ABSTRACT

We have introduced the concept of comb-coil supramolecule into linear (AB)n-type multiblock copolymer and investigated the self-assembly behavior of the copolymer as a function of the unit number n. Linear (polystyrene-block-poly(2-vinylpyridine))n (denoted as (PS-b-P2VP)n) (n =1, 2, 3) with symmetric compositors were complexed with dodecylbenzenesulfonic acid (DBSA) to yield the comb-coil multiblock copolymers in which DBSA bound stoichiometrically with P2VP block by ionic bonding. The phase behavior of the copolymers was studied by temperature-dependent small angle X-ray scattering (SAXS). All three comb-coil block copolymers, including diblock (n=1), tetrablock (n=2) and hexablock (n=3), self-organized to form cylinder-within-lamellae morphology at the lower temperature, where the cylindrical microdomains formed by the PS block embedded in the matrix composed of the lamellar mesophase organized by the P2VP(DBSA) comb block. The disordering of the smaller-scale lamellar mesophase formed by the comb block occurred upon heating. At the same time, the larger-scale cylindrical domains transformed to body-centered-cubic (BCC) packed spheres in the diblock complex and to another hexagonally-packed cylinder (HEX) structure with smaller domain spacing in tetrablock and hexablock complexes, indicating that the order-disorder transition (ODT) of the smaller-scale structure drove an order-order transition (OOT) of the larger-scale structure irrespective of n. The transition temperatures were found to increase with increasing n due to the increase of the enthalpy of transition arising from the larger interfacial energy contribution in the multiblock.
Another aim of this study is to understand the relative orientation between the larger-scale copolymer domain and the smaller-scale lamellae in multiblock comb-coil copolymer. The two-dimensional (2-D) SAXS patterns of the samples treated by large amplitude oscillatory shear revealed that the relative orientation varied with the binding fraction (x) of DBSA to P2VP block, but is independent of n. At the lower binding fraction (x ≤ 0.5), the smaller-scale lamellae showed an edge-on arrangement around the PS cylinders. At the higher binding fraction (x > 0.5), the two type of structures exhibited the orthogonal orientation, where the smaller-scale lamellae stacked along the long axis of the PS cylinders.

CONTENTS

Acknowledgment I
ABSTRACT II
CONTENTS III
List of Figures IV
Chapter 1 Introduction 1
1.1 General introduction of block copolymers 1
1.2 Supramolecular comb-coil diblock copolymers 2
1.3 Self-assembly behavior of linear (AB)n-type multiblock copolymer 4
1.4 Motivation and objective of this study 4
Chapter 2 Experimental Section 13
2.1 Materials 13
2.2 Sample preparation 13
2.3 Characterization 14
Chapter 3 Results and discussion 17
3.1 Hierarchical Structures and Phase Transition of the Comb-Coil Diblock Copolymer (n=1) 17
3.2 Hierarchical Structures and Phase Transition of the Multiblock Comb-Coil Copolymer 18
3.2.1 Tetrablock system (n=2) 18
3.2.2 Hexablock system (n=3) 19
3.3 The relative orientation of the hierarchical structures of comb-coil multiblock copolymers 24
Chapter 4 Conclusions 37
References 38

