Synthesis, molecular, and morphological characterization of initial and modified diblock copolymers with organic acid chloride derivatives
Nikolaos Politakos
Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Search for more papers by this authorCraig J. Weinman
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Search for more papers by this authorMarvin Y. Paik
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Search for more papers by this authorHarihara S. Sundaram
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Search for more papers by this authorCorresponding Author
Christopher K. Ober
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Christopher K. Ober, Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Apostolos Avgeropoulos, Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Search for more papers by this authorCorresponding Author
Apostolos Avgeropoulos
Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Christopher K. Ober, Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Apostolos Avgeropoulos, Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Search for more papers by this authorNikolaos Politakos
Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Search for more papers by this authorCraig J. Weinman
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Search for more papers by this authorMarvin Y. Paik
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Search for more papers by this authorHarihara S. Sundaram
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Search for more papers by this authorCorresponding Author
Christopher K. Ober
Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Christopher K. Ober, Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Apostolos Avgeropoulos, Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Search for more papers by this authorCorresponding Author
Apostolos Avgeropoulos
Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Christopher K. Ober, Department of Materials Science & Engineering, Cornell University, Ithaca, New York 14853-1501
Apostolos Avgeropoulos, Polymers' Laboratory, Department of Materials Science & Engineering, University of Ioannina, University Campus, Ioannina 45110, Greece
Search for more papers by this authorAbstract
Six well defined PS-b-PB1,2 diblock copolymers (PS: polystyrene and PB: polybutadiene) with almost 100% of 1,2 microstructure for the PB segment were synthesized. Size exclusion chromatography (SEC), membrane osmometry (MO) and proton nuclear magnetic resonance spectroscopy (1H NMR) were used for verification of the molecular characteristics and the 100% -1,2 addition for the PB blocks. Modification with heptanoyl or pentadecafluorooctanoyl chloride was accomplished via hydroboration and subsequent oxidation, leading to hydroxylated PB blocks and was verified with 1H NMR and Fourier transform infrared (FTIR) spectroscopy. Only two samples were modified with both organic acid chloride derivatives. Structural characterization was accomplished via transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) in all cases. The self-assembly was more evident in the modified copolymers with the corresponding halides due to the increase of the molecular weight of the modified PB block. Taking into consideration the χN values in each case and comparing the results with those of PS-b-PI copolymers already reported in the literature the discrepancies with the theoretical predictions are very small or minimal. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011
REFERENCES AND NOTES
- 1 Pittman, A. G. In Fluoropolymers; L. A. Wall, Ed.; Willey: New York, 1972; Chapter 25, p 419.
- 2 Schmidt, D. L.; Coburn, C. E.; Dekoven, B. M.; Potter, G. E.; Meyers, G. F.; Fisher, D. A. Nature 1994, 368, 39–41.
- 3(a) Hwang, S. S.; Ober, C. K.; Perutz, S.; Iyengar, D.; Schneggenburger, L. A.; Kramer, E. J. Polymer 1995, 36, 1321–1324; (b) Krishnan, S.; Kwark, Y.-J.; Ober, C. K. Chem Record 2004, 4, 315.
- 4 Iyengar, D.; Perutz, S. M.; Dai, C. A.; Ober, C. K.; Kramer, E. J. Macromolecules 1996, 29, 1229–1234.
- 5 Chapman, T. M.; Benrashid, R.; Marra, K. G.; Keener, J. P. Macromolecules 1995, 28, 331–335.
- 6 Chapman, T. M.; Marra, K. G. Macromolecules 1995, 28, 2081–2085.
- 7 Bescher, P. E.; Noori, A.; Mackenzie, D. J. J Sol-Gel Sci Technol 2004, 32, 69–72.
- 8 Huang, P. H. Sens Actuators 1988, 13, 329–337.
- 9 Doyle, M.; Rajendran, G. In Handbook of Fuel Cells-Fundamentals, Technology and Applications; W. Vielstich; A. Hubert; M. Gasteiger; A. Lamm, Eds.; Wiley: New York, 2003; Vol. 3: Fuel Cell Technology and Applications, pp 351–395.
- 10 Arcella, V.; Ghielmi, A.; Tommasi, G. Ann NY Acad Sci 2003, 984, 226–244.
- 11 Li, Q.; He, R.; Jensen, J. O.; Bjerrum, N. J Chem Mater 2003, 15, 4896–4915.
- 12 Souzy, R.; Ameduri, B. Prog Polym Sci 2005, 30, 644–687.
- 13 Sauguet, L.; Ameduri, B.; Boutevin, B. J Polym Sci Part A: Polym Chem 2007, 45, 1814–1834.
- 14 Timashev, S. F.; Vorobiev, A. V.; Kirichenko, V. I.; Popkov, M.; Volkov, V. I.; Shifrina, R. R.; Lyapunov, A.; Bondarenko, A. G.; Bobrova, L. P. J Membr Sci 1991, 59, 117–131.
- 15 Baradie, B.; Shoichet, M. S.; Shen, Z.; McHugh, M. A.; Hong, L.; Wang, W.; Johnson, J. K.; Beckman, E. J.; Enick, R. M. Macromolecules 2004, 37, 7799–7807.
- 16 Zhao, Y.; Wang, F.; Li, A.; Liu, B.; Wu, Z.; Zhang, D.; Liu, S.; Yi, M. Mater Lett 2004, 58, 2365–2368.
- 17 Assaka, A. M.; Rodrigues, P. C.; Oliveira, A. R. M.; Ding, L.; Hu, B.; Karasz, F. E.; Akcelrud, L. Polymer 2004, 45, 7071–7081.
