Advertisement

The effects of catalyst and deactivator species in atom transfer radical polymerization of n-butyl methacrylate

  • Samira Fakharzadeh Kermani
  • Faramarz Afshar TaromiEmail author
Original Research
  • 13 Downloads

Abstract

Atom transfer radical polymerization (ATRP) of n-butyl methacrylate (n-BMA) was performed using CuIBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) as catalyst and tosyl chloride (TsCl) as initiator, and different poly(n-butyl methacrylate) samples were prepared by changing the ratios of monomer/initiator and monomer/catalyst. Comparison was made with the data of another ATRP system with 4,4′-di(5-nonanyl)-2,2′-bipyridine (dNbpy) ligand (n-BMA/CuIBr/dNbpy/TsCl). 1H NMR spectroscopy was used successfully to study monomer conversion during polymerization. For lower degree of polymerization (DP) ≤ 200, the corresponding products displayed narrow molecular weight distribution (D ≤ 1.1). Number average molecular weights (Mn) obtained by gel permeation chromatography (GPC) were higher than those calculated (Mn,theory), while in products with higher degree of polymerization (DP = 300), the Mn,theory surpassed Mn,GPC and molecular weight distribution enhanced (D ≤ 1.25). UV–visible spectroscopy was employed to study the probable coordination of monomer to copper bromide and/or ligand. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were used for characterization of prepared poly(n-butyl methacrylate)s. Cyclic voltammetry (CV) for CuII/CuI redox couple was performed in solvent mixtures of isobutyl butyrate (saturated form of n-butyl methacrylate) and acetonitrile having different volume fractions (acetonitrile/butyl isobutyrate: 100/0, 80/20, 60/40, 40/60 and 20/80). By introducing moderately nonpolar butyl isobutyrate to polar aprotic acetonitrile, peak-to-peak separation increased. This implied slow electron transfer (lower KET in presence of monomer) that adjusted KATRP.

