lanthanide catalyst and silicone chlorides as third component (in Chinese). Chin J Appl Chem, 1987, 4(1): 13–17

    CAS  Google Scholar 

  15. Wang F S, Pang D R, Sha R Y, Shen Z Q, Shen Q, Chen W Q, Yang G J, Song X Y, Zheng Y L, Jin Y T, Gong Z. The some laws of cis-1,4-stereopecific polymerization of isoprene under the working of lanthanide catalysts. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 100–112

    Google Scholar 

  16. Chen W Q, Song X Y, Zhang Y M. Catalytic activity of lanthanide compounds with various ligands in isoprene polymerization. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 113–123

    Google Scholar 

  17. Wang F S, Jin S, Gong Z. Isoprene polymerization in P507 lanthanide compound catalyst systems. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 134–140

    Google Scholar 

  18. Pang D R. Study on syntheses of cis-1,4-polyisoprene rubber with lanthanide catalysts. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 70–82

    Google Scholar 

  19. Shan C J, Li Y L, Pang S F, Ouyang J. Butadiene polymerization with Nd(OR)3−n Cln-AlEt3 catalytic system. I. Polymerization general laws. butadiene polymerization with Nd(OR)3−n Cln-AlEt3 catalytic system. II Relationship between polymer microstructure and induction effect of catalyst (in Chinese). Acta Chim Sin, 1983, 41(6): 490–504

    CAS  Google Scholar 

  20. Yang J H, Pang S F, Xie D M, Ouyang J, Pan E L, Bian S Z. Effect of various lanthanide elements and various halogen on diene stereo-specific polymerization in LnX3-C2H5OH-Al(C2H5)3 system. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 230–237

    Google Scholar 

  21. Chen W Q, Song X Y, Zhao H G, Wang J F, Zhang J H. Study on cis-1,4-structure and property of lanthanide-polyisoprene rubber. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 255–265

    Google Scholar 

  22. Taniguchi Y, Dong W M, Katsumata T, Shiotuki M, Masuda T. Novel neodymium-based ternary catalyst Nd(OiPr)3/[HNMe2Ph]+ [B(C6F5)4]−/(i-Bu)3Al for isoprene polymerization. Polymer Bull, 2005, 54(3): 173–178

    Article  CAS  Google Scholar 

  23. Furukawa J, Saegusa T, Irako K, Hirooka N, Tsune A. Butadiene-isoprene copolymerization with titanium halidealkyl aluminum catalyst (in Japanese). J Industrial Chem, 1962, 65: 2074–2078

    CAS  Google Scholar 

  24. Sasaki K, Yamasaki K, Kamihara H. Butadiene-isoprene copolymerization with Ziegler type catalyst (in Japanese). Highmolecular Chem, 1964, 21: 9–16

    Google Scholar 

  25. Presleru P S, Molgoplesk B A, Kolechikova M F, Kropacheva Y X. Butadiene-isoprene copolymerization in the presence of coordination-organometallic catalysts (in Russian). Macromol Comp, 1963, 5: 357–362

    Google Scholar 

  26. Weber V.H, Schleimer B, Winter H. The stereoregular homo- and copolymerization of butadienes. Makromol Chem, 1967, 101: 320–336

    Article  CAS  Google Scholar 

  27. Pang S F, Hu J Y, Xie D M, Ouyang J. Butadiene-isoprene copoly-merization with various lanthanide catalytic systems. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 161–173

    Google Scholar 

  28. Ouyang J. Lanthanide Catalysts and Polymerization (in Chinese). Changchun: Jilin Science Technology Publishing House, 1991, 38–41

    Google Scholar 

  29. Throckmorton M C. Comparison of cerium and other transition metal catalyst systems for preparing very high cis-1,4-polybutadiene. Kaut Gummi Kunst, 1969, 22(6): 293–297

