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(α-Diimine)palladium catalyzed ethylene polymerization and (co)polymerization with polar comonomers

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Abstract

In this review, a recent development of cationic α-diimine palladium(II) complexes for ethylene polymerization and copolymerization with polar functionalized comonomers was briefly described. First, the polymerization mechanism for this type of catalysts was discussed. Next, recent advances in ligand design were provided with special focus on the influence of ligand structures on the catalytic polymerization properties. Last, the ethylene homopolymerization and copolymerization with various polar comonomers, especially acrylate and vinyl ethers were summarized.

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References

  1. Ziegler K, Holzkamp E, Briel H, Martin H. Das mülheimer normaldruck-polyäthylen-verfahren. Angew Chem Int Ed, 1955, 67: 541–547

    Article  CAS  Google Scholar 

  2. Natta G, Pino P, Corradini, P, Dannusso F, Mantica E, Mazzanti G, Moraglio G. Crystalline high polymers of a-olefins. J Am Chem Soc, 1955, 77: 1708–1710

    Article  CAS  Google Scholar 

  3. Ittel SD, Johnson LK, Brookhart M. Late-metal catalysts for ethylene homo- and copolymerization. Chem Rev, 2000, 100: 1169–1203

    Article  CAS  Google Scholar 

  4. Coates GW. Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem Rev, 2000, 100: 1223–1252

    Article  CAS  Google Scholar 

  5. Nakamura A, Ito S, Nozaki K. Coordination-insertion copolymerization of fundamental polar monomers. Chem Rev, 2009, 109: 5215–5244

    Article  CAS  Google Scholar 

  6. Chen EYX. Coordination polymerization of polar vinyl monomers by single-site metal catalysts. Chem Rev, 2009, 109: 5157–5214

    Article  CAS  Google Scholar 

  7. Makio H, Terao H, Iwashita A, Fujita T. FI catalysts for olefin polymerization: a comprehensive treatment. Chem Rev, 2011, 111: 2363–2449

    Article  CAS  Google Scholar 

  8. Talaei A, Taromi FA, Arefazar A, Ahmadjo S, Jazani OM. The influence of bridge type on the activity of supported metallocene catalysts in ethylene polymerization. Chinese J Polym Sci, 2014, 2: 137–142

    Article  Google Scholar 

  9. Cai Z, Su H, Shiono T. Precise synthesis of olefin block copolymers using a syndiospecific living polymerization system. Chinese J Polym Sci, 2013, 4: 541–549

    Article  Google Scholar 

  10. Tang J, Li S, Wang Y, Tang T. In situ ethylene copolymerization with an olefin-type monomer for one-pot synthesis of polyethylene tethered on multi-walled carbon nanotubes. Chinese J Polym Sci, 2013, 10: 1329–1333

    Article  Google Scholar 

  11. Hu HB, Gao HY, Zhu FM, Wu Q. Olefin polymerization catalyzed by nickel complexes bearing N,N-bidentate ligands. Sci China Chem, 2012, 42: 628–635

    CAS  Google Scholar 

  12. Li BG, Luo YW, Wang WJ, Fan H, Zhu SP. Polymer product engineering: an emerging discipline of chemical engineering for high performance polymer materials. Sci China Chem, 2014, 44: 1461–1468

    CAS  Google Scholar 

  13. Wang J, Chen JH, Li XZ, Liu HT, Gao MZ. Development of phthalate-free internal electron donors used in Ziegler-Natta catalysts for propylene polymerization. Sci China Chem, 2014, 44: 1705–1713

    CAS  Google Scholar 

  14. Johnson LK, Killian CM, Brookhart M. New Pd(II)- and Ni(II)-based catalysts for polymerization of ethylene and a-olefins. J Am Chem Soc, 1995, 117: 6414–6415

