Synthesis of polysulfone-b-polystyrene block copolymers by mechanistic transformation from condensation polymerization to free radical polymerization

Abstract

Synthesis of polysulfone-b-polystyrene (PSU-b-PS) block copolymers by a combination of condensation polymerization and free radical polymerization processes are described. First, a new macroazoinitiator (MAI) containing polysulfone (PSU) units was prepared by direct esterification of 4,4-azobis(4-cyanopentanoic acid) with α,ω-hydroxyl PSU telechelics at ambient conditions. The macroinitiator was then used in conventional free radical polymerization of styrene leading to the formation of desired block copolymers. In this process, initiating macroradicals were generated by thermal cleavage of the azo group present in the macroazoinitiator structure. The precursor polysulfone macroazoinitiator (PSU-MAI) and resulting block copolymers were characterized by spectral analysis using FT-IR, 1H-NMR, GPC, TGA, and DSC.

This is a preview of subscription content, log in to check access.

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  1. 1.

    Mishra MK, Yagci Y (2009) Handbook of vinyl polymers: radical polymerization, process, and technology. CRC Press, Boca Raton

    Google Scholar 

  2. 2.

    Nalwa HS (2001) Advanced functional molecules and polymers. Gordon & Breach, Australia

    Google Scholar 

  3. 3.

    Zhao DY, Huo QS, Feng JL, Chmelka BF, Stucky GD (1998) Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures. J Am Chem Soc 120(24):6024–6036. doi:10.1021/ja974025i

    Article  CAS  Google Scholar 

  4. 4.

    Bates FS, Fredrickson GH (1999) Block copolymers—designer soft materials. Phys Today 52(2):32–38. doi:10.1063/1.882522

    Article  CAS  Google Scholar 

  5. 5.

    Kataoka K, Harada A, Nagasaki Y (2001) Block copolymer micelles for drug delivery: design, characterization and biological significance. Adv Drug Deliv Rev 47(1):113–131. doi:10.1016/s0169-409x(00)00124-1

    Article  CAS  Google Scholar 

  6. 6.

    Discher DE, Eisenberg A (2002) Polymer vesicles. Science 297(5583):967–973. doi:10.1126/science.1074972

    Article  CAS  Google Scholar 

  7. 7.

    Jeong B, Bae YH, Lee DS, Kim SW (1997) Biodegradable block copolymers as injectable drug-delivery systems. Nature 388(6645):860–862

    Article  CAS  Google Scholar 

  8. 8.

    Liu JQ, Zhang Q, Remsen EE, Wooley KL (2001) Nanostructured materials designed for cell binding and transduction. Biomacromolecules 2(2):362–368. doi:10.1021/bm015515c

    Article  CAS  Google Scholar 

  9. 9.

    Rzaev ZMO, Dincer S, Piskin E (2007) Functional copolymers of n-isopropylacrylamide for bioengineering applications. Prog Polym Sci 32(5):534–595. doi:10.1016/j.progpolymsci.2007.01.006

    Article  CAS  Google Scholar 

  10. 10.

    Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH (1998) Living free-radical polymerization by reversible addition-fragmentation chain transfer: the raft process. Macromolecules 31(16):5559–5562. doi:10.1021/ma9804951

    Article  CAS  Google Scholar 

  11. 11.

    Hawker CJ, Bosman AW, Harth E (2001) New polymer synthesis by nitroxide mediated living radical polymerizations. Chem Rev 101(12):3661–3688. doi:10.1021/cr990119u

    Article  CAS  Google Scholar 

  12. 12.

    Matyjaszewski K, Xia JH (2001) Atom transfer radical polymerization. Chem Rev 101(9):2921–2990. doi:10.1021/cr940534g

    Article  CAS  Google Scholar 

  13. 13.

    Guo YM, Pan CY, Wang J (2001) Block and star block copolymers by mechanism transformation. Vi. Synthesis and characterization of a(4)b(4) miktoarm star copolymers consisting of polystyrene and polytetrahydrofuran prepared by cationic ring-opening polymerization and atom transfer radical polymerization. J Polym Sci 39(13):2134–2142

    Google Scholar 

  14. 14.

    Xu YJ, Pan CY (2000) Block and star-block copolymers by mechanism transformation. 3. S-(PTHF-PSt)(4) and S-(PTHF-PSt-PMMA)(4) from living crop to ATRP. Macromolecules 33(13):4750–4756

    Article  CAS  Google Scholar 

  15. 15.

    Xu YJ, Pan CY (2000) Block and star block copolymers by mechanism transformation. I. Synthesis of PTHF-PST-PTHF by the transformation of ATRP into crop. J Polym Sci A 38(2):337–344

    Article  CAS  Google Scholar 

  16. 16.

