Small-molecule probe diffusion in polymer solutions: Studies by Taylor dispersion and phosphorescence quenching

Macromolecules

Volumn 29, Issue 19, 1996, Pages 6193-6207

  Wisnudel, Marc B ^a   Torkelson, John M ^a  

^a Northwestern University   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ASPECT RATIO; DIFFUSION; PHOSPHORESCENCE; POLYSTYRENES; PROBES; QUENCHING; SOLUTIONS; THERMAL EFFECTS; VOLUME FRACTION;

MODIFIED VRENTAS-DUDA FREE VOLUME THEORY; MOLAR VOLUME; TAYLOR DISPERSION; TETRAHYDROFURAN;

POLYMERS;

EID: 0030576750     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma960635b     Document Type: Article

References (111)

1. Frick, T. S.; Huang, W. J.; Tirrell, M.; Lodge, T. P. J. Polym. Sci., Polym. Phys. Ed. 1990, 28, 2629.
2. Lodge, T. P.; Lee, J. A.; Frick, T. S. J. Polym. Sci., Polym. Phys. Ed. 1990, 28, 2607.
3. Goffloo, K.; Kosfeld, R. Angew. Makromol. Chem. 1974, 37, 105.
4. Kosfeld, R.; Goffloo, K. Kolloid Z. Z. Polym. 1971, 247, 801.
5. Pickup, S.; Blum, F. D. Macromolecules 1989, 22, 3961.
6. Duda, J. L. Pure Appl. Chem. 1985, 57, 1681.
7. Vrentas, J. S.; Duda, J. L. J. Polym. Sci., Polym. Phys. Ed. 1977, 15, 403.
8. Vrentas, J. S.; Duda, J. L. J. Polym. Sci., Polym. Phys. Ed. 1977, 15, 417.
9. Duda, J. L.; Vrentas, J. S.; Ju, S. T.; Liu H. T. AIChE J. 1982, 28, 279.
10. Faldi, A.; Tirrell, M.; Lodge, T. P.; von Meerwall, E. Macromolecules 1994, 27, 4184.
11. Faldi, A.; Tirrell, M.; Lodge, T. P. Macromolecules 1994, 27, 4176.
12. Achillas, D, S.; Kiparissides, C. Macromolecules 1992, 25, 3739.
13. Cardenas, J. N.; O'Driscoll, K. F. J. Polym. Sci., Polym. Chem. Ed. 1976, 14, 883.
14. Hamielec, A. E. Chem. Eng. Commun. 1983, 24, 1.
15. Horie, K.; Mita, I.; Kambe, H. J. Polym. Sci., Polym. Chem. Ed. 1968, 6, 2663.
16. Ito, K. J. Polym. Sci., Polym. Chem. Ed. 1969, 7, 2995.
17. Scheren, P. A. G. M.; Russell, G. T.; Sangster, D. F.; Gilbert, R. G.; German, A.L. Macromolecules 1995, 28, 3637.
18. Vivaldo-Lima, E.; Hamielec, A. E.; Wood, P. E. Polym. React. Eng. 1994, 2, 17.
19. Wisnudel, M. B.; Torkelson, J. M. Macromolecules 1994, 27, 7217.
20. Harland, R. S.; Peppas, N. A. J. Pharm. Sci. 1989, 78, 146.
21. Korsmeyer, R. W.; von Meerwall, E. D.; Peppas, N. A. J. Polym. Sci., Polym. Phys. Ed. 1986, 24, 409.
22. Saltzman, W. M.; Pasternak, S. H.; Langer, R. ACS Symp. Ser. 1987, 348, 15.
23. Waggoner, R. A.; Blum, F. D. J. Coatings Technol. 1989, 61, 51.
24. Koros, W. J. ACS Symp. Ser. 1990, 423, 1.
25. Sakai, K. J. Membr. Sci. 1994, 96, 91.
26. Peppas, N. A.; Wu, J. C.; von Meerwall, E. D. Macromolecules 1994, 27, 5626.
27. Zielinski, J. M.; Duda, J. L. AIChE J. 1992, 38, 405.
28. Ilyina, E.; Sillescu, H. Polymer 1995, 36, 137.
29. von Meerwall, E. D. Adv. Polym. Sci. 1983, 54, 1.
30. von Meerwall, E. D.; Amelar, S.; Smeltzly, M. A.; Lodge, T. P. Macromolecules 1989, 22, 295.
31. Bello, M. S.; Rezzonico, R.; Righetti, P. G. Science 1994, 266, 773.
32. Al-Naafa, M. A.; Selim, M. S. AIChE J. 1994, 40, 1412.
33. Burkey, T. J.; Griller, D.; Lindsay, D. A.; Scaiano, J. C. J. Am. Chem. Soc. 1984, 706, 1983.
34. Huggenberger, C.; Lipscher, J.; Fischer, H. J. Phys. Chem. 1980, 84, 3467.
35. Metaxiotou, Z. A.; Nychas, S. G. AIChE J. 1995, 41, 812.
36. Guo, C. J.; De Kee, D.; Harrison, B. J. Appl. Polym. Sci. 1995, 56, 817; 1995, 56, 823.
37. Guo, C. J.; De Kee, D.; Harrison, B. J. Appl. Polym. Sci. 1995, 56, 817; 1995, 56, 823.
38. Fujita, H. Fortschr. Hochpolym.-Forsch. 1961, 3, 1.