    CAS  Google Scholar 

  30. Wang B L, Cui D M, Lv K. Highly 3,4-selective living polymerization of isoprene with rare earth metal fluorenyl N-heterocyclic carbene precursor. Macromolecules, 2008, 41: 1983–1988

    Article  CAS  Google Scholar 

  31. Kaita S, Yamanaka M, Horiuchi A C, Wakatsuki Y. Butadiene polymerization catalyzed by lanthanide metal-dependent control of 1,4-cis/trans stereoselectivity and molecular weight. Macromolecules, 2006, 39(4): 1359–1363

    Article  CAS  Google Scholar 

  32. Kaita S, HOU Z M, Nishiura M, Doi Y, Kurazumi J, Horiuch A.C, Wakatsuki Y. Ultimately specific 1,4-cis polymerization of 1,3-butadiene with a novel gadolinium catalyst. Macromol Rapid Commun, 2003, 24: 179–184

    Article  CAS  Google Scholar 

  33. Wang D, Li S H, Liu X L, Gao W, Cui D M. Thiophene-NPN ligand supported rare-earth metal bis(alkyl) complexes. Synthesis and catalysis toward highly trans-1,4-selective polymerization of butadiene. Organometallics, 2008, 27: 6531–6538

    Article  CAS  Google Scholar 

  34. Pan E L, Zhong C Q, Xie D M, Ouyang J. Study on determination of the active center numbers for butadiene polymerization and its kinetics with the some neodymium catalyst systems. I. Effect of polymerization conditions on active center concentration (in Chinese). Acta Chim Sin, 1982, 40(4): 301–309

    CAS  Google Scholar 

  35. Pan E L, Zhong C Q, Xie D M, Ouyang J. Study on determination of the active center numbers for butadiene polymerization and its kinetics with the some neodymium catalyst systems. II. Study on the process of polymeric chain propagation chain transfer and chain termination (in Chinese). Acta Chim Sin, 1982, 40(5): 395–405

    CAS  Google Scholar 

  36. Monokov Y B, Benshev Y H, Birg A A, Rafikov S R. Dokl. Akad. Nauk SSSR (in Russian), 1997, 234(5): 1125

    Google Scholar 

  37. Gong Z, Li B L, Yang G J, Wang F S. The kinetics of isoprene polymerization in the presence of Nd(naph)3-Al(i-Bu)3-Al2(C2H5)3Cl3 catalyst systems (in Chinese). Acta polym Sin, 1983(2): 116–121

  38. Zhu X H, Qiao Y Q, Han D N. Study on kinetics of isoprene polymerization catalyzed by rare earth metal (in Chinese). Acta polym Sin, 1984, (3): 207–213

  39. Jin Y T, Li X M, Sun Y F, Ouyang J. Crystalline bimetallic lanthanide complex having polymerization activity for dienes. Chin Sci Bull, 1982, 27(1): 32–32

    Google Scholar 

  40. Shan C J, Lin Y H, Jin S C, Ouyang J, Fan Y G, Yang G D, Yu J S. Crystal structure of [Al3Nd6(μ2Cl)6(μ3Cl)6(μ2Et)9Et5OCH(CH3)2]2 (in Chinese). Acta Chim Sin, 1987, 45(10): 949–954

    CAS  Google Scholar 

  41. Shan C J, Lin Y H, Ouyang J, Fan Y G, Yang G D. Single crystal structure of a polymerization active Nd-Al bimetallic complex. Makromol Chem, 1987, 188: 629–635

    Article  CAS  Google Scholar 

  42. Destri S, Gallzzi M C, Giarrusso A, Porri L. On the stereochemistry of monomer insertion in the 1,4-polymerization of conjugated diolefins. Makromol Chem Rapid Commun, 1980, (1): 293–296

  43. Zhao X J, Wang F S. Active chain terminal property and polymerization mechanism in diene polymerization catalyzed by rare earth metal. Chin Sci Bull, 1982, (12): 731–732