    Article  CAS  Google Scholar 

  15. Gibson VC, Spitzmesser SK. Advances in non-metallocene olefin polymerization catalysis. Chem Rev, 2003, 103: 283–316

    Article  CAS  Google Scholar 

  16. Johnson LK, Mecking S, Brookhart M. Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(II) catalysts. J Am Chem Soc, 1996, 118: 267–268

    Article  CAS  Google Scholar 

  17. Mecking S, Johnson LK, Wang L, Brookhart M. Mechanistic studies of the palladium-catalyzed copolymerization of ethylene and α-olefins with methyl acrylate. J Am Chem Soc, 1998, 120: 888–899

    Article  CAS  Google Scholar 

  18. Gates DP, Svejda SA, Oñate E, Killian CM, Johnson LK, White PS, Brookhart M. Synthesis of branched polyethylene using (α-diimine) nickel(II) catalysts: influence of temperature, ethylene pressure, and ligand structure on polymer properties. Macromolecules, 2000, 33: 2320–2334

    Article  CAS  Google Scholar 

  19. Kang M, Sen A, Zakharov L, Rheingold AL. Diametrically opposite trends in alkene insertion in late and early transition metal compounds: relevance to transition-metal-catalyzed polymerization of polar vinyl monomers. J Am Chem Soc, 2002, 124: 12080–12081

    Article  CAS  Google Scholar 

  20. Chen G, Ma XS, Guan Z. Synthesis of functional olefin copolymers with controllable topologies using a chain-walking catalyst. J Am Chem Soc, 2003, 125: 6697–6704

    Article  CAS  Google Scholar 

  21. Guan Z, Cotts PM, McCord EF, McLain SJ. Chain walking: a new strategy to control polymer topology. Science, 1999, 283: 2059–2061

    Article  CAS  Google Scholar 

  22. Cotts PM, Guan Z, McCord EF, McLain SJ. Novel branching topology in polyethylenes as revealed by light scattering and 13C NMR. Macromolecules, 2000, 33: 6945–6952

    Article  CAS  Google Scholar 

  23. Guan Z. Control of polymer topology by chain-walking catalysts. Chem Eur J, 2002, 8: 3086–3092

    Article  CAS  Google Scholar 

  24. Guan Z. Control of polymer topology through late-transition-metal catalysis. J Polym Sci A: Polym Chem, 2003, 41: 3680–3692

    Article  CAS  Google Scholar 

  25. Xu Y, Xiang P, Ye Z, Wang WJ. Hyperbranched-linear polyethylene block polymers constructed with chain blocks of hybrid chain topologies via one-pot stagewise chain walking ethylene “living” polymerization. Macromolecules, 2010, 43: 8026–8038

    Article  CAS  Google Scholar 

  26. Anselment TMJ, Vagin SI, Rieger B. Activation of late transition metal catalysts for olefin polymerizations and olefin/CO copolymerizations. Dalton Trans, 2008, 34: 4537–4548

    Article  Google Scholar 

  27. Guan Z, Popeney CS. Recent progress in late transition metal α-diimine catalysts for olefin polymerization. Top Organomet Chem, 2009, 26: 179–220

    CAS  Google Scholar 

  28. Luo S, Jordan RF. Copolymerization of silyl vinyl ethers with olefins by (α-diimine)PdR+. J Am Chem Soc, 2006, 128: 12072–12073

    Article  CAS  Google Scholar 

  29. Chen CL, Luo S, Jordan RF. Multiple insertion of a silyl vinyl ether by (α-diimine)PdMe+ species. J Am Chem Soc, 2008, 130: 12892–12893

    Article  CAS  Google Scholar 

  30. Chen CL, Luo S, Jordan RF. Cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe+ species. J Am Chem Soc, 2010, 132: 5273–5284

    Article  CAS  Google Scholar 

  31. Boaen NK, Hillmyer MA. Post-polymerization functionalization of polyolefins. Chem Soc Rev, 2005, 34: 267–275

    Article  CAS  Google Scholar 

  32. Park S, Takeuchi D, Osakada K. Pd complex-promoted cyclopoly-merization of functionalized α,ω-dienes and copolymerization with ethylene to afford polymers with cyclic repeating units. J Am Chem Soc, 2006, 128: 3510–3511