Keywords

ATRP Copper complex Cyclic voltammetry n-Butyl methacrylate PMDETA 

References

  1. 1.
    Wang JS, Matyjaszewski K (1995) Controlled living radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes radical initiator. J Am Chem Soc 117:5614–5615CrossRefGoogle Scholar
  2. 2.
    Kato M, Kamigaito M, Sawamoto M, Higashimura T (1995) Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris(triphenylphosphine) ruthenium(II)/methylaluminium bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28:1721–1723CrossRefGoogle Scholar
  3. 3.
    Coessens V, Pintauer T, Matyjaszewski K (2001) Functional polymers by atom transfer radical polymerization. Prog Polym Sci 26:337–377CrossRefGoogle Scholar
  4. 4.
    Matyjaszewski K, Tsarevsky NV (2014) Macromolecular engineering by atom transfer radical polymerization. J Am Chem Soc 136:6513–6533CrossRefGoogle Scholar
  5. 5.
    Matyjaszewski K, Xia J (2001) Atom transfer radical polymerization. Chem Rev 101:2921–2990CrossRefGoogle Scholar
  6. 6.
    Matyjaszewski K, Davis TP (2002) General concepts and history of living radical polymerization. Handbook of radical polymerization. Wiley, New YorkCrossRefGoogle Scholar
  7. 7.
    Ouchi M, Terashima T, Sawamoto M (2009) Transition metal-catalyzed living radical polymerization: toward perfection in catalysis and precision polymer synthesis. Chem Rev 109:4963–5050CrossRefGoogle Scholar
  8. 8.
    Kamigaito M, Ando T, Sawamoto M (2001) Metal-catalyzed living radical polymerization. Chem Rev 101:3689–3745CrossRefGoogle Scholar
  9. 9.
    Tsarevsky NV, Braunecker WA, Vacca A, Gans P, Matyjaszewski K (2007) Competitive equilibria in atom transfer radical polymerization. Macromol Symp 248:60–70CrossRefGoogle Scholar
  10. 10.
    Krys P, Matyjaszewski K (2017) Kinetics of atom transfer radical polymerization. Eur Polym J 89:482–523CrossRefGoogle Scholar
  11. 11.
    Fantin M, Lorandi F, Gennaro A, Isse AA, Matyjaszewski K (2017) Electron transfer reactions in atom transfer radical polymerization. Synthesis 49:3311–3322CrossRefGoogle Scholar
  12. 12.
    Horn M, Matyjaszewski K (2013) Solvent effects on the activation rate constant in atom transfer radical polymerization. Macromolecules 46:3350–3357CrossRefGoogle Scholar
  13. 13.
    Coullerez G, Malmstrom E, Jonsson M (2006) Solvent effects on the redox properties of Cu complexes used as mediators in atom transfer radical polymerization. J Phys Chem A 110:10355–10360CrossRefGoogle Scholar
  14. 14.
    Pintauer T, Reinöhl U, Feth M, Bertagnolli H, Matyjaszewski K (2003) Extended X-ray absorption fine structure study of copper(I) and copper(II) complexes in atom transfer radical polymerization. Eur J Inorg Chem 11:2082–2094CrossRefGoogle Scholar
  15. 15.
    Pintauer T, Matyjaszewski K (2005) Structural aspects of copper catalyzed atom transfer radical polymerization. Coord Chem Rev 249:1155–1184CrossRefGoogle Scholar
  16. 16.
    Kickelbick G, Pintauer T, Matyjaszewski K (2002) Structural comparison of CuII complexes in atom transfer radical polymerization. New J Chem 26:462–468CrossRefGoogle Scholar
  17. 17.
    de Vries A, Klumperman A, de Wet-Roos D, Sanderson RD (2001) The effect of reducing monosacharides on the atom transfer radical polymerization of butyl methacrylate. Macromol Chem Phys 202:1645–1648CrossRefGoogle Scholar
  18. 18.
    Davis KA, Matyjaszewski K (2004) Investigation of the ATRP of n-butyl methacrylate using the Cu(I)/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalyst system. Chin J Polym Sci 22:195–204Google Scholar
  19. 19.
    Qiu J, Gaynor SG, Matyjaszewski K (1999) Emulsion polymerization of n-butyl methacrylate by reverse atom transfer radical polymerization. Macromolecules 32:2872–2875CrossRefGoogle Scholar
  20. 20.
    Gaynor SG, Qiu J, Matyjaszewski K (1998) Controlled/“living” radical polymerization applied to water-borne system. Macromolecules 31:5951–5954CrossRefGoogle Scholar
  21. 21.
    Peng H, Cheng Sh, Fan Zh (2005) Studies on atom transfer radical emulsion polymerization of n-butyl methacrylate. Polym Eng Sci 45:297–302CrossRefGoogle Scholar
  22. 22.
