Synthesis of acrylate-1-hexene based functional polyolefin using activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP)

Document Type : Original research

Authors

Reliance Research Development Group, Reliance Industries Ltd., Reliance Corporate Park, Ghansoli, Navi Mumbai, Maharashtra – 400701, India

Abstract

The copolymerization of methyl acrylate (MA) and glycidyl methacrylate (GMA) with 1-hexene was carried out using activator regenerator by electron transfer atom transfer radical polymerization (ARGET ATRP) employing Cu(0)/CuBr2 as a catalyst, pentamethyl diethylenetriamine (PMDETA) as a ligand, and ethyl 2-bromoisopropionate (EBriP) as the initiator, all at a reaction temperature of 70°C. This process resulted in the production of viscous and transparent copolymers, namely poly (methyl acrylate-co-1-hexene) or PMH and poly (glycidyl methacrylate-co- 1-hexene) or PGMH. For the MA/1-Hex copolymer, conversion rates ranged from a maximum of 31 wt.% to a minimum of 12 wt.%, while the GMA/1-hexene copolymer exhibited conversion rates ranging from a maximum of 42 wt.% to a minimum of 12 wt.%. It was observed that increasing the amount of 1-hexene during the synthesis led to a higher incorporation of 1-hexene content in both the MA and GMA polymer backbones, with a maximum of 15 wt.% and 18 wt.% of 1-hexene being incorporated into PMH and PGMH, respectively. The incorporation of 1-hexene was confirmed through Nuclear Magnetic Resonance (NMR) studies, including 1H, 13C, and DEPT 135 studies. Additionally, the copolymer PMH and PGMH exhibited monomodal molecular weight distribution curves when evaluated using the size exclusion chromatography (SEC) high-performance liquid chromatography (HPLC) technique, with polydispersity values in the range of 1.19-1.37 and 1.07-1.11, respectively. These findings indicate that the copolymerization process was well-controlled and followed a radical polymerization mechanism.

