Skip to main content
SpringerLink
Log in

The synthesis of (N1E,N4E)-N1,N4-bis(pyridine-2-YL) ethylene benzene-1,4-diamine and investigation of its efficiency as new binuclear catalyst complex in copper-based ATRP

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

(N1E,N4E)-N1,N4-bis(pyridin-2-yl) ethylene benzene-1,4-diamine (BPEBD) was synthesized by condensation of 2-acetyl pyridine and 1,4-diaminobenzene and its efficiency as a catalyst in Cu-based atom transfer radical polymerizations (ATRP) of methyl methacrylate (MMA) and styrene (S) was investigated. Linear first-order kinetic plots were obtained. However, there were induction periods. The apparent rate constant values of ATRP of MMA with CuCl/BPEBD catalyst system in toluene were found to be between 2.10 × 10−5 and 9.83 × 10−5 s−1, while they were between 6.67 × 10−6 and 3.30 × 10−5 s−1 in the case of acetonitrile, indicating the presence of a low radical concentration throughout the polymerizations. Low apparent rate constant values denote a good control over ATRP in general. Apparent rate constant vs [ligand]/[catalyst] ratio plots showed a maximum at the [ligand]/[catalyst] ratio of 1. In the ATRP of MMA in toluene, M n,GPC values increased linearly with conversion and these molecular weight values were close to M n,th in comparison to that of in acetonitrile. In the polymerization of S, the control of molecular weights was not good, although the reactions were first-order kinetics. Cyclic voltammetry measurements confirmed that CuCl/BPEBD complex in acetonitrile gives quasi-reversible redox couples, and copper (I) centers in CuCl/BPEBD binuclear catalyst complexes are readily oxidized and it potentially suits to facile ATRP.

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

Scheme 1
Fig. 1
Fig. 2
Scheme 2
Fig. 3
Fig. 4
Fig. 5
Scheme 3
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Wang JS, Matyjaszewski K (1995) Controlled/”living” radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes. J Am Chem Soc 117(20):5614

    Article  CAS  Google Scholar 

  2. Kato M, Kamigaito M, Sawamoto M, Higashimura T (1995) Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris- (triphenylphosphine) ruthenium (II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28(5):1721–1723

    Article  CAS  Google Scholar 

  3. Percec V, Barboiu B (1995) “Living” radical polymerization of styrene initiated by arene- sulfonyl chlorides and CuI(bpy)nCl. Macromolecules 28(23):7970–7972

    Article  CAS  Google Scholar 

  4. Kamigaito M, Ando T, Sawamoto M (2001) Metal-catalyzed living radical polymerization. Chem Rev 101:3689–3746

    Article  CAS  Google Scholar 

  5. Quchi M, Terashima T, Sawamoto M (2009) Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis. Chem Rev 109:4963–5050

    Article  CAS  Google Scholar 

  6. Lena F, Matyjaszewski K (2010) Transition metal catalysts for controlled radical polymerization. Prog Polym Sci 35:959–1021

    Article  CAS  Google Scholar 

  7. Davis KA, Matyjaszewski K (2000) Atom transfer radical polymerization of tert-butyl acrylate and preparation of block copolymers. Macromolecules 33:4039–4047

    Article  CAS  Google Scholar 

  8. Gurr PA, Mills MF, Qiao GG, Solomon DH (2005) Initiator efficiency in ATRP: the tosyl chloride/CuBr/PMDETA system. Polymer 46:2097–2104

    Article  CAS  Google Scholar 

  9. Mühlebach A, Gaynor SG, Matyjaszewski K (1998) Synthesis of amphiphilic block copolymers by atom transfer radical polymerization (ATRP). Macromolecules 31:6046–6052

    Article  Google Scholar 

  10. Shen Y, Zhu S, Zeng F, Pelton R (2000) Atom transfer radical polymerization of methyl methacrylate by silica gel supported copper bromide/multidentate amine. Macromolecules 33:5427–5431

    Article  CAS  Google Scholar 

  11. Wootthikanokkhan J, Peesan M, Phinyocheep P (2001) Atom transfer radical polymerizations of (meth)acrylic monomers and isoprene. Eur Polym J 37:2063–2071