  44. Shan C J, Ji X Z, Pang S F, Sun T, Yang J H. Butadiene polymerization with multinuclear Nd-Al bimetallic complex I. Relationship between molecular weight and microstructure as well as discussion of polymerization mechanism (in Chinese). Acta Polym Sin, 1989, (6): 709–713

  45. Shan C J, Lin Y H, Wang M Y, Shi E D, Ouyang J. Crystal of Nd-Al bimetallic complex having polymerization catalytic activity. Chin Sci Bull, 1986, 31(2): 123–123

    Google Scholar 

  46. Gao W, Cui D M. 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, 2008, 130(14): 4984–4991

    Article  CAS  Google Scholar 

  47. Tobisch S. Theoretical investigation of the mechanism of cis-trans regulation for the alkylnickel(II)-catalyzed 1,4 polymerization of butadiene. Acc Chem Res, 2002, 35(2): 96–104

    Article  CAS  Google Scholar 

  48. Shen Z Q, Ouyang J, Wang F S, Hu Z Y, Yu F S, Qian B G. The characteristics of lanthanide coordination catalysts and the cis-polydienes prepared therewith. J Polym Sci Polym Chem Ed, 1980, 18(12): 3345–3357

    Article  Google Scholar 

  49. Friebe L, Nuyken O, Obrecht W. Neodymium-based Ziegler-Natta catalysts and their application in diene polymerization. Adv Polym Sic, 2006, 204(11): 1–154

    Article  CAS  Google Scholar 

  50. Marina N G, Monokov Y B, Sabiov Z M etal. Lanthanide compounds-catalysts of stereospecific polymerization of diene monomers (Review). Polym Sci USSR (Engltrans), 1991, 33(3): 387–417

    Article  Google Scholar 

  51. Wilson D J. Recent advances in the neodymium catalyzed polymerization of 1,3-dienes. Makromol Chem Macromol Symp, 1993, 66(96): 273–288

    CAS  Google Scholar 

  52. Yang S T, Xu G S, Bao X Y, Gu Y M, Liu Y R. Study on basic and practical properties of Nd-BR (in Chinese). Tire Industry, 2001, 21(12): 713–719

    CAS  Google Scholar 

  53. Zhao S Q, Dong W M, Shi L Y, Jiang L S, Zhang X Q. Developments of rare earth catalyst for cis-1,4-polybutadiene rubber (in Chinese). Chin Synth Rubber Indu, 2008, 31(2): 81–86

    CAS  Google Scholar 

  54. Zhang X H, Li B L, Zhang X Q, Jiang L S, Lu B, Shi L Y, Gu Z M, Lu G G, Li B. Properties of domestic cis-1,4-polybutadiene rubber polymerized with rare-earth catalyst (in Chinese). Chin Synth Rubber Indu, 2006, 29(1): 11–13

    Google Scholar 

  55. Dong W M, Jiang L S, Zhang X Q. Synthesis of cis-1,4-polybutadiene with narrow relative molecular mass distribution by using homogeneous neodymium catalyst (in Chinese). Chin Synth Rubber Indu, 2005, 28(5): 388–388

    CAS  Google Scholar 

  56. Zhang X H, Li B L, Dong W M, Yu Q Z, Zhang X Q, Zhang Z Q, Lin S G, Shi L Y. Effects of relative molecular mass and its distribution on properties of rare-earth catalyst-based cis-1,4-polybutadiene rubber (in Chinese). Chin Synth Rubber Indu, 2007, 30(5): 391–394

    CAS  Google Scholar 

  57. Yang C Y, Zheng Y L, Wang F S. Isoprene polymerization homogeneous catalyst (in Chinese). Chin Synthe Rubber Indu, 1991, 14(3): 183–187

    CAS  Google Scholar 

  58. Gong Z, Guo C L, Zheng Y L, Zhao L Q, Wang F S. Study on bulk polymerization of isoprene catalyzed by Nd(naph)3-Al(i-Bu)2H-CH3SiHCl2 system (in Chinese). Chin J Catal, 1991, 12(1): 47–51