References
1. Ruokolainen, J.; Makinen, R.; Torkkeli, M.; Makela, T.; Serimaa, R.;ten Brinke, G.; Ikkala, O. Science 1998, 280, 557.
2. Matsen, M. W.; Bates, F. S. J. Chem. Phys. 1997, 106, 2436.
3. Hadjichristis, N.; Pispas, S.; Floudas, G. Block Copolymer: Synthetic Srategies, Physical Properties, and Applications 2003
4. Helfand, E. J. Chem. Phys. 1975, 62, 999-1005
5. Helfand, E. Macromolecules 1975, 8, 522.
6. Helfand, E.; Wasserman Z. R. Macromolecules 1976, 9, 879.
7. Helfand, E.; Wasserman Z. R. Macromolecules 1980, 13, 994.
8. Helfand, E.; Wasserman Z. R. Macromolecules 1978, 11, 961.
9. Leary, D.; Williams, M. Journal of Polymer Science Part B: Polymer Physics 1979, 8, 335.
10. Leary, D.; Williams, M. Journal of Polymer Science Part B: Polymer Physics 1973, 11, 345.
11. Leary, D.; Williams, M. Journal of Polymer Science Part B: Polymer Physics 1974, 12, 265.
12. Matsen, M. W.; Bates, F. S. Journal of Polymer Science Part B: Polymer Physics 1997, 35, 945.
13. Leibler, L. Macromolecules 1980, 13, 1602.
14. Kawasaki, K.; Ohta, T. Physical A 1986, 139, 223.
15. Vavasour, J. D.; Whitmore, M. D. Macromolecules 1992, 25, 5477.
16. Matsen, M. W.; Schick, M. Physical Review Letters 1994, 72, 2660.
17. Matsen, M. W.; Bates, F. S. Macromolecules 1996, 29, 1091.
18. Matsen, M. W.; Bates, F. S. Macromolecules 1996, 29, 7641.
19. Bates, F. S. Science 1991, 251, 898.
20. Fredrickson, H.; Bates, F. S. Annu. Rev. Mater. Sci. 1996, 26, 501.
21. Ikkala, O.; ten Brinke, G. Science 2002, 295, 2407.
22. Antonietti, M.; Conrad, J.; Thu¨nemann, A. Macromolecules 1994, 27,6007.
23. Ikkala, O.; Ruokolainen, J.; ten Brinke, G.; Torkkeli, M.; Serimaa, R. Macromolecules 1995, 28, 7088.
24. Ruokolainen, J.; ten Brinke, G.; Ikkala, O.; Torkkeli, M.; Serimaa, R. Macromolecules 1996, 29, 3409.
25. ten Brinke, G.; Ikkala, O. Trends Polym. Sci. 1997, 5, 213.
26. Ikkala, O.; Knaapila, M.; Ruokolainen, J.; Torkkeli, M.; Serimaa, R.; Jokela, K.; Horsburgh, L.; Monkman, A.; ten Brinke, G. AdV. Mater.1999, 11, 1206.
27. Chen, H. L.; Hsiao, M. S. Macromolecules 1999, 32, 2967.
28. Ruokolainen, J.; Eerikainen, H.; Torkkeli, M.; Serimaa, R.; Jussila, M.; Ikkala, O. Macromolecules 2000, 33, 9272.
29. Hartikainen, J.; Lahtinen, M.; Torkkeli, M.; Serimaa, R.; Valkonen, J.; Rissanen, K.; Ikkala, O. Macromolecules 2001, 34, 7789.
30. Kato, T.; Mizoshita, N.; Kanei, K. Macrol. Rapid Commun. 2001, 22, 797.
31. Ruokolainen, J.; Saariaho, M.; Ikkala, O.; ten Brinke, G.; Thomas, E. L.; Torkkeli, M.; Serimaa, R. Macromolecules 1999, 32, 1152.
32. Ruokolainen, J.; ten Brinke, G.; Ikkala, O. Adv. Mater. 1999, 11, 777.
33. Ruotsalainen, T.; Torkkeli, M.; Serimaa, R.; Ma¨kela¨, T.; Ma¨ki- Ontto, R.; Ruokolainen, J.; ten Brinke, G.; Ikkala, O. Macromolecules 2003, 36, 9437.
34. Polushkin, E.; Alberda van Ekenstein, G.; Dolbnya, I.; Bras, W.; Ikkala, O.; ten Brinke, G. Macromolecules 2003, 36, 1421.
35. Alberda van Ekenstein, G.; Polushkin, E.; Nijland, H.; Ikkala, O.; ten Brinke, G. Macromolecules 2003, 36, 3684.
36. Valkama, S.; Ruotsalainen, T.; Kosonen, H.; Ruokolainen, J.; Torkkeli, M.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Macromolecules 2003, 36, 3986.
37. Kosonen, H.; Valkama, S.; Ruokolainen, J.; Torkkeli, M.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Eur. Phys. J. E 2003, 10, 69.
38. Valkama, S.; Kosonen, H.; Ruokolainen, J.; Haatainen, T.; Torkkeli, M.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Nat. Mater. 2004, 3, 872.
39. Ikkala, O.; ten Brinke, G. Chem. Commun. 2004, 19, 2131.
40. Bondzic, S.; de Wit, J.; Polushkin, E.; Schouten, A. J.; ten Brinke, G.; Ruokolainen, J.; Ikkala, O.; Dolbnya, I.; Bras, W. Macromolecules 2004, 37, 9517.
41. Tsao, C.-S.; Chen, H.-L. Macromolecules 2004, 37, 8984.
42. ten Brinke, G.; Ikkala, O. Chem. Rec. 2004, 4, 219.
43. Polushkin, E.; Bondzic, S.; de Wit, J.; Alberda van Ekenstein, G.; Dolbnya, I.; Bras, W.; Ikkala, O.; ten Brinke, Macromolecules 2005, 38, 1804.
44. Valkama, S.; Ruotsalainen, T.; Nykanen, A.; Laiho, A.; Kosonen, H.; ten Brinke, G.; Ikkala, O.; Ruokolainen, J. Macromolecules 2006, 39, 9327−9336.
45. Chen, H. L.; Lu, J. S.; Yu, C. H.; Yeh, C. L.; Jeng, U. S.; Chen, W. C. Macromolecules 2007, 40, 3271.
46. Chiang, W. S.; Lin, C. H.; Yeh, C. L.; Nandan, B.; Hsu, P. N.; Lin, C. W.; Chen, H. L.; Chen, W. C. Macromolecules 2009, 42, 2304.
47. Zielinski, J. M.; Spontak, R. J. Macromolecules 1992, 25, 653.
48. Matsen, M. W.; Schick, M. Macromolecules 1994, 27, 7157.
49. Nandan, B.; Lee, C.-H.; Chen, H.-L.; Chen, W.-C. Macromolecules 2005, 38, 10117.
50. Nandan, B.; Lee, C.-H.; Chen, H.-L.; Chen, W.-C. Macromolecules 2006, 39, 4460.
51. Matsen, M. W. Macromolecule 2012, 45, 2161.
52. Spontak, R. J., Zielinski, J. M. and Lipscomb, G. G. Macromolecules 1992, 25, 6270