- 18 Carter, R. K.; DiPietro, A. R.; Sanchez, I. M.; Swanson, A. S. Chem Mater 2001, 13, 213–221.
- 19 Yang, Y.; Ramalingam, S.; Wu, G.; Hsu, S. L.; Kleiner, L.W.; Tang, F. W.; Ding, N.; Hossainy, S. Polymer 2008, 49, 1926–1933.
- 20 Krishnan, S.; Weinman, C. J.; Ober, C. K. J Mater Chem 2008, 18, 3405–3413.
- 21 Vogler, E. A. Water in Biomaterials Surface Science, 1st ed.; M. Morra Ed.; Wiley: New York, 2001, Chapter 10, p 269.
- 22 Floudas, G.; Antonietti, M.; Forster, S. J Chem Phys 2000, 113, 3447–3451.
- 23 Ciardelli, F.; Aglietto, M.; Mirabello, M.; Passaglia, E.; Giancristoforo, S.; Castelvetro, V.; Ruggeri, G. Pro Org Coat 1997, 32, 43–50.
- 24 Grambel, R. D.; Ming, W.; Gildenpfennig, A.; Gennip, W. J. H.; Krupers, M. J.; Laven, J.; Niemantsverdriet, J. W.; Brongersma, H. H.; Linde, R. Prog Org Coat 2002, 45, 273–279.
- 25(a) Casazza, E.; Mariani, A.; Ricco, L.; Russo, S. Polymer 2002, 43, 1207–1214; (b) Krishnan, S.; Ayothi, R.; Hexemer, A.; Finlay, J. A.; Sohn, K. E.; Perry, R.; Ober, C. K.; Kramer, E. J.; Callow, M. E.; Callow, J. A.; Fischer, D. A. Langmuir 2006, 22, 5075–5086.
- 26 Toniolo, L.; Poli, T.; Castelvetro, V.; Manariti, A.; Chiantore, O.; Lazzari, M. J Cultural Heritage 2002, 3, 309–316.
- 27 Hopken, J.; Moller, M. Macromolecules 1992, 25, 1461–1467.
- 28 Wang, J.; Mao, G.; Ober, C.K.; Kramer, E. J. Macromolecules 1997, 30, 1906–1914.
- 29 Perrier, S.; Jackson, G. S.; Haddleton, M. D.; Ameduri, B.; Boutevin, B. Macromolecules 2003, 36, 9042–9049.
- 30 Wynne, K.; Ho, T.; Vu, A.; Chen, X.; Gardella, J. A. Polym Prepr (Am Chem Soc Div Polym Chem) 1995, 36, 67–68.
- 31 Pike, J. K.; Ho, T.; Wynne, K. J. Chem Mater 1996, 8, 856–860.
- 32 Krishnan, S.; Ober, C. K.; Ayothi, R.; Lin, Q.; Paik, M.; Hexemer, A.; Kramer, E. J.; Fischer, D. Polym Prepr (Am Chem Soc Div Polym Chem) 2005, 46, 613–614.
- 33(a) Hadjichristidis, N.; Iatrou, H.; Pispas, S.; Pitsikalis, M. J Polym Sci Part A: Polym Chem 2000, 38, 3211–3234; (b) Uhring, D.; Mays, J. W. J Polym Sci Part A: Polym Chem 2005, 43, 6179–6222.
- 34 Balsara, N. P. In Physical Properties of Polymer Handbook; J. E. Marc, Ed.; Air Press: New York, 1996; Chapter 19.
- 35(a) Rangou, S.; Theodorakis, P. E.; Gergidis, L. N.; Avgeropoulos, A.; Efthymiopoulos, P.; Smyrnaios, D.; Kosmas, M.; Vlahos, C.; Giannopoulos, T. Polymer 2007, 48, 652–663; (b) Avgeropoulos, A.; Paraskeva, S.; Hadjichristidis, N.; Thomas, E. L. Macromolecules 2002, 35, 4030–4035.
- 36(a)
Avgeropoulos, A.;
Rangou, S.;
Krikorian, V.;
Thomas, E. L.;
Macromol Symp
2008,
267,
16–20;
(b)
Pispas, S.;
Avgeropoulos, A.;
Hadjichristidis, N.;
Roovers, J.
J Polym Sci Part B: Polym Phys
1999,
37,
1329–1335;
10.1002/(SICI)1099-0488(19990615)37:12<1329::AID-POLB11>3.0.CO;2-T CAS Web of Science® Google Scholar(c) Hadjichristidis, N.; Tselikas, Y.; Iatrou, H.; Efstratiadis, V.; Avgeropoylos, A. J Macromol Sci Part A: Pure Appl Chem 1996, A33, 1447–1457.
- 37 Brandrup, J.; Immergut, E. H.; Grulke, E. A. Polymer Handbook, 4th ed.; Wiley-Interscience, 1999, p III/55.
- 38(a) Bywater, S.; Worsfold, D. J.; Mackerron, D. H. J Polym Sci Part A: Polym Chem Ed 1985, 23, 1997–2003; (b) Worsfold, D. J.; Bywater, S.; Schue, F.; Sledz, J.; Marti-Collet, V. Makromol Chem Rapid Commun 1982, 3, 239–242.
- 39
Hatada, K.;
Kitayama, T.
NMR Spectroscopy of Polymers;
Springer-Verlag:
Berlin,
2004, p
113.
10.1007/978-3-662-08982-8 Google Scholar
- 40 Fredrickson, G. H.; Bates, F. S. Annu Rev Mater Sci 1996, 26, 501–550.