    Article  CAS  Google Scholar 

  12. Brar AS, Kaur S (2005) Tetramethylguanidino-tris(2-aminoethyl)amine: a novel ligand for copper-based atom transfer radical polymerization. J Polym Sci Part A: Polym Chem 43:5906–5922

    Article  CAS  Google Scholar 

  13. Teodorescu M, Matyjaszewski K (1999) Atom transfer radical polymerization of (meth)acrylamides. Macromolecules 32:4826–4831

    Article  CAS  Google Scholar 

  14. Tsarevsky NV, Braunecker WA, Tang W, Brooks SJ, Matyjaszewski K, Weisman GR, Wong EH (2006) Copper-based ATRP catalysts of very high activity derived from dimethyl cross-bridged cyclam. J Mol Cat A: Chem 257:132–140

    Article  CAS  Google Scholar 

  15. Pintauer T, Matyjaszewski K (2005) Structural aspects of copper catalyzed atom transfer radical polymerization. Coord Chem Rev 249:1155–1184

    Article  CAS  Google Scholar 

  16. Tsarevsky NV, Matyjaszewski K (2007) “Green” atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials. Chem Rev 107:2270–2299

    Article  CAS  Google Scholar 

  17. Tang W, Matyjaszewski K (2006) Effect of ligand structure on activation rate constants in ATRP. Macromolecules 39:4953–4959

    Article  CAS  Google Scholar 

  18. Zhang H, Klumperman B, Linde R (2002) Synthesis of anthracene end-capped poly(methyl methacrylate)s via atom transfer radical polymerization and its kinetic analyses. Macromolecules 35:2261

    Article  CAS  Google Scholar 

  19. Zhang H, Van Der Linde R (2002) Atom transfer radical polymerization of n-butyl acrylate catalyzed by CuBr/N-(n-hexyl)-2-pyridylmethanimine. J Polym Sci Part A: Polym Chem 40(21):3549–3561

    Article  CAS  Google Scholar 

  20. Haddleton DM, Clark AJ, Crossman MC, Duncalf DJ, Heming AM, Morsley SR, Shooter A (1997) Atom transfer radical polymerisation (ATRP) of methyl methacrylate in the presence of radical inhibitors. J Chem Soc Chem Commun (13):1173–1174

  21. Raghunadh V, Baskaran D, Sivaram S (2004) Efficiency of ligands in atom transfer radical polymerization of lauryl methacrylate and block copolymerization with methyl methacrylate. Polymer 45:3149–3155

    Article  CAS  Google Scholar 

  22. Mittal A, Sivaram S (2005) A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate. J Polym Sci Part A: Polym Chem 43:4996–5008

    Article  CAS  Google Scholar 

  23. Haddleton DM, Crossman MC, Dana BH, Duncalf DJ, Heming AM, Kukulj D, Shooter A (1999) Atom transfer polymerization of methyl methacrylate mediated by alkylpyridylmethanimine type ligands, copper(I) bromide, and alkyl halides in hydrocarbon solution. J Macromolecules 32:2110–2119

    Article  CAS  Google Scholar 

  24. Iovu M, Maithufi N, Mapolie S (2003) Copper-mediated ATRP of methyl methacrylate in polar solvents using a bifunctional pyridinal diimine ligand. Macromol Symp 193:209–226

    Article  CAS  Google Scholar 

  25. Haddleton DM, Jackson SG, Bon SAF (2000) Copper(I)-mediated living radical polymerization under fluorous biphasic conditions. J Am Chem Soc 122:1542–1543

    Article  CAS  Google Scholar 

  26. Yuan X, Lu J, Xu Q, Wang L (2005) Atom transfer radical polymerization of styrene initiated by 2-(4-chloromethyl-phenyl)-benzoxazole with high activity and fluorescent property. Polymer 46:9186–9191

    Article  CAS  Google Scholar 

  27. Beers KL, Matyjaszewski K (2001) The atom transfer radical polymerization of lauryl-acrylate. J Macromol Sci Pure Appl Chem A38(7):731–739

    Article  CAS  Google Scholar 

  28. Zhu S, Yan D (2000) Atom transfer radical polymerization of methyl methacrylate catalyzed by iron II chloride/isophthalic acid system. Macromolecules 33:8233–8238