    Guo YM, Pan CY (2001) Block and star block copolymers by mechanism transformation. Part V. Syntheses of polystyrene/polytetrahydrofuran A2B2 miktoarm star copolymers by transformation of crop into ATRP. Polymer 42(7):2863–2869

    Article  CAS  Google Scholar 

  17. 17.

    Yagci Y, Serhatli IE, Kubisa P, Biedron T (1993) Synthesis of block copolymers by combination of an activated monomer and free-radical polymerization mechanism. Macromolecules 26(10):2397–2399

    Article  CAS  Google Scholar 

  18. 18.

    Yagci Y, Tasdelen MA (2006) Mechanistic transformations involving living and controlled/living polymerization methods. Prog Polym Sci 31(12):1133–1170. doi:10.1016/j.progpolymsci.2006.07.003

    Article  CAS  Google Scholar 

  19. 19.

    Cianga I, Senyo T, Ito K, Yagci Y (2004) Electron transfer reactions of radical anions with tempo: a versatile route for transformation of living anionic polymerization into stable radical-mediated polymerization. Macromol Rapid Comm 25(19):1697–1702

    Article  CAS  Google Scholar 

  20. 20.

    Tasdelen MA, Yagci Y, Demirel AL, Biedron T, Kubisa P (2007) Synthesis and characterization of block-graft copolymers poly(epichlorohydrin-b-styrene)-g-poly(methyl methacrylate) by combination of activated monomer polymerization, nmp and atrp. Polym Bull 58(4):653–663. doi:10.1007/s00289-006-0708-y

    Article  CAS  Google Scholar 

  21. 21.

    Yagci Y, Duz AB, Onen A (1997) Controlled radical polymerization initiated by stable radical terminated polytetrahydrofuran. Polymer 38(11):2861–2863

    Article  CAS  Google Scholar 

  22. 22.

    Yagci Y (1985) Block copolymers by combinations of cationic and radical routes.1. A new difunctional azo-oxocarbenium initiator for cationic polymerization. Polymer. Communications 26(1):7–8

    CAS  Google Scholar 

  23. 23.

    Hizal G, Yagci Y, Schnabel W (1994) N-alkoxy pyridinium ion terminated polytetrahydrofurans—synthesis and their use in photoinitiated block copolymerization. Polymer 35(20):4443–4448

    Article  CAS  Google Scholar 

  24. 24.

    Galli G, Chiellini E, Yagci Y, Serhatli EI, Laus M, Bignozzi MC, Angeloni AS (1993) Block copolymers with crystalline and side-chain liquid-crystalline blocks. Makromol Chem, Rapid Commun 14(3):185–193

    Article  CAS  Google Scholar 

  25. 25.

    Yagci Y, Onen A, Schnabel W (1991) Block copolymers by combination of radical and promoted cationic polymerization routes. Macromolecules 24(16):4620–4623

    Article  CAS  Google Scholar 

  26. 26.

    Duz AB, Yagci Y (1999) Synthesis of block copolymers by combination of atom transfer radical and promoted cationic polymerization mechanisms. Eur Polym J 35(11):2031–2038

    Article  CAS  Google Scholar 

  27. 27.

    Durmaz YY, Kukut M, Moszner N, Yagci Y (2009) Sequential photodecomposition of bisacylgermane type photoinitiator: synthesis of block copolymers by combination of free radical promoted cationic and free radical polymerization mechanisms. J Polym Sci A 47(18):4793–4799. doi:10.1002/pola.23533

    Article  CAS  Google Scholar 

  28. 28.

    Serhatli IE, Galli G, Yagci Y, Chiellini E (1995) Synthesis of hybrid liquid-crystalline block-copolymers by combination of cationic or promoted cationic and free-radical polymerizations. Polym Bull 34(5–6):539–546. doi:10.1007/bf00423349

    Article  CAS  Google Scholar 

  29. 29.

    Hizal G, Sarman A, Yagci Y (1995) Synthesis of hydroxy-terminated polytetrahydrofuran by photoinduced process. Polym Bull 35(5):567–573

    Article  CAS  Google Scholar 

  30. 30.

    Durmaz YY, Yilmaz G, Yagci Y (2007) N-alkoxy pyridinium ion terminated polystyrenes: a facile route to photoinduced block copolymerization. J Polym Sci A 45(3):423–428

    Article  CAS  Google Scholar 

  31. 31.

    Acik G, Kahveci MU, Yagci Y (2010) Synthesis of block copolymers by combination of atom transfer radical polymerization and visible light radical photopolymerization methods. Macromolecules 43(21):9198–9201. doi:10.1021/ma101967w

    Article  CAS  Google Scholar 

  32. 32.

