Synthesis and identification of polystyrene via conventional and controlled radical polymerization methods: Effect of temperature, initiator and transfer agent on molecular weight and reaction rate

Document Type: Original research

Authors

Polymer Reaction Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box: 14115-114, Tehran, I.R. Iran

Abstract

Polystyrene (PSt) has been known as one of the important polymers with a wide range of applications. Ability to synthesize PSt with different but predictable molecular weights for various applications is very important in the laboratories and industries. In this study, using various simple and inexpensive techniques with only free radical mechanism, it was tried to synthesize PSt with different low (< 2×104 g mol-1) to high (> 105 g mol-1) molecular weights. PSts with high and moderate molecular weights (2×104-105 g mol-1) were synthesized using thermal and conventional free radical polymerizations, respectively. Reverse iodine transfer radical polymerization (RITP) was utilized to synthesize PSt with a low and controlled molecular weight. Conversion, molecular weight distribution and PSt structure were analyzed using 1H-NMR spectroscopy and size exclusion chromatography (SEC), respectively. Moreover, ω-iodo poly(dimethylsiloxane), i.e. PDMS-I, was also used as a macrotransfer agent for ITP of styrene. Diblock copolymer of PDMS-b-PSt was characterized by 1H-NMR and SEC analyses.

Keywords

Main Subjects


  1. Tsukahara Y, Tsutsumi K, Yamashita Y, Shimada S (1990) Radical polymerization behavior of macromonomers. 2. Comparison of styrene macromonomers having a methacryloyl end group and a vinylbenzyl end group. Macromolecules 23: 5201-5208
  2. Hasebe T, Kamigaito M, Sawamoto M (1996) Living cationic polymerization of styrene with TiCl3(OiPr) as a lewis acid activator. Macromolecules 29: 6100-6103
  3. Lin CH, Xiang JS, Matyjaszewski K (1993) "Living" cationic polymerization of styrene in the presence of tetrabutylammonium salts. Macromolecules 26: 2785-2790
  4. Geacintov C, Smid J, Szwarc M (1962) Kinetics of anionic polymerization of styrene in tetrahydrofuran. J Am Chem Soc 84: 2508-2514
  5. Stretch C, Allen G (1961) Anionic polymerization of styrene. Polymer 2: 151-160
  6. Percec V, Barboiu B, Neumann A, Ronda JC, Zhao M (1996) Metal-catalyzed “living” radical polymerization of styrene initiated with arenesulfonyl chlorides: From heterogeneous to homogeneous catalysis. Macromolecules 29: 3665-3668
  7. Scheirs J (2003) Historical Overview of styrenic polymers. in: Modern styrenic polymers: Polystyrenes and styrenic copolymers, Scheirs J, Priddy DB (Eds), John Wiley & Sons Ltd., Wiltshire, 1-24
  8. Srinivasan S, Lee MW, Grady MC, Soroush M, Rappe AM (2010) Self-initiation mechanism in spontaneous thermal polymerization of ethyl and n-butyl acrylate: A theoretical study. J Phys Chem A 114: 7975-7983
  9. Stickler M, Meyerhoff G (1981) The spontaneous thermal polymerization of methyl methacrylate: 5. Experimental study and computer simulation of the high conversion reaction at 130°C. Polymer 22: 928-933
  10. Christie DI, Gilbert RG, Congalidis JP, Richards JR, McMinn JH (2001) Spontaneous polymerization in the emulsion polymerization of styrene and chlorobutadiene. Macromolecules 34: 5158-5168
  11. Katzer J, Pauer W, Moritz H-U (2012) Thermal polymerization of styrene, part 1 – bulk polymerization. Macromol React Eng 6: 213-224
  12. Katzer J, Pauer W, Moritz H-U, Wulkow M (2012) Thermal polymerization of styrene, part 2 – (mini) emulsion polymerization. Macromol React Eng 6: 225-238
  13. Borecka B, Chojnowski J, Cypryk M, Michalski J, Zielinska J (1979) Synthetic and mechanistic aspects of the reaction of trialkylsilyl halides with thio and seleno esters of phosphorus. J Organomet Chem 171: 17-34
  14. Kotoulas C, Krallis A, Pladis P, Kiparissides C (2003) A comprehensive kinetic model for the combined chemical and thermal polymerization of styrene up to high conversions. Macromol Chem Phys 204: 1305-1314
  15. Matheson MS, Auer EE, Bevilacqua EB, Hart EJ (1951) Rate constants in free radical polymerization. III. styrene1. J Am Chem Soc 73: 1700-1706