    Article  CAS  Google Scholar 

  29. Sarbu T, Lin K, Spanswick J, Gil RR, Siegwart DJ, Matyjaszewski K (2004) Synthesis of hydroxy-telechelic poly(methyl acrylate) and polystyrene by atom transfer radical coupling. Macromolecules 37:9694

    Article  CAS  Google Scholar 

  30. Cai Y, Hartenstein M, Müller AHE (2004) Synthesis of amphiphilic graft copolymers of n-butyl acrylate and acrylic acid by atom transfer radical copolymerization of macromonomers. Macromolecules 37:7484

    Article  CAS  Google Scholar 

  31. Chung IS, Matyjaszewski K (2003) Synthesis of degradable poly(methyl methacrylate) via ATRP: atom transfer radical ring-opening copolymerization of 5-Methylene-2-phenyl-1,3-dioxolan-4-one and methyl methacrylate. Macromolecules 36:2995

    Article  CAS  Google Scholar 

  32. Coessens V, Pintauer T, Matyjaszewski K (2001) Functional polymers by atom transfer radical polymerization. Prog Polym Sci 26:337–377

    Article  CAS  Google Scholar 

  33. Muthukrishnan S, Jutz G, Andre X, Mori H, Müller AHE (2005) Synthesis of hyperbranched glycopolymers via self-condensing atom transfer radical copolymerization of a sugar-carrying acrylate. Macromolecules 38:9–18

    Article  CAS  Google Scholar 

  34. Muthukrishnan S, Mori H, Müller AHE (2005) Synthesis and characterization of methacrylate-type hyperbranched glycopolymers via self-condensing atom transfer radical copolymerization. Macromolecules 38:3108–3119

    Article  CAS  Google Scholar 

  35. Senkal BF, Hizal G, Bicak N (2001) Atom transfer radical polymerization through N-chlorosulfonamides. J Polym Sci Part A: Polym Chem 39:2691–2695

    Article  CAS  Google Scholar 

  36. Ydens I, Degee P, Dubois P, Libiszowski J, Duda A, Penczek S (2003) Combining ATRP of methacrylates and ROP of L, L-dilactide and ε-caprolactone. Macromol Chem Phys 204:171–179

    Article  CAS  Google Scholar 

  37. Zhang Z, Ying S, Zhang Q, Xu X (2001) Well-controlled radical copolymerization of styrene with 2-[(perfluorononenyl)oxy] ethyl methacrylate and characterization of its copolymers. J Polym Sci Part A: Polym Chem 39:2670–2676

    Article  CAS  Google Scholar 

  38. Batt-Coutrot D, Haddleton DM, Jarvis AP, Kelly RL (2003) Synthesis and properties of amphiphilic vinyl acetate triblock copolymers prepared by copper mediated living radical polymerisation. Eur Polym J 39:2243–2252

    Article  CAS  Google Scholar 

  39. Strissel C, Matyjaszewski K, Nuyken O (2003) Block copolymers from organomodified siloxane-containing macroinitiators by atom transfer radical polymerization. Macromol Chem Phys 204:1169–1177

    Article  CAS  Google Scholar 

  40. Lee SB, Russell AJ, Matyjaszewski K (2003) ATRP synthesis of amphiphilic random, gradient, and block copolymers of 2-(dimethylamino)ethyl methacrylate and n-butyl methacrylate in aqueous media. Biomacromolecules 4:1386–1393

    Article  CAS  Google Scholar 

  41. Cassebras M, Pascual S, Polton A, Tardi M, Vairon J (1999) Synthesis of di- and triblock copolymers of styrene and butyl acrylate by controlled atom transfer radical polymerization. Macromol Rapid Commun 20:261–264

    Article  CAS  Google Scholar 

  42. Zhang M, Breiner T, Mori H, Müller AHE (2003) Amphiphilic cylindrical brushes with poly(acrylic acid) core and poly(n-butyl acrylate) shell and narrow length distribution. Polymer 44:1449–1458

    Article  CAS  Google Scholar 

  43. Arslan H, Yesilyurt N, Hazer B (2007) The synthesis of poly(3-hydroxybutyrate)-g-poly(methylmethacrylate) brush type graft copolymers by atom transfer radical polymerization method. J Appl Polym Sci 106:1742–1750