    CAS  Google Scholar 

  59. Li G L, Dong W M, Jiang L S, Zhang X Q, Wang F S. Homogenous Nd(vers)3/AliBu2H/AliBu2Cl catalyst for isoprene polymerization (in Chinese). Chin Synth Rubber Indu, 2006, 29(3): 181–185

    CAS  Google Scholar 

  60. Wang F S, Wang Y L, Sha R Y, Shen Z Q, Pang D R, Zhang X H, Gong Z. Effects of molecular weight and its distribution of lanthanide polyisoprene rubber on its property. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 250–254

    Google Scholar 

  61. Yu Q Z, Li B L, Li G L, Zhang X Q, Zhang X H. Effects of relative molecular mass on the properties of lanthanide-polyisoprene rubber (in Chinese). Special Purpose Rubber Products, 2008, 29(4): 4–7

    Google Scholar 

  62. Ji X Z, Pang S F, Li Y L, Ouyang J. Living polymerization of butadiene with lanthanide-coordination catalyst, Scentia Sinica Ser B, 1985, (2): 120–127

  63. Ruan A N, Zhong C Q, Yang J H, Pang S F, Hu J Y, Xie D M, Pan E L. Preparation of butadiene-isoprene copolymer rubber with lanthanide catalyst in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 174–189

    Google Scholar 

  64. Huang B T, Shen Z Q. The Progress of Olefin and Diene Coordination Polymerization (in Chinese). Beijing: Science Press, 1998, 219–245

    Google Scholar 

  65. Shen Z Q, Song X Y, Xiao S X, Yang J P, Kan X L. Butadiene-isoprene copolymerization in lanthanide chloride-alcohol-trialkyalaluminum catalytic system. Scentia Sinica Ser B, 1981, 1340–1349

  66. Shen Z Q, Song X Y, Yang J P, Kan X L. Coordination copolymerization of butadiene and isoprene with rare earth chloride-aluminum trialkyls catalytic systems. J Appl Poly Sci, 1983, 28: 1585–1592

    Article  CAS  Google Scholar 

  67. Oehme A. Gebauer U. Gehrke K. Beyer P. Hartmann B. Lechner M D. The influence of the catalyst preparation on the homo and copolymerization of butadiene and isoprene. Macromol Chem Phys, 1994, 195: 3773–3781

    Article  CAS  Google Scholar 

  68. Yu Y L, Fang T R, Shen Q, Song X Y, Xiao S X, Li J F, Yang G J, Jin Y T, Chen Q R, Gao S Z, Zhang Y M. Study on syntheses of butadiene-isoprene copolymerization rubber with lanthanide catalytic system. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 190–201

    Google Scholar 

  69. Wang F S, Shen Q, Song X Y, Xiao S X, Yang G J. Study on diene polymerization process in lanthanide catalytic system. in: The Collected Papers of Lanthanide-Catalyzed Synthetic Rubber (in Chinese). Beijing: Science Press, 1980. 238–245

    Google Scholar 

  70. Zhang L X, Suzuki T, Luo Y, Nishiura M, Hou Z M. Cationic alkyl rare-earth metal complexes bearing an ancillary bis(phosphinophenyl) amido ligand: A catalytic system for living cis-1,4-polymerization and copolymerization of isoprene and butadiene, Angew Chem Int Ed, 2007, 46: 1909–1913

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    WenQi Chen & FoSong Wang

Authors
  1. WenQi Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. FoSong Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to WenQi Chen or FoSong Wang.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chen, W., Wang, F. Synthetic rubbers prepared by lanthanide coordination catalysts. Sci. China Ser. B-Chem. 52, 1520–1543 (2009). https://doi.org/10.1007/s11426-009-0214-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-009-0214-9

Keywords

Search

Navigation