Anthracene-functionalized polystyrene random copolymers: Effects of side-chain modification on polymer structure and behavior

Macromolecules

Volumn 37, Issue 1, 2004, Pages 92-98

  Shenhar, Roy ^a   Sanyal, Amitav ^a   Uzun, Oktay ^a   Rotello, Vincent M ^a  

^a UNIVERSITY OF MASSACHUSETTS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACIDS; COPOLYMERIZATION; ESTERS; GLASS TRANSITION; PHASE SEPARATION; POLYSTYRENES; STYRENE; TEMPERATURE;

ANTHRACENE; ANTHRACENECARBOXYLIC ACID; CHAIN PACKING DENSITY; CHLOROMETHYLSTYRENE; MICROPHASE SEPARATION; SIDE CHAIN FUNCTIONALITY;

BLOCK COPOLYMERS;

EID: 1642578121     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma035488d     Document Type: Article

References (57)

1. Decher, G. Science 1997, 277, 1232.
2. Onitsuka, O.; Fou, A. C.; Ferreira, M.; Hsieh, B. R.; Rubner, M. F. J. Appl. Phys. 1996, 80, 4067.
3. Donath, E.; Sukhorukov, G. B.; Caruso, F.; Davis, S. A.; Möwald, H. Angew. Chem., Int. Ed. 1998, 37, 2202.
4. Boal, A. K.; Ilhan, F.; DeRouchey, J. E.; Thurn-Albrecht, T.; Russell, T. P.; Rotello, V. M. Nature (London) 2000, 404, 746.
5. Das, K.; Penelle, J.; Rotello, V. M. Langmuir 2003, 19, 3921.
6. Duffy, D. J.; Das, K.; Hsu, S. L.; Penelle, J.; Rotello, V. M.; Stidham, H. D. J. Am. Chem. Soc. 2002, 124, 8290.
7. Tripp, J. A.; Stein, J. A.; Svec, F.; Frechet, J. M. J. Org. Lett. 2000, 2, 195.
8. Tripp J. A.; Svec, F.; Frechet, J. M. J. J. Comb. Chem. 2001, 3, 216.
9. Wang, J.; Kara, S.; Long, T. E.; Ward, T. C. J. Polym. Sci., Polym. Chem. 2000, 38, 3742.
10. Thurn-Albrecht, T.; Schotter, J.; Kästle, C. A.; Emley, N.; Shibauchi, T.; Krusin-Elbaum, L.; Guarini, K.; Black, C. T.; Tuominen, M. T.; Russell, T. P. Science 2000, 290, 2126.
11. Chan, V. Z.-H.; Hoffman, J.; Lee, V. Y.; Iatrou, H.; Avgeropoulos, A.; Hadjichristidis, N.; Miller, R. D.; Thomas, E. L. Science 1999, 286, 1716.
12. Park, M.; Harrison, C.; Chaikin, P. M.; Register, R. A.; Adamson, D. H. Science 1997, 276, 1401.
13. Bendejacq, D.; Ponsinet, V.; Joanicot, M.; Vacher, A.; Airiau, M. Macromolecules 2003, 36, 7289.
14. Ruokolainen, J.; Mäkinen, R.; Torkkeli, M.; Mäkelä, T.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Science 1998, 280, 557.
15. Ikkala, O.; ten Brinke, G. Science 2002, 295, 2407.
16. The effect of an atom substitution on the phase behavior of polymers was investigated in blends. Jablonski, E. L.; Gorga, R. E.; Narasimhan, B. Polymer 2003, 44, 729.
17. Gorga, R. E.; Jablonski, E. L.; Thiyagarajan, P.; Seifert, S.; Narasimhan, B. J. Polym. Sci., Part B: Polym. Phys. 2002, 40, 255.
18. Alberda, G. O. R.; Meyboom, R.; ten Brinke, G.; Ikkala, O. Macromolecules 2000, 33, 3752.
19. Oudhuis, A. A. C. M.; ten Brinke, G.; Karasz, F. E. Polymer 1993, 34, 1991.
20. Salomons, W.; ten Brinke, G.; Karasz, F. E. Polym. Commun. 1991, 32, 185.
21. Ring-opening metathesis polymerization (ROMP) provides an exception in the sense that it is relatively tolerant to a wide variety of preexisting monomer functionality. Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100.
22. Lynn, D. M.; Kanaoka, S.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 784.
23. Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503.
24. Hillmyer, M. A.; Laredo, W. R.; Grubbs, R. H. Macromolecules 1995, 28, 6311.
25. Stumpf, A. W.; Saive, E.; Demonceau, A.; Noels, A. F. J. Chem. Soc., Chem. Commun. 1995, 1127.
26. Fraser, C.; Grubbs, R. H. Macromolecules 1995, 28, 7248.
27. Lee, H. J.; Nakayama, Y.; Matsuda, T. Macromolecules 1999, 32, 6989.
28. Worl, L. A.; Jones, W. E., Jr.; Strouse, G. F.; Younathan, J. N.; Danielson, E.; Maxwell, K. A.; Sykora, M.; Meyer, T. J. Inorg. Chem. 1999, 38, 2705.
29. Park, Y. H.; Shin, H. C.; Lee, Y.; Son, Y.; Baik, D. H. Macromolecules 1999, 32, 4615.
30. Dependent on the functionality, at high CMS:S ratios some processing parameters such as solubility and the ability to achieve complete postpolymerization functionalization become problematic.
31. Benoit, D.; Chaplinski, V.; Braslau, R.; Hawker, C. J. J. Am. Chem. Soc. 1999, 121, 3904.