    Matyjaszewski K, Qiu J, Tsarevsky NV, Charleux B (2000) Atom transfer radical polymerization of n-butyl methacrylate in an aqueous dispersed system: a miniemulsion approach. J Polym Sci A Polym Chem 38:4724–4734CrossRefGoogle Scholar
  23. 23.
    Simms R, Cunningham MF (2008) High molecular weight poly(butyl methacrylate) via ATRP miniemulsion. Macromol Symp 261:32–35CrossRefGoogle Scholar
  24. 24.
    Bortolamei N, Isse AA, Di Marco WB, Gennaro A, Matyjaszewsk K (2010) Thermodynamic properties of copper complexes used as catalysts in atom transfer radical polymerization. Macromolecules 43:9257–9267CrossRefGoogle Scholar
  25. 25.
    Rahimi-Nasrabadi M, Ganjali MR, Gholivand MB, Ahmadi F, Norouzi P, Salavati-Niasari M (2008) A cyclic voltammetry investigation of the complex formation between Cu2+ and some Schiff bases in binary acetonitrile/dimethylformamide mixtures. J Mol Struct 885:76–81CrossRefGoogle Scholar
  26. 26.
    Fakharzadeh Kermani S, Afshar Taromi F, Eslami H, Notash B (2017) Synthesis and structural analysis of a new polymorph of [CuII(PMDETA)Br2]. Inorg Nano Metal Chem 47:730–736CrossRefGoogle Scholar
  27. 27.
    Braunecker WA, Pintauer T, Tsarevsky NV, Kickelbick G, Matyjaszewski K (2005) Toward understanding monomer coordination in atom transfer radical polymerization: synthesis of [CuI(PMDETA)(π-M)][BPh4](M = methyl acrylate, styrene, 1-octene, and methyl methacylate) and structural studies by FT-IR and H1 NMR spectroscopy and X-ray crystallography. J Organomet Chem 690:916–924CrossRefGoogle Scholar
  28. 28.
    Tang W, Matyjaszewski K (2006) Effect of ligand structure on activation rate constant in ATRP. Macromolecules 39:4953–4959CrossRefGoogle Scholar
  29. 29.
    Hongchen D, Matyjaszewski K (2008) ARGET ATRP of 2-(dimethylamino) ethyl methacrylate as an intrinsic reducing agent. Macromolecules 41:6868–6870CrossRefGoogle Scholar
  30. 30.
    Matyjaszewski K, Gobelt B, Paik H-J, Horwitz CP (2001) Tridentate nitrogen-based ligands in Cu-based ATRP: a structure-activity study. Macromolecules 34:430–440CrossRefGoogle Scholar
  31. 31.
    Gurr PA, Mills MF, Qiao GG, Solomon DH (2005) Initiator efficiency in ATRP: the tosyl chloride/CuBr/PMDETA system. Polymer 46:2097–2104CrossRefGoogle Scholar
  32. 32.
    Huang J, Pintauer T, Matyjaszewski K (2004) Effect of variation of [PMDETA]0/[CuBr]0 ratio on atom transfer radical polymerization of n-butyl acrylate. J Polym Sci Part A 42:3285–3292CrossRefGoogle Scholar
  33. 33.
    Reynaud S, Qiu J, Matyjaszewski K (2001) Atom transfer radical polymerization of methyl methacrylate in water–borne system. Macromolecules 34:6641–6648CrossRefGoogle Scholar
  34. 34.
    Xu W, Zhu X, Cheng Zh, Chen J (2003) Atom transfer radical polymerization of lauryl methacrylate. J Appl Polym Sci 90:1117–1125CrossRefGoogle Scholar
  35. 35.
    Najafi M, Roghani-Mamaqani H, Haddadi-Asl V, Salami-Kalajahi M (2011) A simulation of kinetics and chain length distribution of styrene FRP and ATRP: chain-length-dependent. Adv Polym Technol 30:257–268CrossRefGoogle Scholar
  36. 36.
    Coats J (2000) Interpretation of infrared spectra, a practical approach. In: Meyers RA (ed) Encyclopedia of analytical chemistry. Wiley, Chichester, pp 10815–10837Google Scholar
  37. 37.
    Qiu J, Matyjaszewski K, Thouin L, Amatore Ch (2000) Cyclic voltammetric studies of copper complexes catalyzing atom transfer radical polymerization. Macromol Chem Phys 201:1625–1631CrossRefGoogle Scholar
  38. 38.
    Bard AJ, Faulkner LR (1980) Electrochemical methods fundamental and application. Wiley, New YorkGoogle Scholar
  39. 39.
    Xia J, Zhang X, Matyjaszewski K (1999) The effect of ligands on copper-mediated atom transfer radical polymerization. ACS Symp Ser 760:207–223CrossRefGoogle Scholar

Copyright information

© Iran Polymer and Petrochemical Institute 2019

Authors and Affiliations

  • Samira Fakharzadeh Kermani
    • 1
  • Faramarz Afshar Taromi
    • 2
    Email author
  1. 1.Department of Polymer EngineeringAmirkabir University of TechnologyMahshahrIran
  2. 2.Department of Polymer Engineering and Color TechnologyAmirkabir University of TechnologyTehranIran

Personalised recommendations