    Yagci Y (1986) Block copolymers by combinations of cationic and radical routes. 2. Use of polymers with acyl chloride terminal groups in oxocarbenium polymerization. Polymer. Communications 27(1):21–22

    CAS  Google Scholar 

  33. 33.

    Denizligil S, Baskan A, Yagci Y (1995) Bifunctional polytetrahydrofuran initiator for sequential photochemical and thermal initiation. Macromol Rapid Comm 16(5):387–391

    Article  CAS  Google Scholar 

  34. 34.

    Ren Q, Zhang HJ, Zhang XK, Huang BT (1993) Hydrogenated polybutadiene polymethyl methacrylate (HPB PMMA) block copolymer .1. Synthesis of polybutadiene polymethyl methacrylate (PB PMMA) block copolymer. J Polym Sci A 31(4):847–851. doi:10.1002/pola.1993.080310401

    Google Scholar 

  35. 35.

    Tunca U, Serhatli IE, Yagci Y (1989) Polymerization of acrylamide initiated by the redox system Ce(IV)-4,4′-azobis (4-cyano pentanol). Polym Bull 22(5–6):483–488

    Article  CAS  Google Scholar 

  36. 36.

    Hizal G, Yagci Y (1989) Block copolymers by combination of cationic and radical routes.4. Cationic polymerization of tetrahydrofuran initiated by difunctional azo-oxocarbenium initiator. Polymer 30(4):722–725. doi:10.1016/0032-3861(89)90162-6

    Article  CAS  Google Scholar 

  37. 37.

    Hazer B, Erdem B, Lenz RW (1994) Styrene polymerization with some new macro or macromonomeric azoinitiators having peg units. J Polym Sci A 32(9):1739–1746. doi:10.1002/pola.1994.080320916

    Article  CAS  Google Scholar 

  38. 38.

    Haneda Y, Terada H, Yoshida M, Ueda A, Nagai S (1994) Macro-azo-initiators composed of various polyesters—their syntheses, thermal-properties, and application to block copolymerization. J Polym Sci A 32(14):2641–2652. doi:10.1002/pola.1994.080321405

    Article  CAS  Google Scholar 

  39. 39.

    Simionescu CI, David G, Ioanid A, Paraschiv V, Riess G, Simionescu BC (1994) Solution polymerization of vinyl monomers in the presence of poly(n-acetyliminoethylene) macroazoinitiators. J Polym Sci A 32(16):3123–3132. doi:10.1002/pola.1994.080321612

    Article  CAS  Google Scholar 

  40. 40.

    Tunca U, Yagci Y (1990) Synthesis, decomposition, and initiator properties of macroazonitriles for the preparation of polymers with crown ether units. J Polym Sci A 28(7):1721–1733. doi:10.1002/pola.1990.080280705

    Article  CAS  Google Scholar 

  41. 41.

    Nuyken O, Weidner R (1986) Graft and block copolymers via polymeric azo initiators. Adv Polym Sci 73–74:145–199

    Article  Google Scholar 

  42. 42.

    Kim DK, Lee SB, Doh KS, Nam YW (1999) Synthesis of block copolymers having perfluoroalkyl and silicone-containing side chains using diazo macroinitiator and their surface properties. J Appl Polym Sci 74(8):1917–1926. doi:10.1002/(SICI)1097-4628(19991121)74:8<1917:AID-APP5>3.0.CO;2-G

    Article  CAS  Google Scholar 

  43. 43.

    Cheikhalard T, Tighzert L, Pascault JP (1996) Polyurethane macroazoinitiators based on 2,2′-azobis(2-cyanopropanol) kinetic studies. J Appl Polym Sci 62(13):2365–2375. doi:10.1002/(SICI)1097-4628(19961226)62:13<2365:AID-APP22>3.0.CO;2-0

    Article  CAS  Google Scholar 

  44. 44.

    Uyanik N, Baysal BM (1990) Preparation of polystyrene-block-(ethylene oxide)s and characterization of the products. J Appl Polym Sci 41(9–10):1981–1993. doi:10.1002/app.1990.070410905

    Article  CAS  Google Scholar 

  45. 45.

    Chang TC, Chen HB, Chen YC, Ho SY (1996) Characterization of azo-containing polydimethylsiloxanes and their copolymers with methyl methacrylate. J Polym Sci A 34(13):2613–2620. doi:10.1002/(SICI)1099-0518(19960930)34:13<2613:AID-POLA7>3.0.CO;2-S

    Article  CAS  Google Scholar 

  46. 46.