    Article  CAS  Google Scholar 

  44. Arslan H (2012) Polymerization/Book 1 “block and graft copolymerization by controlled/“Living” radical polymerization methods” Edited by Ailton De Souza Gomes, ISBN 978-953-51-0745-3, Published by INTECH pp 279–320

  45. Zhang L, Tang H, Tang J, Shen Y, Meng L, Radosz M, Arulsamy N (2009) Pentadentate copper halide complexes have higher catalytic activity in atom transfer radical polymerization of methyl acrylate than hexadentate complexes. Macromolecules 42:4531–4538

    Article  CAS  Google Scholar 

  46. Tang H, Arulsamy N, Radosz M, Shen Y, Tsarevsky NV, Braunecker WA, Tang W, Matyjaszewski K (2006) Highly active copper-based catalyst for atom transfer radical polymerization. J Am Chem Soc 128:16277–16285

    Article  CAS  Google Scholar 

  47. Lahtinen P, Lankinen E, Leskela M, Repo T (2005) Insight into copper oxidation catalysts: kinetics, catalytic active species and their deactivation. Appl Catal A 295:177–184

    Article  CAS  Google Scholar 

  48. Xu Y, Lu J, Xu Q, Wang L (2005) Atom transfer radical polymerization of styrene initiated by triphenylmethyl chloride. Eur Polymer J 41:2422–2427

    Article  CAS  Google Scholar 

  49. Al-Harthi M, Sardashti A, Soares JBP, Simon LC (2007) Atom transfer radical polymerization (ATRP) of styrene and acrylonitrile with monofunctional and bifunctional initiators. Polymer 48:1954–1961

    Article  CAS  Google Scholar 

  50. Becer CR, Hoogenboom R, Fournier D, Schubert US (2007) Cu(II)-Mediated ATRP of MMA by Using a Novel Tetradentate Amine Ligand with Oligo(ethylene glycol) Pendant Groups. Macromol Rapid Commun 28:1161–1166

    Article  CAS  Google Scholar 

  51. Zhao K, Cheng Z, Zhang Z, Zhu J, Zhu X (2009) Synthesis of fluorescent poly(methyl methacrylate) via AGET ATRP. Polym Bull 63:355–364

    Article  CAS  Google Scholar 

  52. Jonsson M, Nyström D, Nordin O, Malmström E (2009) Surface modification of thermally expandable microspheres by grafting poly(glycidyl methacrylate) using ARGET ATRP. Eur Polym J 45:2374–2382

    Article  CAS  Google Scholar 

  53. Hu Z, Shen X, Qiu H, Lai G, Wu J, Li W (2009) AGET ATRP of methyl methacrylate with poly(ethylene glycol) (PEG) as solvent and TMEDA as both ligand and reducing agent. Eur Polym J 45:2313–2318

    Article  CAS  Google Scholar 

  54. Chen H, Liang Y, Meng Y, Yang L, Chen L, Niu Y (2009) Reverse ATRP of 4-vinylpyridine with Diethyl 2,3-Dicyano-2,3-Diphenylsuccinate/CuCl2/5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetradecane. Mater Sci Eng C 29:1604–1608

    Article  CAS  Google Scholar 

  55. Qiu J, Matyjaszewski K, Thouin L, Amatore C (2000) Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization. Macromol Chem Phys 201:1625–1631

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by Bülent Ecevit University Research Fund, Turkey (AFP Project No.: 2012-10-03-11).

Author information

Authors and Affiliations

  1. Chemistry Department, Bülent Ecevit University, 67100, Zonguldak, Turkey

    Hülya Arslan, M. Gürkan Kaptan, Orçun Zirtil, M. Emre Hanhan & Şadi Şen

Authors
  1. Hülya Arslan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Gürkan Kaptan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Orçun Zirtil
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Emre Hanhan
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Şadi Şen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hülya Arslan.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Arslan, H., Kaptan, M.G., Zirtil, O. et al. The synthesis of (N1E,N4E)-N1,N4-bis(pyridine-2-YL) ethylene benzene-1,4-diamine and investigation of its efficiency as new binuclear catalyst complex in copper-based ATRP. Polym. Bull. 71, 1043–1059 (2014). https://doi.org/10.1007/s00289-014-1110-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-014-1110-9

Keywords

Search

Navigation