    Article  CAS  Google Scholar 

  33. Okada T, Park S, Takeuchi D, Osakada K. Pd-catalyzed polymerization of dienes that involves chain-walking isomerization of the growing polymer end: synthesis of polymers composed of polymethylene and five-membered-ring units. Angew Chem Int Ed, 2007, 46: 6141–6143

    Article  CAS  Google Scholar 

  34. Park S, Okada T, Takeuchi D, Osakada K. Cyclopolymerization and copolymerization of functionalized 1,6-heptadienes catalyzed by Pd complexes: mechanism and application to physical-gel formation. Chem Eur J, 2010, 16: 8662–8678

    Article  CAS  Google Scholar 

  35. Takeuchi D. Novel controlled polymerization of cyclo-olefins, dienes, and trienes by utilizing reaction properties of late transition metals. Macromo Chem Phys, 2011, 212: 1545–1551

    Article  CAS  Google Scholar 

  36. Kiesewetter J, Kaminsky W. Ethene/norbornene copolymerization with palladium(II) α-diimine catalysts: from ligand screening to discrete catalyst species. Chem Eur J, 2003, 9: 1750–1758

    Article  CAS  Google Scholar 

  37. Kiesewetter J, Arikan B, Kaminsky W. Copolymerization of ethene with norbornene using palladium(II) α-diimine catalysts: influence of feed composition, polymerization temperature, and ligand structure on copolymer properties and microstructure. Polymer, 2006, 47: 3302–3314

    Article  CAS  Google Scholar 

  38. Zhang Y, Ye Z. Homogeneous polyhedral oligomeric silsesquioxane (POSS)-supported Pd-diimine complex and synthesis of polyethylenes end-tethered with a POSS nanoparticle via ethylene “living” polymerization. Chem Commun, 2008, 10: 1178–1180

    Article  Google Scholar 

  39. Zhang K, Ye Z, Subramanian R. Synthesis of block copolymers of ethylene with styrene and n-butyl acrylate via a tandem strategy combining ethylene “living” polymerization catalyzed by a functionalized Pd-diimine catalyst with atom transfer radical polymerization. Macromolecules, 2008, 41: 640–649

    Article  CAS  Google Scholar 

  40. Zhang K, Ye Z, Subramanian R. A trinuclear Pd-diimine catalyst for “core-first” synthesis of three-arm star polyethylenes via ethylene “living” polymerization. Macromolecules, 2009, 42: 2313–2316

    Article  CAS  Google Scholar 

  41. Chen G, Huynh D, Felgner PL, Guan Z. Tandem chain walking polymerization and atom transferRadical polymerization for efficient synthesis of dendritic nanoparticles for bioconjugation. J Am Chem Soc, 2006, 128: 4298–4302

    Article  CAS  Google Scholar 

  42. Ye Z, Xu L, Dong Z, Xiang P. Designing polyethylenes of complex chain architectures via Pd-diimine-catalyzed “living” ethylene polymerization. Chem Commun, 2013, 49: 6235–6255

    Article  CAS  Google Scholar 

  43. Dong Z, Ye Z. Hyperbranched polyethylenes by chain walking polymerization: synthesis, properties, functionalization, and applications. Polym Chem, 2012, 3: 286–301

    Article  CAS  Google Scholar 

  44. Chen Y, Wang L, Yu H, Zhao Y, Sun R, Jing G, Huang J, Khalid H, Abbasi NM, Akram M. Synthesis and application of polyethylene-based functionalized hyperbranched polymer. Pro Polym Sci, 2015, doi: 10.1016/j.progpolymsci.2015.01.004

