Influence of diethyl zinc on ethylene-norbornene copolymerization

Document Type: Original research

Authors

Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora Eloisa Mano-IMA-UFRJ Av. Horácio Macedo, 2030, Centro de Tecnologia Bloco J. Cidade Universitária. Rio de Janeiro, RJ, Brazil

Abstract

Ethylene-norbornene copolymers were synthesized with a homogeneous catalyst system based on bis(imino) pyridine iron with the addition of diethyl zinc (DEZ) as alkyd transfer agent to promote immortal copolymerization. The addition of DEZ did not influence the catalytic activity in copolymerization with 7.5 mmol of norbornene (NB), but in the reactions with 70 mmol, the comonomer promoted an increase of activity. We observed by thermal analysis that the norbornene inserted in the chains promoted an increase in thermal stability of the synthesized material with higher amounts of comonomer, since the temperature of initial degradation was much higher for these copolymers compared to polyethylene. In addition, for the copolymers with 7.5 mmol of norbornene, the DEZ served as alkyd transfer agent, as shown by the gel permeation chromatography analysis, leading to a decrease in both molar mass and polydispersity. The UV-Vis spectra showed that the diethyl zinc did not change the catalytically active center, but only acted as an alkyd transfer agent.

Keywords

Main Subjects


  1. Janiak C, Lassahn PG (2001) Metal catalysts for the vinyl polymerization of norbornene. J Mol Catal A: Chem 166: 193–209
  2. Floros G, Saragas N, Paraskevopoulou P, Psaroudakis N, Koinis S, Pitsikalis M, Hadjichristidis N, Mertis K (2012) Ring opening metathesis polymerization of norbornene and derivatives by the triply bonded ditungsten complex Na[W2(μ-Cl)3Cl4(THF)2]•(THF)3. Polymers 4:1657-1673
  3. Madan R, Srivastava A, Anand RC, Varma IK (1998) Polymers derived from bicylo[2.2.1] heptene and its derivatives. Prog Polym Sci 23: 621–663
  4. Woodman TJ, Sarazin Y, Garratt S, Fink G, Bochmann M (2005) Chromium allyl and alkyl catalysts for the vinyl polymerization of norbornene and ethylene–norbornene copolymerizations. J Mol Catal A-Chem 235: 88–97
  5. Ravasio A, Zampa C, Boggioni L, Tritto I, Hitzbleck J, Okuda J (2008) Copolymerization of ethylene with norbornene catalyzed by cationic rare-earth metal half-sandwich complexes. Macromolecules 41: 9565–9569
  6. Ravasio A, Boggioni L, Tritto I (2011) Copolymerization of ethylene with norbornene by neutral aryl phosphine sulfonate palladium catalyst. Macromolecules 44: 4180–4186
  7. Wendt R A, Fink G (2003) Ethene–norbornene copolymerizations using two different homogeneous metallocene catalyst systems and investigations of the copolymer microstructure. J Mol Catal A-Chem 203: 101–111
  8. Gao H, Hu H, Wu Q (2010) High norbornene incorporation in ethylene-norbornene copolymerization with a bis(α-alkyloxoimine) titanium-MAO catalyst. Sci China Chem 53: 1634-1640
  9. Cai Z, Harada R, Nakayama Y, Shiono T (2010) Highly active living random copolymerization of norbornene and 1-alkene with ansa-fluorenylamido dimethyltitanium derivative: Substituent effects on fluorenyl ligand. Macromolecules 43: 4527–4531
  10. Kim K-N, Kimm H, Lee J-W (2001) Effect of interlayer structure, matrix viscosity and composition of a functionaiized polymer on the phase structure of polypropylene-montmorillonite nanocomposites. Polym Eng Sci 41: 1963-1969
  11. Padmanabhan S, Vijayakrishna K, Mani R (2010) Copolymerization of ethylene and norbornene by zirconium complexes containing symmetrically tuned trianionic ligands. Polym Bull 65: 13–23
  12. Kaminsky W, Tran P-D, Werner R (2004) New polymers by copolymerization of ethylene and norbornene with metallocene catalysts. Macromol Symp 213: 101–108
