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Iron(III)-mediated ATRP systems of n-docosyl acrylate with AIBN and BPO

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Abstract

Well-defined poly(n-docosyl acrylate) (PDA) with narrow molecular weight distribution has been synthesized by atom transfer radical polymerization (ATRP) and reverse ATRP of n-docosyl acrylate (DA) at 80 °C in N,N-dimethylformamide using the carbon tetrabromide/FeCl3/2,2′-bipyridine (bpy) initiation system in the presence of 2,2′-azobisisobutyronitrile (AIBN) and benzoyl peroxide (BPO) as the source of reducing agent. The rates of polymerization for both the systems exhibit first-order kinetics with respect to the monomer, however, peroxide-initiated system shows slow rate of polymerization as compared to the azo-system. The effect of various reaction parameters on number average molecular weight (M n ) and molecular weight distribution (M w/M n ) have been investigated. The resulting PDA that obtained in presence of AIBN and BPO systems has been compared for both the conventional and reverse ATRP. The reverse ATRP initiated by peroxides behaves differently than that of the azo initiators. In reverse ATRP with BPO, the rate of polymerization (R p) has been significantly increased with the increase of BPO resulting higher M n and broader M w/M n . The reverse ATRP of DA did not exhibit living characteristics with BPO system. PDA has been characterized by GPC, FTIR, and NMR spectroscopy.

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References

  1. Wang J-S, Matyjaszewski K (1995) Controlled/”living” radical polymerization. Atom transfer radical polymerization in the presence of transition–metal complex. J Am Chem Soc 117:5614–5615

    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 28:1721–1723

    Article  CAS  Google Scholar 

  3. Matyjaszewski K, Xia J (2001) Atom transfer radical polymerization. Chem Rev 101:2921–2990

    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. Braunecker WA, Matyjaszewski K (2007) Controlled/living radical polymerization: features, developments, and perspectives. Prog Polym Sci 32:93–146

    Article  CAS  Google Scholar 

  6. Ye P, Dong H, Zhong M, Matyjaszewski K (2011) Synthesis of binary polymer brushes via two-step reverse atom transfer radical polymerization. Macromolecules 44:2253–2260

    Article  CAS  Google Scholar 

  7. Matyjaszewski K, Tsarevsky NV (2009) Nanostructured functional materials prepared by atom transfer radical polymerization. Nat Chem 1:276–288

    Article  CAS  Google Scholar 

  8. Davis KA, Matyjaszewski K (2002) Statistical, gradient and segmented copolymers by controlled/living radical polymerizations. Adv Polym Sci 159:2–191

    CAS  Google Scholar 

  9. Qiu J, Pintaeur T, Gaynor SG, Matyjaszewski K, Charleux B, Vairon J-P (2000) Mechanistic aspect of reverse atom transfer radical polymerization of n-butyl methacrylate in aqueous dispersed system. Macromolecules 33:7310–7320

    Article  CAS  Google Scholar 

  10. Jakubowski W, Matyjaszewski K (2005) Activator generated by electron transfer for atom transfer radical polymerization. Macromolecules 38:4139–4146

    Article  CAS  Google Scholar 

  11. Jakubowski W, Matyjaszewski K (2006) Activators regenerated by electron transfer for atom-transfer radical polymerization of (meth)acrylates and related block copolymers. Angew Chem Int Ed 45:482–4486

    Article  Google Scholar 

  12. Zhang L, Miao J, Cheng ZP, Zhu XL (2010) Iron-mediated ICAR ATRP of styrene and methyl methacrylate in the absence of thermal radical initiator. Macromol Rapid Commun 31:275–280

    Article  CAS  Google Scholar 

  13. Wang Y, Zhang Y, Parker B, Matyjaszewski K (2011) ATRP of MMA with ppm levels of iron catalyst. Macromolecules 44:4022–4025

    Article  CAS  Google Scholar 

  14. Wang J-S, Matyjaszewski K (1995) “Living”/controlled radical polymerization. Transition–metal-catalyzed atom transfer radical polymerization in the presence of a conventional radical initiator. Macromolecules 28:7572–7573

    Article  CAS  Google Scholar 

  15. Xia JH, Matyjaszewski K (1997) Controlled/“living” radical polymerization. Homogeneous reverse atom transfer radical polymerization using AIBN as the initiator. Macromolecules 30:7692–7696

    Article  CAS  Google Scholar 

  16. Moineau G, Dubois Ph, Jerome R, Senninger T, Teyssie Ph (1998) Alternative atom transfer radical polymerization for MMA using FeCl3 and AIBN in the presence of triphenylphosphine: an easy way to well-controlled PMMA. Macromolecules 31:545–547

    Article  CAS  Google Scholar 

  17. Wang G, Zhu X, Cheng Z, Zhu J (2006) New ligands for the Fe(III)-mediated reverse atom transfer radical polymerization of methyl methacrylate. J Polym Sci Part A Polym Chem 44:2912–2921

    Article  CAS  Google Scholar 

  18. Zhou W, Chen H, Liang Y, Yu M, Chen L (2009) Synthesis of poly(methyl methacrylate) via reverse atom transfer radical polymerization catalyzed by FeCl3/lactic Acid. J Appl Polym Sci 114:1593–1597