    Google Scholar 

  45. Van Asselt R, Elsevier CJ, Smeets WWJ, Spek AL. Zerovalent palladium and platinum complexes containing rigid bidentate nitrogen ligands and alkenes: synthesis, characterization, alkene rotation and substitution reactions. X-ray crystal structure of [bis((2,6-diisopropylphenyl)imino)acenaphthene](maleic anhydride) palladium(0). Inorg Chem, 1994, 33: 1521–1531

    Article  Google Scholar 

  46. Salo EV, Guan Z. Late-transition-metal complexes with bisazaferrocene ligands for ethylene oligomerization. Organometallics, 2003, 22: 5033–5046

    Article  CAS  Google Scholar 

  47. Shultz LH, Tempel DJ, Brookhart M. Palladium(II) β-agostic alkyl cations and alkyl ethylene complexes: investigation of polymer chain isomerization mechanisms. J Am Chem Soc, 2001, 123: 11539–11555

    Article  CAS  Google Scholar 

  48. Deng L, Margl P, Ziegler T. A density functional study of nickel(II) diimide catalyzed polymerization of ethylene. J Am Chem Soc, 1997, 119: 1094–1100

    Article  CAS  Google Scholar 

  49. Deng L, Woo TK, Cavallo L, Margl PM, Ziegler T. The role of bulky substituents in Brookhart-type Ni(II) diimine catalyzed olefin polymerization: a combined density functional theory and molecular mechanics study. J Am Chem Soc, 1997, 119: 6177–6186

    Article  CAS  Google Scholar 

  50. Tempel DJ, Johnson LK, Huff RL, White PS, Brookhart M. Mechanistic studies of Pd(II)-α-diimine-catalyzed olefin polymerizations. J Am Chem Soc, 2000, 122: 6686–6700

    Article  CAS  Google Scholar 

  51. Guo L, Gao H, Guan Q, Hu H, Deng J, Liu J, Liu F, Wu Q. Substituent effects of the backbone in α-diimine palladium catalysts on homo- and copolymerization of ethylene with methyl acrylate. Organometallics, 2012, 31: 6054–6062

    Article  CAS  Google Scholar 

  52. Camacho DH, Salo EV, Ziller JW, Guan Z. Cyclophane-based highly active late-transition-metal catalysts for ethylene polymerization. Angew Chem Int Ed, 2004, 43: 1821–1825

    Article  CAS  Google Scholar 

  53. Popeney CS, Camacho DH, Guan Z. Efficient incorporation of polar comonomers in copolymerizations with ethylene using a cyclophane-based Pd(II) α-diimine catalyst. J Am Chem Soc, 2007, 129: 10062–10063

    Article  CAS  Google Scholar 

  54. Popeney CS, Guan Z. A mechanistic investigation on copolymerization of ethylene with polar monomers using a cyclophane-based Pd(II) α-diimine catalyst. J Am Chem Soc, 2009, 131: 12384–12393

    Article  CAS  Google Scholar 

  55. Popeney CS, Rheingold AL, Guan Z. Nickel(II) and palladium(II) polymerization catalysts bearing a fluorinated cyclophane ligand: stabilization of the reactive intermediate. Organometallics, 2009, 28: 4452–4463

    Article  CAS  Google Scholar 

  56. Camacho DH, Salo EV, Guan Z, Ziller JW. Nickel(II) and palladium(II) complexes with an alkane-bridged macrocyclic ligand: synthesis, characterization, and polymerization tests. Organometallics, 2005, 24: 4933–4939

    Article  CAS  Google Scholar 

  57. Leung DH, Ziller JW, Guan Z. Axial donating ligands: a new strategy for late transition metal olefin polymerization catalysis. J Am Chem Soc, 2008, 130: 7538–7539

    Article  CAS  Google Scholar 

  58. Allen KE, Campos J, Daugulis O, Brookhart M. Living polymerization of ethylene and copolymerization of ethylene/methyl acrylate using “sandwich” diimine palladium catalysts. ACS Catal, 2015, 5: 456–464