32. Harth, E.; Hawker, C. J.; Fan, W.; Waymouth, R. M. Macromolecules 2001, 34, 3856.
33. Hawker, C. J. J. Am. Chem. Soc. 1994, 116, 11185.
34. Ilhan, F.; Gray, M.; Blanchette, K.; Rotello, V. M. Macromolecules 1999, 32, 6159.
35. Polymer Handbook, 4th ed.; Brandrup, J., Immergut, E. H., Grulke, E. A., Eds.; Wiley-Interscience Publication: New York, 1999.
36. Van Krevelen, D. W. Properties of Polymers: Their Correlation with Chemical Structure; Their Numerical Estimation and Prediction from Additive Group Contributions, 3rd ed; Elsevier: Amsterdam, 1990.
37. Bicerano, J. Prediction of Polymer Properties, 3rd ed.; Marcel Dekker: New York, 2002.
38. 19 We find that within this range the variation of our quantitative results is marginal (e.g., volume fractions vary by about 1%).
39. In general, we refrained from casting the samples from solution to avoid kinetic entrapment effects caused by selectivity of the solvent to either block. Nevertheless, we note that annealed samples cast from toluene still exhibited the same SAXS characteristics as those annealed from the powder form, which therefore leads us to believe that the investigated melts were in equilibrium.
40. Physical Properties of Polymers Handbook; Mark, J. E. Ed.; American Institute of Physics: Woodbury, NY, 1996.
41. In these calculations we neglected the difference between CMS and styrene. Calculated volume fractions of the Anth functionality in PS/S-Anth/CMS (19, 7%, 13%) and (19, 12%, 8%) are 0.16 and 0.26, respectively. For data pertaining to the fully converted PS/S-Anth (19, 20%) and (25, 50%) see Table 2.
42. Mitchell, G. R.; Windle, A. H. Polymer 1984, 25, 906.
43. Strobl, G. The Physics of Polymers; Springer: Berlin, 1996.
44. Fredrickson, G. H.; Bates, F. S. Annu. Rev. Mater. Sci. 1996, 26, 501.
45. Bates, F. S.; Fredrickson, G. H. Annu. Rev. Phys. Chem. 1990, 41, 525.
46. Leibler, L. Macromolecules 1980, 13, 1602.
47. 2I vs q (instead of I vs q) under the assumption that the polymers feature lamellar morphology, based on the range of calculated volume fractions of the functionalized blocks (0.36-0.55) and mean-field theory.
48. This situation does not result from lack of electron density contrast that may arise from a small number of Anth functionalities in the PS/S-Anth (27: 13, 17%) polymer; other polymers that feature the same low functionality content but longer functionalized blocks (with up to twice the total number of Anth units per polymer) do not exhibit a distinct SAXS peak as well.
49. func-PS = 0.40), as in perfectly symmetric diblock copolymers it is completely absent.
50. Fedors, R. F. Polym. Eng. Sci. 1974, 14, 147.
51. Fedors, R. F. Polym. Eng. Sci. 1974, 14, 472.
52. For consistency, all the variables appearing in eqs 2 and 3 were also evaluated using the topological indices.
53. Semenov, A. N. Sov. Phys. JETP 1985, 61, 733.
54. For a detailed discussion and references, see: Ren, Y.; Lodge, T. P.; Hillmyer, M. A. Macromolecules 2000, 33, 866
55. Ren, Y.; Lodge, T. P.; Hillmyer, M. A. Macromolecules 2002, 35, 3889.
56. All precursors to polymers of series B were synthesized from the same batch of PS block, with exactly the same styrene/CMS mixture composition (i.e., comonomer quantities); thus, the differences between the functionalized blocks of these polymers resulted only from different polymerization times.
57. Despite the lack of secondary scattering peaks in the SAXS curves of the polymers of series B, we consider the melts of these polymers, quenched from 150 °C, as phase-separated, since only weak dependence of the scattering behavior on annealing temperature or annealing scheme was observed. For example, annealing at 150 °C for a few hours, then at 125 °C for 2 days, and then slowly cooling the samples to room temperature did not result in a significant change in the principal peak location/width or appearance of secondary scattering peaks. Therefore, the absence of secondary secondary scattering peaks is attributed to weak segregation (and possibly also to low electron density contrast) rather than to disorder.