    Article  CAS  Google Scholar 

  19. Xia JH, Matyjaszewski K (1999) Homogeneous reverse atom transfer radical polymerization of styrene initiated by peroxides. Macromolecules 32:5199–5202

    Article  CAS  Google Scholar 

  20. Qin DQ, Qin SH, Chen XP, Qiu KY (2000) Living/controlled radical polymerization of methyl methacrylate by reverse ATRP with DCDPS/FeCl3/PPh3 initiating system. Polymer 41:7347–7353

    Article  CAS  Google Scholar 

  21. Qin DQ, Qin SH, Qiu KY (2000) A reverse ATRP process with a hexasubstituted ethane thermal iniferter diethyl 2,3-dicyano-2,3-di(p-tolyl)succinate as the initiator. Macromolecules 33:6987–6992

    Article  CAS  Google Scholar 

  22. Mishra MK, Saxton R-G (1998) Pour point depressants via anionic polymerization of (meth)acrylic monomers. US Patent 5834408

  23. Wirtz H, von Halasz S-P, Feustel M, Balzer J (1994) New copolymers, mixtures thereof with poly(meth)acrylate esters and the use thereof for improving the cold fluidity of crude oils. US Patent 5349019

  24. Baruah SD, Laskar NC, Subrahmanyam B (1994) Experimental investigation on high conversion free radical polymerization of behenyl acrylate. J Appl Polym Sci 51:1701–1707

    Article  CAS  Google Scholar 

  25. Kawabata N, Tsuruta T (1965) Elementary reactions of metal alkyl in anionic polymerization. I. Reaction mode of n-butyllithium in the initiation step of methyl acrylate and methyl methacrylate polymerization. Die Makromolekulare Chemie 86:231–252

    Article  CAS  Google Scholar 

  26. Qin S, Matyjaszewski K, Xu H, Sheiko SS (2003) Synthesis and visualization of densely grafted molecular brushes with crystallizable poly(octadecyl methacrylate) block segments. Macromolecules 36:605–612

    Article  CAS  Google Scholar 

  27. Saikia PJ, Goswami A, Baruah SD (2002) Transition metal-catalyzed atom transfer radical polymerization of stearyl methacrylate in the presence of carbon tetrabromide and conventional radical initiator. J Appl Polym Sci 86:386–394

    Article  CAS  Google Scholar 

  28. Saikia PJ, Dass NN, Baruah SD (2005) Kinetic study of the atom transfer radical polymerization of n-docosyl acrylate. J Appl Polym Sci 97:2147–2154

    Article  CAS  Google Scholar 

  29. Destarac M, Bessiere J-M, Boutevin B (1998) Atom transfer radical polymerization of styrene initiated by polychloroalkanes and catalyzed by CuCl/2,2′-bipyridine: a kinetic and mechanistic study. J Polym Sci Part A Polym Chem 36:2933–2947

    Article  CAS  Google Scholar 

  30. Rosin H, Daren SLJ, Asscher M, Vofsi D (1972) Telomeric plasticizers: cotelomers based on vinyl chloride and carbon tetrachloride. J Appl Polym Sci 16:1687–1700

    Article  CAS  Google Scholar 

  31. Boutevin B (2000) From telomerization to living radical polymerization. J Polym Sci Part A Polym Chem 38:3235–3243

    Article  CAS  Google Scholar 

  32. Destarac M, Matyjaszewsk K, Boutevin B (2000) Polychloroalkane initiators in copper-catalyzed atom transfer radical polymerization of (meth)acrylates. Macromol Chem Phys 201:265–272

    Article  CAS  Google Scholar 

  33. Asscher M, Vofsi D (1968) The oxidation of ferrous and cuprous chloride by carbon tetrachloride. J Chem Soc 947–952

  34. Gromoda J, Matyjaszewski K (2001) Simultaneous reverse and normal initiation in atom transfer radical polymerization. Macromolecules 34:7664–7671

    Article  Google Scholar 

  35. Junkers T, Barner-Kowollik C (2008) The role of mid-chain radicals in acrylate free radical polymerization: branching and scission. J Polym Sci Part A Polym Chem 46:7585–7605

    Article  CAS  Google Scholar 

  36. Farcet CI, Belleney JI, Charleux B, Pirri R (2002) Structural characterization of nitroxide-terminated poly (n-butyl acrylate) prepared in bulk and miniemulsion polymerizations. Macromolecules 35:4912–4918

    Article  CAS  Google Scholar 

  37. Yokota K, Kougo T, Hirabayashi T (1983) Synthesis, structure, and thermal properties of widely-spaced comb-like polymers. Polym J 15:891–898

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors wish to thank Dr. P.G. Rao, Director, CSIR-NEIST, Jorhat for permission to publish the results.

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Correspondence to Prakash J. Saikia.

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Saikia, P.J., Hazarika, A.K. & Baruah, S.D. Iron(III)-mediated ATRP systems of n-docosyl acrylate with AIBN and BPO. Polym. Bull. 70, 1483–1498 (2013). https://doi.org/10.1007/s00289-012-0902-z

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  • DOI: https://doi.org/10.1007/s00289-012-0902-z

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