  16. Meister BJ,Cummings CJ (2003) Commercial processes for the manufacture of polystyrene. in modern styrenic polymers: polystyrenes and styrenic copolymers, Ed., John Wiley & Sons, Ltd. 43-72
  17. Yamada B, Zetterlund PB (2003) General chemistry of radical polymerization. In: handbook of radical polymerization, Matyjaszewski K, Davis TP (Eds), John Wiley & Sons Inc, 117-186
  18. Braunecker WA, Matyjaszewski K (2007) Controlled/living radical polymerization: features, developments, and perspectives. Prog Polym Sci 32: 93-146
  19. Goto A,Fukuda T (2004) Kinetics of living radical polymerization. Prog Polym Sci 29: 329-385
  20. Matyjaszewski K,Spanswick J (2005) Controlled/ living radical polymerization. Mater Today 8: 26- 33
  21. Cunningham MF (2002) Living/controlled radical polymerizations in dispersed phase systems. Prog Polym Sci 27: 1039-1067
  22. Gaynor SG, Wang J-S, Matyjaszewski K (1995) Controlled radical polymerization by degenerative transfer: effect of the structure of the transfer agent. Macromolecules 28: 8051-8056
  23. Goto A, Ohno K, Fukuda T (1998) Mechanism and kinetics of iodide-mediated polymerization of styrene. Macromolecules 31: 2809-2814
  24. Matyjaszewski K, Gaynor S, Wang J-S (1995) Controlled radical polymerizations: the use of alkyl iodides in degenerative transfer. Macromolecules 28: 2093-2095
  25. Kim K, Ko NR, Rhee SE, Lee BH, Choe S (2012) Molecular control of polystyrene in the reverse iodine transfer polymerization (RITP) – Suspension process. Polymer 53: 4054-4059
  26. Oh HG, Shin H, Jung H, Lee BH, Choe S (2011) Control of molecular weight of polystyrene using the reverse iodine transfer polymerization (RITP) – Emulsion technique. J Colloid Interf Sci 353: 459-466
  27. Tonnar J, Lacroix-Desmazes P, Boutevin B (2006) Controlled radical polymerization of styrene by reverse iodine transfer polymerization (ritp) in miniemulsion: Use of hydrogen peroxide as oxidant. Macromolecules 40: 186-190
  28. Tonnar J, Severac R, Lacroix-Desmazes P, Boutevin B (2008) Controlled radical polymerization of styrene by reverse iodine transfer polymerization (RITP). Polym Prepr 49: 68-69
  29. Semsarzadeh MA, Abdollahi M (2012) Atom transfer radical polymerization of styrene and methyl (meth)acrylates initiated with poly(dimethylsiloxane) macroinitiator: Synthesis and characterization of triblock copolymers. J Appl Polym Sci 123: 2423-2430
  30. Pouget E, Tonnar J, Eloy C, Lacroix-Desmazes P, Boutevin B (2006) Synthesis of poly(styrene)-b-poly(dimethylsiloxane)-b-poly(styrene) triblock copolymers by iodine transfer polymerization in miniemulsion. Macromolecules 39: 6009-6016
  31. Farrokhi M,Abdollahi M (2016) ω-Iodinated poly(dimethylsiloxane) as a chain transfer agent in iodine transfer radical polymerization of vinyl acetate and dibutyl maleate: Synthesis and structural characterization. J Polym Res 23: 1-11
  32. Trifan DS,Bartlett PD (1959) Iodine and styrene. I. Four reactions between iodine and styrene. J Am Chem Soc 81: 5573-5581
  33. Wright T, Chirowodza H, Pasch H (2012) NMR studies on the mechanism of reverse iodine transfer polymerization of styrene. Macromolecules 45: 2995-3003
  34. Shiman DI, Kostyuk SV, Gaponik LV, Kaputskii FN (2010) Controlled radical polymerization of styrene in the presence of molecular iodine. Russ J Appl Chem 83: 2028-2034
  35. Brandrup J, Immergut EH, Grulke EA (1999). Polymer handbook John Wiley & Sons
  36. Moad G, Solomon DH, Johns SR, Willing RI (1984) Fate of the initiator in the azobisisobutyronitrile-initiated polymerization of styrene. Macromolecules 17: 1094-1099
  37. Farrokhi M,Abdollahi M (2014) Synthesis and characterization of ω-halogenated poly(dimethylsiloxane). Iran J Polym Sci Tech 26: 475-484
  38. Staisch I (2008) Novel siloxane block copolymers. Stellenbosch University, PhD Thesis
  39. Tonnar J, Pouget E, Lacroix-Desmazes P, Boutevin B (2008) Synthesis of poly(vinyl acetate)-b-poly(dimethylsiloxane)-b-poly(vinyl acetate) triblock copolymers by iodine transfer polymerization. Eur Polym J 44: 318-328