  13. Jansen JC, Mendichi R, Sacchi MC, Tritto I (2003) Kinetic studies of the copolymerization of ethylene with norbornene by ansa-zirconocene/ methylaluminoxane catalysts: Evidence of a long-lasting “quasi-living” initial period. Macromol Chem Phys 204: 522–530
  14. Tritto I, Marestin C, Boggioni L, Zetta L, Provasoli A, Ferro DR (2000) Ethylene−norbornene copolymer microstructure. Assessment and advances based on assignments of 13C-NMR spectra. Macromolecules 33: 8931–8944
  15. Tritto I, Boggioni L, Jansen JC, Thorshaug K, Sacchi MC, Ferro DR (2002) Ethylene− norbornene copolymers from metallocene-based catalysts: Microstructure at tetrad level and reactivity ratios. Macromolecules 35: 616–623
  16. He L-P, Liu J-Y, Li Y-G, Liu S-R, Li Y-S (2009) High-temperature living copolymerization of ethylene with norbornene by titanium complexes bearing bidentate [O, P] ligands. Macromolecules 42: 8566–8570
  17. Vijayakrishna K, Sundararajan G (2006) Non- Cp type titanium precatalysts for ethylene/ norbornene copolymerization. Polymer 47: 8289–8296
  18. Hu H, Gao H, Song K, Liu F, Long J, Zhang L F, Q. Wu Zhu (2008) Novel bis(benzoin) titanium catalyst for homo and copolymerization of norbornene with ethylene: Synthesis, characterization and catalytic properties. Polymer 49: 4552–4558
  19. Nomura K, Tsubota M, Fujiki M (2003) Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)titanium(IV) complexes− MAO catalyst system. Macromolecules 36: 3797–3799
  20. Thorshaug K, Mendichi R, Boggioni L, Tritto I, Trinkle S, Friedrich C, Mülhaupt R (2002) Poly(ethene-co-norbornene) obtained with a constrained geometry catalyst. A study of reaction kinetics and copolymer properties. Macromolecules 35: 2903–2911
  21. Schrock RR (1990) Living ring-opening metathesis polymerization catalyzed by well-characterized transition-metal alkylidene complexes. Acc Chem Res 23: 158–165
  22. Yoshida, Y et al. (2004) Living copolymerization of ethylene with norbornene catalyzed by bis(pyrrolide−imine) titanium complexes with MAO. Am Chem Soc 126: 12023-12032
  23. Ravasio A, Boggioni L, Scalcione G, Bertini F, Piovani D, Tritto I (2012) Living copolymerization of ethylene with norbornene by fluorinated enolato-imine titanium catalyst J Polym Sci Pol Chem 50: 3867-3874
  24. Long YY, Ye WP, Shi XC, Li YS (2009) Living copolymerization of ethylene with norbornene mediated by heteroligated (salicylaldiminato) (β-enaminoketonato)titanium catalysts. J Polym Sci Pol Chem 47: 6072–6082
  25. Yoshida Y, Saito J, Mitani M, Takagi Y, Matsui S, Ishii S-i, Nakano T, Kashiwa N, Fujita T (2002) Living ethylene/norbornene copolymerisation catalyzed by titanium complexes having two pyrrolide-imine chelate ligands. Chem Commun 1298-1299
  26. Byun D-J, Kim SY (2000) Selective chain transfer reactions in metallocene catalyzed copolymerization of ethylene with allylbenzene. Macromolecules 33: 1921–1923
  27. Britovsek, GJP et al. (2002) Iron-catalyzed polyethylene chain growth on zinc: Linear α-olefins with a poisson distribution. Angew Chem Int Ed 41: 489-491
  28. Meurs M, Britovsek GJP, Gibson VC, Cohen SA (2005) Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: A comparative investigation of highly active catalyst systems across the transition series. J Am Chem Soc 127: 9913–9923
  29. Arriola DJ, Carnahan EM, Hustad PD, Kuhlman R L, Wenzel TT (2006) Catalytic production of olefin block copolymers via chain shuttling polymerization. Science 312: 714-719
  30. Cai Z, Ikeda T, Akita M, Shiono T (2005) Living polymerization of α-olefins at elevated temperatures catalyzed by a highly active and robust cyclophane-based nickel catalyst. Macromolecules 38: 2544–2546
  31. Cai Z, Nakayama Y, Shiono T (2008) Catalytic synthesis of a monodisperse olefin block copolymer using a living polymerization system. Macromol Rapid Commun 29: 525-529
  32. Hsueh M-L, Huang B-H, Lin C-C (2002) Reactions of 2,2‘-(2-methoxybenzylidene) bis(4-methyl-6-tert-butylphenol) with trimethyl-aluminum: Novel efficient catalysts for “living” and “immortal” polymerization of ε-caprolactone. Macromolecules 35: 5763–5768