Keywords

Main Subjects


  1. Hong SC, Jia S, Teodorescu M, Kowalewski T, Matyjaszewski K, Gottfried AC, Brookhart M (2002) Polyolefin graft copolymers via living polymerization techniques: Preparation of poly (n-butyl acrylate)-graft-polyethylene through the combination of Pd-mediated living olefin polymerization and atom transfer radical polymerization. J Polym Sci Pol Chem 40:2736-2749
  2. Godoy Lopez R, D'Agosto F, Boisson C (2007) Synthesis of well-defined polymer architectures by successive catalytic olefin polymerization and living/controlled polymerization reactions. Polym Sci 32: 419-454
  3. Kashiwa N, Matsugi T, Kojoh SI, Kawahara HN, Matsuo S, Nobori T, Imuta J (2003) Functionalization of polyethylene based on metallocene catalysis and its application to syntheses of new graft copolymers possessing polar polymer segments. J Polym Sci Pol Chem 41: 3657-3666
  4. Di Lena F, Matyjaszewski K (2010) Transition metal catalysts for controlled radical polymerization. Prog Polym Sci 35: 959–1021
  5. Yanjarappa MJ, Sivaram S (2002) Recent developments in the synthesis of functional poly(olefin)s Prog Polym Sci 27: 1347
  6. Zheng Y, Pan L, Li Y-G, Li Y-S (2008) Synthesis and characterisation of novel functional polyolefin containing sulfonic acid groups. Eur Polym J 44: 475-482
  7. Braunecker WA, Matyjaszewski K (2006) Recent mechanistic developments in atom transfer radical polymerization J mol Catal A Chem 254: 155-164
  8. Chung TC (2002) Synthesis of functional polyolefin copolymers with graft and block structures. Prog Polym Sci 27: 39-85
  9. Salamone JC (1986) Polymeric Material Encyclopedia, Ed., CRC Press, Florida, 1, 57
  10. Britovsek GJP, Gibson VC, Wass DF (1999) The search for new-generation olefin polymerization catalysts: life beyond metallocenes. Angew Chem Int Ed 38: 428-447
  11. Ittel SD, Johnson LK, Brookhart M (2000) Late-metal catalysts for ethylene homo- and copolymerization. Chem Rev 100: 1169-1204
  12. Boffa LS, Novak BM (2000) Copolymerization of polar monomers with olefins using transitionmetal complexes. Chem Rev 100: 1479
  13. Odian G (1991) Principles of polymerization, John Wiley: New York
  14. Kricheldorf HR (1992) Handbook of polymer synthesis Ed, Marcel Decker, New York, Chapter 4
  15. Kricheldorf HR (1992) Handbook of polymer synthesis, Marcel Decker, New York, Chapter 1.
  16. 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-tertbutylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28: 1721
  17. Wang JS, Matyjaszewski K (1995) Controlled/"living" radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process. Macromolecules 28: 7901
  18. Matyjaszewski K, Xia J (2001) Atom transfer radical polymerization. Chem Rev 101: 2921-2990
  19. Pintauer T, Matyjaszewski K (2008) Atom transfer radical addition and polymerization reactions catalyzed by ppm amounts of copper complexes. Chem Soc Rev 37: 1087-1097
  20. Matyjaszewski K, Jakubowski W, Min K, Tang W, Huang J, Braunecker WA, Tsarevsky NV (2006) Diminishing catalyst concentration in atom transfer radical polymerization with reducing agents. Proceeding of National Academy of Science, USA 103: 15309-15314
  21. Min K, Gao H, Matyjaszewski K (2007) Use of ascorbic acid as reducing agent for synthesis of well-defined polymers by arget atrp. Macromolecules 40: 1789-1791
  22. Liu S, Elyashiv S, Sen A (2001) Copper-mediated controlled copolymerization of methyl acrylate with 1-alkenes under mild conditions. J Am Chem Soc 123: 12738-12739
  23. Borkar S, Sen A (2005) Novel fluoroalkene-methyl acrylate copolymers by atom transfer radical polymerization. Macromolecules 38: 3029-3032
  24. Luo R, Sen A (2007) Rate enhancement in controlled radical polymerization of acrylates using recyclable heterogeneous lewis acid. Macromolecules 40:154-156
  25. Venkatesh R, Harrisson S, Haddleton DM, Klumperman K (2004) Olefin copolymerization via controlled radical polymerization: copolymerization of acrylate and 1-octene. Macromolecules 37: 4406-4416
  26. Venkatesh R, Klumperman K (2004) Olefin copolymerization via controlled radical polymerization: copolymerization of methyl methacrylate and 1-octene. Macromolecules 37:1226-1233
  27. Tanaka K, Matyjaszewski K (2008) Copolymerization of (meth)acrylates with olefins using activators regenerated by electron transfer for atom transfer radical polymerization (ARGET ATRP). Macro Symp 37: 1-9
  28. Matyjaszewski K, Tsarevsky NV, Braunecker WA, Dong H, Huang J, Jakubowski, W, Kwak Y, Nicolay R, Tang W, Yoon JA (2007) Role of Cu0 in Controlled/“Living” Radical Polymerization. Macromolecules 40: 7795-7806
  29. Kaur S, Singh G, Gupta VK (2006) Titanium tetrachloride supported on atom transfer radical polymerized poly (methyl acrylate-co-1-octene) as catalyst for ethylene polymerization. J Poly Sci Pol Chem 46: 7299-7309
  30. Brar AS, Kaur S (2005) Microstructure determination of methyl methacrylate and n-butyl acrylate copolymers synthesized by atom transfer radical polymerization with two-dimensional NMR spectroscopy. J Poly Sci Pol Chem 43:1100-1118
  31. Brar AS, Kaur S (2005) A novel ligand for copper-based atom transfer radical polymerization. J Poly Sci Pol Chem 44:5906-5922
  32. Kaur S, Singh G, Kothari A, Gupta VK (2009) Methyl acrylate/1-octene copolymers: Lewis acid-mediated polymerization J App Poly Sci 111: 87-93
Volume 10, Issue 4 - Serial Number 22
November 2023
Pages 235-242
  • Receive Date: 23 July 2023
  • Revise Date: 15 September 2023
  • Accept Date: 23 September 2023
  • First Publish Date: 26 September 2023