Well-defined PE-b-PTFE diblock copolymers via combination of coordination chain transfer polymerization and condensation reaction: Facile preparation and surface modification of polyethylene film

Document Type: Original research

Authors

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Abstract

In this paper, a series of well-defined polyethylene-b-polytetrafluoroethylene diblock copolymers (PE–b– PTFEs) were prepared by a coupling reaction of hydroxyl-terminated polyethylene (PE–OH) and isocyanateterminated 1H,1H-perfluoro-1-tetradecanol (PFDO–NCO). PE–OH was prepared by the coordination chain transfer polymerization using 2,6-bis[1-(2,6-diisopropylphenyl)imino ethyl] pyridine iron (II) dichloride /dry ethylaluminoxane/ZnEt2 as catalyst and subsequent in situ oxidation with oxygen. PFDO–NCO was synthesized through the condensation reaction of 1H,1H- perfluoro-1-tetradecanol (PFDO) with isophoronediisocyanate (IPDI). Subsequently, the thermal characterization and the application of these diblock copolymers were investigated. The relationship between the molecular structure and the properties was disclosed. The results indicated that the diblock copolymers were effective surface modification agents for linear low density polyethylene (LLDPE). After that the PE–b–PTFE being spin-coated onto the surface of LLDPE film, the film was dramatically turned into a superhydrophobic film with a water contact angle as high as 151.4º. This kind of film is potential to be used as selfcleaning, anti-icing and anticorrosion material.

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Main Subjects


  1. Grainger DW, Stewart CW (2001) Fluorinated coatings and films; motivation and significance. In: Fluorinated surfaces, coatings, and films, Castner DG, Grainger DW, Eds., ACS Sym Ser 787, 1-14
  2. Chen SI, Sheu YL, Sheu JL, Lee CT, Lin JS (1997) Morphology of perfluoroalkylacrylate/ stearyl methacrylate polymers and their effect on water/oil repellency. J Appl Polym Sci 63: 903- 909
  3. Furukawa Y, Kotera M (2003) Water and oil repellency of polysiloxanes with highly fluorinated alkyl side chains. J Appl Polym Sci 87:1085-1091
  4. Lazzari M, Aglietto M, Castelvetro V, Chiantore O (2001) Photochemical stability of partially fluorinated acrylic protective coatings. 2. Copolymers of 1H,1H,2H,2H-perfluorodecyl methacrylate with unfluorinated acrylic esters. Chem Mater 13: 2843-2849
  5. Walters KB, Schwark DW, Hirt DE (2003) Surface characterization of linear low-density polyethylene films modified with fluorinated additives. Langmuir 19: 5851-5860
  6. Thanawala SK, Chaudhury MK (2000) Surface modification of silicone elastomer using perfluorinated ether. Langmuir 16: 1256-1260
  7. Waltman RJ, Shieh MG (2001) Chain flexibility and bonding kinetics of Zdol-TX perfluoropolyether lubricant films supported on amorphous carbon surfaces. Macromolecules 34: 6776-6782
  8. Schmidt DL, Brady RF, Lam K, Schmidt DC, Chaudhury MK (2004) Contact angle hysteresis, adhesion, and marine biofouling. Langmuir 20: 2830-2836
  9. Friedrich K (2012) Friction and wear of polymer composites. Elsevier, Amsterdam, p. 138
  10. Marton L (1980) Marton C, Vacuum physics and technology. Academic Press, New York
  11. Ghidont D, Fasulo GC, Mori F, Nocci R (1992) Stabilization of high-impact polystyrene/ polyethylene blends. J Mater Sci 27: 499-503
  12. Ishida T (1994) Mechanical alloying of polytetrafluoroethylene with polyethylene. J Mater Sci Lett 13: 623-628
  13. Uyama M, Kanda M, Nishi Y (2014) Creation of adhesive force between laminated sheets of PTFE and PE by homogeneous low energy electron beam irradiation prior to hot-press for bio-adaptable application. Mater Trans 55: 566-571
  14. Hardman SJ, Hutchings LR, Clarke N, Kimani SM, Mears LLE, Smith EF, Webster JRP, Thompson RL (2012) Surface modification of polyethylene with multi-end-functional polyethylene additives. Langmuir 28: 5125-5137
  15. Valente A, Mortreux A, Visseaux M, Zinck P (2013) Coordinative chain transfer polymerization. Chem Rev 113: 3836-3857
  16. Kempe R (2007) How to polymerize ethylene in a highly controlled fashion? Chemistry 13: 2764- 2773
  17. Small BL, Brookhart M, Bennett AM (1998) Highly active iron and cobalt catalysts for the polymerization of ethylene. J Am Chem Soc 120: 4049-4050
  18. Li LD, Wang Q (2004) Synthesis of polyethylene with bimodal molecular weight by supported iron-based catalyst. J Polym Sci Pol Chem 42: 5662-5669
  19. Wang Q, Li LD(2004) Effect of aluminoxane on molecular weight and molecular weight distribution of polyethylene prepared by an iron-based catalyst. Polym Int 53: 1473-1478
  20. Wang Q, Li LD, Fan ZQ (2004) Polyethylene with bimodal molecular weight distribution synthesized by 2,6-bis(imino)pyridyl complexes of Fe(II) activated with various activators. Eur Polym J 40: 1881-1886
  21. Wang Q, Li LD, Fan ZQ (2005) Effects of tetraalkylaluminoxane activators on ethylene polymerization catalyzed by iron-based complexes. Eur Polym J 41: 1170-1176
  22. Kaneyoshi H, Inove Y, Matyjaszewski K (2005) Synthesis of block and graft copolymers with linear polyethylene segments by combination of degenerative transfer coordination polymerization and atom transfer radical polymerization. Macromolecules 38: 5425-5435
  23. Xiong J, Sun F, Du HG (2007) Determination of isocyanate group in polyurethane by ‘di-n- Butylamine-Acetone’ method (Chinese). Chin J Anal Lab 26: 73-76
  24. Fu ZS, Liu M, Xu XJ, Wang Q, Fan ZQ (2011) Surface modification of linear low-density polyethylene film by amphiphilic graft copolymers based on poly(higher α-olefin)-graft-poly(ethylene glycol). J Appl Polym Sci 119: 1111-1121
  25. Erbil HY, Demirel AL, Avci Y, Mert O (2003) Transformation of a simple plastic into a superhydrophobic surface. Science 299: 1377- 1380
  26. Nakajima A, Hashimoto K, Watanabe T (2001) Recent studies on super-hydrophobic films. Monatsh Chem 132: 31-41 198
  27. Coulson SR, Woodward I, Badyal JPS, Brewer SA, WillisC (2000) Super-repellent composite fluoropolymer surfaces. J Phys Chem Pol Phys 104: 8836-8840
  28. Stuart BH (2004) Infrared spectroscopy: Fundamentals and application. John Wiely & Sons, Ltd., Chichester, 113-136