  33. Inoue S (2000) Immortal polymerization: The outset, development, and application. J Polym Sci Part A: Polym Chem 38: 2861-2871
  34. Ko B-T, Lin C-C (1999) Efficient “Living” and “Immortal” Polymerization of Lactones and Diblock Copolymer of ε-CL and δ-VL Catalyzed by Aluminum Alkoxides. Macromolecules 32: 8296–8300
  35. Liu Y-C, Ko B-T, Lin C-C (2001) A Highly Efficient Catalyst for the “Living” and “Immortal” Polymerization of ε-Caprolactone and l-Lactide. Macromolecules 34: 6196–6201
  36. Britovsek GJP, Cohen SA, Gibson VC, Meurs M (2004) Iron catalyzed polyethylene chain growth on zinc: A study of the factors delineating chain transfer versus catalyzed chain growth in zinc and related metal alkyl systems. J Am Chem Soc 126: 10701–10712
  37. Britovsek GJP, Bruce M, Gibson VC, Kimberley BS, Maddox PJ, Mastroianni S, McTavish SJ, Redshaw C, Solan GA, Strömberg S, White AJP, Williams DJJ (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
  38. Souane R, Isel F, Peruch F, Lutz PJ (2002) Pyridine bis(imine) cobalt or iron complexes for ethylene and 1-hexene (co)polymerisation. Comptes Rendus Chim 5: 43-48
  39. Pereira LQ, Marques MFV (2014) Performance of a bis(imine)pyridine iron catalyst System in ethylene/norbornene copolymerization with zinc diethyl. Macromol Symp 343: 8-17
  40. Kaivalchatchawal P, Suttipitakwong P, Samingprai S, Praserthdam P, Jongsomjit B (2011) The influence of comonomer on ethylene/ α-olefin copolymers prepared using [bis(N-(3- tert butylsalicylidene)anilinato)] titanium (IV) dichloride complex. Molecules 16: 1655-1666
  41. Vanegas ME, Quijada R, Galland GB (2010) Syndiotactic poly(propene-co-norbornene): Synthesis and properties at low norbornene incorporation. Polymer 51: 4627-4631
  42. Yoshida Y, Saito J, Mitani M, Takagi Y, Matsui S, Ishii S, Nakano T, Kashiwa N, Fujita T (2002) Living ethylene/norbornene copolymerisation catalyzed by titanium complexes having two pyrrolide-imine chelate ligands. Chem Commun 1298-1299
  43. Yoshida Y, Mohri J, Ishii S, Mitani M, Saito J, Matsui S, Makio H, Nakano T, Tanaka H, Onda M, Yamamoto Y, Mizuno A, Fujita T (2004) Living copolymerization of ethylene with norbornenecatalyzed by bis(Pyrrolide−Imine) titanium complexes with MAO. J Am Chem Soc 126: 12023–12032
  44. Li Y, Gao H, Wu Q (2008) Homo-and copolymerization of ethylene and norbornene with bis(β-diketiminato) titanium complexes activated with methylaluminoxane. J Polym Sci Pol Chem 46: 93-101
  45. Ruchatz D, Fink G (1998) Ethene−norbornene copolymerization using homogenous metallocene and half-sandwich catalysts: Kinetics and relationships between catalyst structure and polymer structure. 2. Comparative study of different metallocene- and half-sandwich/ methylaluminoxane catalysts and analysis of the copolymers by 13C nuclear magnetic resonance spectroscopy. Macromolecules 31: 4674–4680
  46. Wendt RA, Fink G (2003) Ethene–norbornene copolymerizations using two different homogeneous metallocene catalyst systems and investigations of the copolymer microstructure. J Mol Catal A-Chem 203: 101-111
  47. 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– 8509
  48. Zintl M, Rieger B (2207) Novel olefin block copolymers through chain-shuttling polymerization. Angew Chem Int Ed 46: 333-335
  49. Karpiniec S, McGuinness D S, Britovsek G J P, Davies N W, Patel J (2011). Evaluation of mid-to-late transition metal imine catalysts for acetylene oligomerisation: A high activity bis(imino) pyridine iron(II) catalyst. Catalysis Today 178: 64-71
  50. 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

Volume 5, Issue 1
Winter and Spring 2018
Pages 71-84
  • Receive Date: 27 July 2017
  • Revise Date: 11 September 2017
  • Accept Date: 16 September 2017