39. Navari, R. M.; Hall, K. R.; Gainer, J. L. AIChE J. 1971, 17, 1028.
40. Vrentas, J. S.; Duda, J. L.; Ling, H. C. J. Polym Sci., Polym. Phys. Ed. 1985, 23, 275.
41. MacElroy, J. M. D.; Kelly, J. J. AIChE J. 1985, 31, 35.
42. Waggoner, R. A.; Blum, F. D.; MacElroy, J. M. D. Macromolecules 1993, 26, 6841.
43. Glasstone, S.; Laidler, K. J.; Eyring, H. The Theory of Rate Processes; McGraw-Hill: New York, 1941.
44. Gainer, J. L. Ind. Eng. Chem. Res. 1994, 33, 2341.
45. Mackie, J. S.; Meares, P. Proc. R. Soc. London, A 1955, 232, 498.
46. Maxwell, J. C. A Treatise on Electricity and Magnetism; Clarendon Press: Oxford, U.K., 1881.
47. Fricke, H. Phys. Rev. 1924, 24, 575.
48. Taylor, G. Proc. R. Soc. London, A 1953, 219, 186.
49. Taylor, G. Proc. R. Soc. London, A 1954, 225, 473.
50. Aris, R. Proc. R. Soc. London, A 1956, 235, 67.
51. Ouano, A. C. Ind. Eng. Chem. 1972, 11, 268.
52. Pratt, K. C.; Wakeham, W. A. Proc. R. Soc. London, A 1974, 336, 393.
53. Grushka, E.; Kikta, E. J., Jr. J. Phys. Chem. 1974, 78, 2297.
54. Alizadeh, A.; Nieto de Castro, C. A.; Wakeham, W. A. Int. J. Thermophys. 1980, 1, 243.
55. Wisnudel, M. B.; Torkelson, J. M. AIChE J. 1996, 42, 1157.
56. Vartuli, M.; Hulin, J. P.; Daccord, G. AIChE J. 1995, 47, 1622.
57. Yu, D. H. S.; Torkelson, J. M. Macromolecules 1988, 21, 1033.
58. Wisnudel, M. B.; Torkelson, J. M. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1993, 34 (2), 500.
59. Birks, J. B. Organic Molecular Photophysics; Wiley: New York, 1975.
60. Gebert, M. S.; Yu, D. H. S.; Torkelson, J. M. Macromolecules 1992, 25, 4160.
61. Ferguson, R. D.; von Meerwall, E. J. Polym. Sci., Polym. Phys. Ed. 1980, 18, 1285.
62. Cohen, M. H.; Turnbull, D. J. Chem. Phys. 1959, 31, 1164.
63. Arnould, D.; Laurence, R. L. Ind. Eng. Chem. Res. 1992, 31, 218.
64. Vrentas, J. S.; Vrentas, C. M.; Faridi, N. Macromolecules 1996, 29, 3272.
65. von Meerwall, E. D.; Amis, E. J.; Ferry, J. D. Macromolecules 1985, 18, 260.
66. Huang, W. J.; Frick, T. S.; Landry, M. R.; Lee, J. A.; Lodge, T. P.; Tirrell, M. AIChE J. 1987, 33, 573.
67. Landry, M. R.; Gu, Q.; Yu, H. Macromolecules 1988, 21, 1158.
68. D, the apparent activation energy for diffusion.
69. Gisser, D. J.; Johnson, B. S.; Ediger, M. D.; von Meerwall, E. D. Macromolecules 1993, 26, 512.
70. Johnson, B. S.; Ediger, M. D.; Yamaguchi, Y.; Matsushita, Y.; Noda, I. Polymer 1992, 33, 3916.
71. Inoue T.; Cicerone, M. T.; Ediger, M. D. Macromolecules 1995, 28, 3425.
72. Wesson, J. A.; Noh, I.; Kitano, T.; Yu, H. Macromolecules 1984, 17, 782.
73. Nemoto, N.; Landry, M. R.; Noh, I.; Kitano, T.; Wesson, J. A.; Yu, H. Macromolecules 1985, 18, 308.
74. Amis, E. J.; Han, C. C. Polymer 1982, 23, 1403.
75. Gebert, M. S.; Torkelson, J. M. Polymer 1990, 31, 2402.
76. Pratt K. C.; Wakeham, W. A. Proc. R. Soc. London, A 1975, 342, 401.
77. Janssen, L. A. M. Chem. Eng. Sci. 1976, 31, 215.
78. Wisnudel, M. B. Ph.D. Thesis, Northwestern University, Evanston, IL, 1996.
79. Reid R. C.; Prausnitz, J. M.; Poling, B. E. The Properties of Gases and Liquids; McGraw Hill: New York, 1987.
80. Haward, R. N. J. Macromol. Sci., Rev. Macromol. Chem. 1970, C42, 191.
81. Wilke, C. R.; Chang, P. AIChE J. 1955, 1, 264.
82. von Meerwall, E.; Skowronski, D.; Hariharan, A. Macromolecules 1991, 24, 2441.
83. Ehlich, D.; Sillescu, H. Macromolecules 1990, 23, 1600.
84. Berry, G. C.; Fox, T. G. Adv. Polym. Sci. 1968, 5, 261.
85. Vrentas, J. S.; Duda, J. L.; Ling, H. C. J. Polym. Sci., Polym. Phys. Ed. 1984, 22, 459.