    Shimura Y, Chen DJ (1993) Thermodegradable polyurethanes having azo groups in the main chains. 1. Synthesis and thermal properties. Macromolecules 26(19):5004–5008. doi:10.1021/ma00071a003

    Article  CAS  Google Scholar 

  47. 47.

    Olabisi O (1997) Handbook of thermoplastics. Marcel Dekker, New York. http://worldcat.org; http://search.ebscohost.com/login.aspx?direct=true&scope=site&db=nlebk&db=nlabk&AN=12621

  48. 48.

    Wang F, Hickner M, Kim YS, Zawodzinski TA, McGrath JE (2002) Direct polymerization of sulfonated poly(arylene ether sulfone) random (statistical) copolymers: candidates for new proton exchange membranes. J Membr Sci 197(1–2):231–242. doi:10.1016/s0376-7388(01)00620-2

    Article  CAS  Google Scholar 

  49. 49.

    Hickner MA, Ghassemi H, Kim YS, Einsla BR, McGrath JE (2004) Alternative polymer systems for proton exchange membranes (PEMs). Chem Rev 104(10):4587–4611. doi:10.1021/cr020711a

    Article  CAS  Google Scholar 

  50. 50.

    Guiver MD, Robertson GP, Yoshikawa M, Tam CM (2000) Functionalized polysulfones: Methods for chemical modification and membrane applications. In: Pinnau I, Freeman BD (eds) Membrane formation and modification, vol 744, ACS symposium series, pp 137–161

  51. 51.

    Paul M, Park HB, Freeman BD, Roy A, McGrath JE, Riffle JS (2008) Synthesis and crosslinking of partially disulfonated poly(arylene ether sulfone) random copolymers as candidates for chlorine resistant reverse osmosis membranes. Polymer 49(9):2243–2252. doi:10.1016/j.polymer.2008.02.039

    Article  CAS  Google Scholar 

  52. 52.

    Higuchi A, Sugiyama K, Yoon BO, Sakurai M, Hara M, Sumita M, Sugawara S, Shirai T (2003) Serum protein adsorption and platelet adhesion on pluronic (TM)-adsorbed polysulfone membranes. Biomaterials 24(19):3235–3245. doi:10.1016/s0142-9612(03)00186-8

    Article  CAS  Google Scholar 

  53. 53.

    Zhao CS, Liu XD, Nomizu M, Nishi N (2003) Blood compatible aspects of DNA-modified polysulfone membrane-protein adsorption and platelet adhesion. Biomaterials 24(21):3747–3755. doi:10.1016/s0142-9612(03)00250-3

    Article  CAS  Google Scholar 

  54. 54.

    Cureton LT, Beyer FL, Turner SR (2010) Synthesis and characterization of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) and polydimethylsiloxane segmented block copolymers. Polymer 51(8):1679–1686. doi:10.1016/j.polymer.2010.02.010

    Article  CAS  Google Scholar 

  55. 55.

    Bai Z, Houtz MD, Mirau PA, Dang TD (2007) Structures and properties of highly sulfonated poly(arylenethioethersulfone)s as proton exchange membranes. Polymer 48(22):6598–6604. doi:10.1016/j.polymer.2007.08.052

    Article  CAS  Google Scholar 

  56. 56.

    Chen Y, Guo R, Lee CH, Lee M, McGrath JE (2012) Partly fluorinated poly(arylene ether ketone sulfone) hydrophilic-hydrophobic multiblock copolymers for fuel cell membranes. Int J Hydrogen Energy 37(7):6132–6139. doi:10.1016/j.ijhyene.2011.06.139

    Article  CAS  Google Scholar 

  57. 57.

    Lee CH, Xie W, VanHouten D, McGrath JE, Freeman BD, Spano J, Wi S, Park CH, Lee YM (2012) Hydrophilic silica additives for disulfonated poly(arylene ether sulfone) random copolymer membranes. J Membrane Sci 392:157–166. doi:10.1016/j.memsci.2011.12.015

    Article  Google Scholar 

  58. 58.

    Dizman C, Ates S, Torun L, Yagci Y (2010) Synthesis, characterization and photoinduced curing of polysulfones with (meth)acrylate functionalities. Beilstein J Org Chem 6:56. doi:10.3762/bjoc.6.56

  59. 59.

    Ates S, Dizman C, Aydogan B, Kiskan B, Torun L, Yagci Y (2011) Synthesis, characterization and thermally activated curing of polysulfones with benzoxazine end groups. Polymer 52(7):1504–1509. doi:10.1016/j.polymer.2011.01.051

    Article  CAS  Google Scholar 

  60. 60.