    Article  CAS  Google Scholar 

  59. Takano S, Takeuchi D, Osakada K, Akamatsu N, Shishido A. Dipalladium catalyst for olefin polymerization: introduction of acrylate units into the main chain of branched polyethylene. Angew Chem Int Ed, 2014, 53: 9246–9250

    Article  CAS  Google Scholar 

  60. Delferro M, Marks TJ. Multinuclear olefin polymerization catalysts. Chem Rev, 2011, 111: 2450–2485

    Article  CAS  Google Scholar 

  61. Zhu L, Fu ZS, Pan HJ, Feng W, Chen CL, Fan ZQ. Synthesis and application of binuclear α-diimine nickel/palladium catalysts with a conjugated backbone. Dalton Trans, 2014, 43: 2900–2906

    Article  CAS  Google Scholar 

  62. Popeney CS, Guan Z. Ligand electronic effects on late transition metal polymerization catalysts. Organometallics, 2005, 24: 1145–1155

    Article  CAS  Google Scholar 

  63. Popeney CS, Guan Z. Effect of ligand electronics on the stability and chain transfer rates of substituted Pd(II) α-diimine catalysts. Macromolecules, 2010, 43: 4091–4097

    Article  CAS  Google Scholar 

  64. Popeney CS, Levins CM, Guan Z. Systematic investigation of ligand substitution effects in cyclophane-based nickel(II) and palladium(II) olefin polymerization catalysts. Organometallics, 2011, 30: 2432–2452

    Article  CAS  Google Scholar 

  65. Gottfried AC, Brookhart M. Living polymerization of ethylene using Pd(II) a-diimine catalysts. Macromolecules, 2001, 34: 1140–1142

    Article  CAS  Google Scholar 

  66. Gottfried AC, Brookhart M. Living and block copolymerization of ethylene and α-olefins using palladium(II)-α-diimine catalysts. Macromolecules, 2003, 36: 3085–3100

    Article  Google Scholar 

  67. Foley SR, Stockland RA Jr, Shen H, Jordan RF. Reaction of vinyl chloride with late transition metal olefin polymerization catalysts. J Am Chem Soc, 2003, 125: 4350–4361

    Article  CAS  Google Scholar 

  68. Williams BS, Leatherman MD, White PS, Brookhart M. Reactions of vinyl acetate and vinyl trifluoroacetate with cationic diimine Pd(II) and Ni(II) alkyl complexes: identification of problems connected with copolymerizations of these monomers with ethylene. J Am Chem Soc, 2005, 127: 5132–5146

    Article  CAS  Google Scholar 

  69. Li W, Zhang X, Meetsma A, Hessen B. Palladium-catalyzed copolymerization of ethene with acrolein dimethyl acetal: catalyst action and deactivation. J Am Chem Soc, 2004, 126: 12246–12247

    Article  CAS  Google Scholar 

  70. Chen CL, Jordan RF. Palladium-catalyzed dimerization of vinyl ethers to acetals. J Am Chem Soc, 2010, 132: 10254–10255

    Article  CAS  Google Scholar 

  71. Li W, Zhang X, Meetsma A, Hessen B. Reactions of cationic palladium α-diimine complexes with nitrogen-containing olefins: branched polyethylene with carbazole functionalities. Organometallics, 2008, 27: 2052–2057

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai, 201620, China

    Lihua Guo

  2. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165, China

    Lihua Guo

  3. Key Laboratory of Soft Matter Chemistry, Chinese Academy of Sciences; Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Changle Chen

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  1. Lihua Guo
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Correspondence to Changle Chen.

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Guo, L., Chen, C. (α-Diimine)palladium catalyzed ethylene polymerization and (co)polymerization with polar comonomers. Sci. China Chem. 58, 1663–1673 (2015). https://doi.org/10.1007/s11426-015-5433-7

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  • DOI: https://doi.org/10.1007/s11426-015-5433-7

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