86. probe in the limit of zero polymer concentration. Solvent diffusion data have reportedly deviated from free volume theory at extremely high solvent concentrations when Fujita free volume theory was fit to diffusivities in polyisobutylene-benzene (Boss, B. D.; Stejskal, E. O.; Ferry, J. D. J. Phys. Chem. 1967, 71, 1501) and oil - Natsyn (von Meerwall, E. D.; Ferguson, R. D. J. Appl. Polym. Sci. 1979, 23, 877) systems over very broad ranges of concentration (from 0 to ≥ 0.7 volume fraction polymer). An extra increase in diffusivity unrelated to free volume in dilute solution might be expected on the basis of a hypothesis by Cohen and Turnbull (ref 61) that the diffusivity of a molecule in dilute solution might be higher due to motion of the cage (cooperativity between polymer and solvent) than if the cage were fixed (polymer-fixed reference frame). Also see ref 60. Based on these hydrodynamic considerations, one might expect a transition in diffusivity near the polymer overlap concentration that no free volume theory could adequately describe. We do not observe such a disparity between Vrentas-Duda theory and our data, although additional measurements below 100 g/L polymer concentration would need to be made in order to reach a more definitive conclusion. Furthermore, comparisons of Fujita free volume theory to the data should be re-evaluated in consideration of recent improvements to the theory (Fujita, H. Macromolecules 1993, 26, 643).
87. probe in the limit of zero polymer concentration. Solvent diffusion data have reportedly deviated from free volume theory at extremely high solvent concentrations when Fujita free volume theory was fit to diffusivities in polyisobutylene-benzene (Boss, B. D.; Stejskal, E. O.; Ferry, J. D. J. Phys. Chem. 1967, 71, 1501) and oil - Natsyn (von Meerwall, E. D.; Ferguson, R. D. J. Appl. Polym. Sci. 1979, 23, 877) systems over very broad ranges of concentration (from 0 to ≥ 0.7 volume fraction polymer). An extra increase in diffusivity unrelated to free volume in dilute solution might be expected on the basis of a hypothesis by Cohen and Turnbull (ref 61) that the diffusivity of a molecule in dilute solution might be higher due to motion of the cage (cooperativity between polymer and solvent) than if the cage were fixed (polymer-fixed reference frame). Also see ref 60. Based on these hydrodynamic considerations, one might expect a transition in diffusivity near the polymer overlap concentration that no free volume theory could adequately describe. We do not observe such a disparity between Vrentas-Duda theory and our data, although additional measurements below 100 g/L polymer concentration would need to be made in order to reach a more definitive conclusion. Furthermore, comparisons of Fujita free volume theory to the data should be re-evaluated in consideration of recent improvements to the theory (Fujita, H. Macromolecules 1993, 26, 643).