    Dizman C, Ates S, Uyar T, Tasdelen MA, Torun L, Yagci Y (2011) Polysulfone/clay nanocomposites by in situ photoinduced crosslinking polymerization. Macromol Mater Eng 296(12):1101–1106. doi:10.1002/mame.201100114

    Article  CAS  Google Scholar 

  61. 61.

    Dizman C, Demirkol DO, Ates S, Torun L, Sakarya S, Timur S, Yagci Y (2011) Photochemically prepared polysulfone/poly(ethylene glycol) amphiphilic networks and their biomolecule adsorption properties. Colloids Surf B 88(1):265–270. doi:10.1016/j.colsurfb.2011.06.042

    Article  CAS  Google Scholar 

  62. 62.

    Toiserkani H, Yilmaz G, Yagci Y, Torun L (2010) Functionalization of polysulfones by click chemistry. Macromol Chem Physic 211(22):2389–2395. doi:10.1002/macp.201000245

    Article  CAS  Google Scholar 

  63. 63.

    Karadag M, Yilmaz G, Toiserkani H, Demirkol DO, Sakarya S, Torun L, Timur S, Yagci Y (2011) Polysulfone/pyrene membranes: a new microwell assay platform for bioapplications. Macromol Biosci 11(9):1235–1243. doi:10.1002/mabi.201100024

    Article  CAS  Google Scholar 

  64. 64.

    Yilmaz G, Toiserkani H, Demirkol DO, Sakarya S, Timur S, Torun L, Yagci Y (2011) Polysulfone based amphiphilic graft copolymers by click chemistry as bioinert membranes. Mater Sci Eng C 31(5):1091–1097. doi:10.1016/j.msec.2011.03.010

    Article  CAS  Google Scholar 

  65. 65.

    Yilmaz G, Toiserkani H, Demirkol DO, Sakarya S, Timur S, Yagci Y, Torun L (2011) Modification of polysulfones by click chemistry: amphiphilic graft copolymers and their protein adsorption and cell adhesion properties. J Polym Sci A 49(1):110–117. doi:10.1002/pola.24424

    Article  CAS  Google Scholar 

  66. 66.

    Hazer B, Ayas A, Besirli N, Saltek N, Baysal BM (1989) Preparation of ABCBA-type block copolymers by use of macro-initiators containing peroxy and azo groups. Makromol Chem 190(8):1987–1996

    Article  CAS  Google Scholar 

  67. 67.

    Tasdelen MA, Kahveci MU, Yagci Y (2011) Telechelic polymers by living and controlled/living polymerization methods. Prog Polym Sci 36(4):455–567. doi:10.1016/j.progpolymsci.2010.10.002

    Article  CAS  Google Scholar 

  68. 68.

    Yagci Y, Mishra MK (1994) Macroinitiators in multi-mode polymerization. In: Mishra MK (ed) Macromolecular design: concept and practice (macromonomers, macroinitiators, macroiniferters, macroinimers, macroinifers, macroiniters). Polymer Frontiers International, Hopewell Jct, New York

  69. 69.

    Simon J, Bajpai A (2001) Synthesis of macroazoinitiator by direct polycondensation for block copolymerization of styrene and butadiene. J Appl Polym Sci 82(12):2922–2933. doi:10.1002/app.2148

    Article  CAS  Google Scholar 

  70. 70.

    Markova D, Kumar A, Klapper M, Muellen K (2009) Phosphonic acid-containing homo-, AB and BAB block copolymers via ATRP designed for fuel cell applications. Polymer 50(15):3411–3421. doi:10.1016/j.polymer.2009.06.011

    Article  CAS  Google Scholar 

  71. 71.

    Kumar A, Pisula W, Markova D, Klapper M, Muellen K (2012) Proton-conducting poly(phenylene oxide)–poly(vinyl benzyl phosphonic acid) block copolymers via atom transfer radical polymerization. Macromol Chem Phys 213(5):489–499. doi:10.1002/macp.201100429

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank Istanbul Technical University Research Fund and the State Planning Organization of Turkey (DPT) (Project No: 2005K120920) for the financial support.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Yusuf Yagci.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Dizman, C., Kahveci, M.U. & Yagci, Y. Synthesis of polysulfone-b-polystyrene block copolymers by mechanistic transformation from condensation polymerization to free radical polymerization. Polym. Bull. 70, 2097–2109 (2013). https://doi.org/10.1007/s00289-013-0931-2

Download citation

Keywords

  • Block copolymer
  • Condensation polymerization
  • Free radical polymerization
  • Macroazoinitiator
  • Polysulfone
  • Polystyrene