88. probe in the limit of zero polymer concentration. Solvent diffusion data have reportedly deviated from free volume theory at extremely high solvent concentrations when Fujita free volume theory was fit to diffusivities in polyisobutylene-benzene (Boss, B. D.; Stejskal, E. O.; Ferry, J. D. J. Phys. Chem. 1967, 71, 1501) and oil - Natsyn (von Meerwall, E. D.; Ferguson, R. D. J. Appl. Polym. Sci. 1979, 23, 877) systems over very broad ranges of concentration (from 0 to ≥ 0.7 volume fraction polymer). An extra increase in diffusivity unrelated to free volume in dilute solution might be expected on the basis of a hypothesis by Cohen and Turnbull (ref 61) that the diffusivity of a molecule in dilute solution might be higher due to motion of the cage (cooperativity between polymer and solvent) than if the cage were fixed (polymer-fixed reference frame). Also see ref 60. Based on these hydrodynamic considerations, one might expect a transition in diffusivity near the polymer overlap concentration that no free volume theory could adequately describe. We do not observe such a disparity between Vrentas-Duda theory and our data, although additional measurements below 100 g/L polymer concentration would need to be made in order to reach a more definitive conclusion. Furthermore, comparisons of Fujita free volume theory to the data should be re-evaluated in consideration of recent improvements to the theory (Fujita, H. Macromolecules 1993, 26, 643).
89. Mauritz, K. A.; Storey, R. F.; George, S. E. Macromolecules 1990, 23, 441.
90. Mauritz, K. A.; Storey, R. F. Macromolecules 1990, 23, 2033.
91. Zielinski, J. M.; Duda, J. L. J. Polym. Sci., Polym. Phys. Ed. 1992, 30, 1081.
92. Vrentas, J. S.; Duda, J. L.; Liu, H. T. J. Appl. Polym. Sci. 1980, 25, 1793.
93. Deppe, D. D.; Dhinojwala, A.; Torkelson, J. M. Macromolecules 1996, 29, 3898.
94. Deppe, D. D.; Miller, R. D.; Torkelson, J. M., J. Polym. Sci., Polym. Phys. Ed., in press.
95. Deppe, D. D.; Torkelson, J. M. Polym. Mater. Sci. Eng. 1995, 73, 338.
96. Cicerone, M. T.; Blackburn, F. R.; Ediger, M. D. Macromolecules 1995, 28, 8224.
97. Hadj Romdhane, I.; Danner, R. P.; Duda, J. L. Ind. Eng. Chem. Res. 1995, 34, 2833.
98. probe,p = 1-00.
99. Mita, I.; Horie, K. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 1987, C27, 91.
100. Richtol, H. H.; Klappmeier, F. H. J. Chem. Phys. 1966, 44, 1519.
101. To our knowledge, phosphorescence of 3,4-hexanedione has not been reported elsewhere.
102. Gouterman, M. The Porphyrins, III; Academic: New York, 1978.
103. Khalil, G.-E.; Gouterman, M.; Green, E. U.S. Patent No. 4,810,655, 1989.
104. Donkerbroek, J. J.; Elzas, J. J.; Frei, R. W.; Veithorst, N. H. Talanta 1981, 28, 717.
105. Won, J.; Onyenemezu, C.; Miller, W. G.; Lodge, T. P. Macromolecules 1994, 27, 7389.
106. Vrentas, J. S.; von Meerwall, E.; Drake, M. C.; Chu, C. H. J. Polym. Sci., Polym. Phys. Ed. 1989, 27, 1179.
107. Blum, F. D.; Pickup, S.; Foster, K. R. J. Colloid Interface Sci. 1986, 113, 336.
108. Cohen and Turnbull (ref 61) state that "if the impurity molecule (probe) is smaller than the solvent molecule ..., it will diffuse at the same rate as the solvent since the diffusive transport is completed only by the jumping of a neighboring solvent molecule into the void."
109. probe,s was determined.
110. Lee, J. A.; Lodge, T. P. J. Phys. Chem. 1987, 91, 5546.
111. probe,s which is too large to allow inclusion in Figure 12. Since probe-polymer interactions complicate studies of probe diffusion in solution, they were avoided in this study as much as possible. We are unaware of any interactions between the probes of Figure 1 and polystyrene that may have led to anomalous diffusion. Furthermore, phosphorescence quenching interactions involving two of the probes, anthracene and benzil, in another study (ref 56) were well-behaved in a number of polymer solutions including polystyrene, poly(methyl methacrylate), and poly butadiene.