Porogen and cross-linking effects on the surface area, pore volume distribution, and morphology of macroporous polymers obtained by bulk polymerization 3

Macromolecules

Volumn 34, Issue 3, 2001, Pages 658-661

  Santora, Brian P ^a,b   Gagné, Michel R ^a,b   Moloyt, Kenneth G ^a,b   Radu, Nora S ^a,b  

^a University of North Carolina at Chapel Hill   (United States)

^b DUPONT COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BULK POLYMERIZATION; MACROPOROUS POLYMERS; POROGENS;

CROSSLINKING; FREE RADICAL POLYMERIZATION; ION EXCHANGE RESINS; MORPHOLOGY; ORGANIC SOLVENTS; PORE SIZE; POROUS MATERIALS; SCANNING ELECTRON MICROSCOPY;

RESINS;

EID: 0035111730     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma0004817     Document Type: Article

References (34)

1. This work was carried out by BPS while an industrial intern at DuPont.
2. Abrams, I. M.; Millar, J. R. React. Funct. Polytn. 1997, 35, 7-22 and references therein.
3. For a general review of cross-linked polymer supports, see: Sherrington, D. G. Chem. Commun. 1998, 2275-2286.
4. For example, see: (a) Nozaki, K.; Itoi, Y.; Shibahara, F.; Shirakawa, E.; Ohta, T.; Takaya, H.; Hiyama, T. J. Am. Chem. Soc. 1998, 120, 4051-4052.
5. (b) Nozaki, K.; Shibahara, F.; Itoi, Y.; Shirakawa, E.; Ohta, T.; Takaya, H.; Hiyama, T. Bull. Chem. Soc. Jpn. 1999, 72, 1911-1918.
6. Santora, B. P.; Larsen, A. 0.; Gagné, M. R. Organometallics 1998, 17, 3138-3140.
7. Santora, B. P.; White, P. S.; Gagné, M. R. Organometallics 1999, 18, 2557-2560.
8. (e) Taylor, R. A.; Santora, B. P.; Gagné, M. R. Org. Lett. 2000, 2, 17811783.
9. (f) Polborn, K; Severin, K. Chem. Commun. 1999, 2481-2482.
10. (g) Canali, L.; Sherrington, D. C. Chem. Soc. Reu. 1999, 28, 85-93, and references therein,
11. (h) Salvadori, P.; Fini, D.; Pétri, A. J. Am. Chem. Soc. 1997, 119, 69296930, and references therein,
12. Matsui, J.; Nichols, I. A.; Karube, L; Mosbach, K J. Org. Chem. 1996, 61, 5414-5417.
13. Millar, J. R.; Smith, D. G.; Marr, W. E.; Kressman, T. R. E. J. Chem. Soc. 1963, 218-225.
14. As pointed out by a referee, some of the reasons for this might include the fact that monomer droplets in suspension polymerization are water-saturated and are highly agitated. The latter might act to reduce the number of entanglement cross-links and affect the onset of phase separation.
15. Svec, F.; Fréchet, J. M. J. Chem. Mater. 1995, 7, 707-715
16. (b) Viklund, G.; Svec, F.; Fréchet, J. M. J.; Irgum, K. Chem Mater. 1996, 8, 744-750.
17. For a series of polymer morphology studies of macroporous trimethylolpropane trimethacrylate .(TRIM) resins made under bulk polymerizations conditions, see: (a) Rosenberg, J. E.; Flodin, P. Macromolecules 1986, 19, 1543-1546.
18. (b) Rosenberg, J. E.; Flodin, P. Macromolecules 1987, 20, 15181522.
19. Rosenberg, J. E.; Flodin, P. Macromolecules 1987, 20, 1522-1526.
20. See for example: (a) Wulff, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1812-1813.
21. (b) Sellergen, B.; Shea, K. J. J. Chromatogr. 1993, 635, 31-49.
22. Wulff, G.ACS Symp. Ser. 1986, 308, 186-230.
23. Wulff, G.; Schauhoff, S. J. Org. Chem. 1991, 56, 395-400.
24. The true cross-link density is generally substantially lower than the feed ratio. See: Law, R. V.; Sherrington, D. C.; Snape, C. E.; Ando, L; Kuroso, H. Macromolecules 1996, 29, 6284-6293.
25. For similar results in porous polymer monoliths, see: Xie, S.; Svec, F.; Fréchet, J. M. J. Chem. Mater. 1998, 10, 40724078, and references therein.
26. For lucid descriptions of these phenomena in suspension and bulk polymerizations, see: footnote 3 and Viklund, C.; Svec, F.; Fréchet, J. M. J.; Irgum, K. Chem. Mater. 1996, 8, 744750.
27. Heptane (and benzyl alcohol) similarly lead to low surface areas (<1 m2/g) in TRIM resins.7b
28. For nitrogen adsorption measurements, pore size ranges become uncertain at the upper limit of the mesopore region: Cheng, C. E.; Micale, F. J.; Vanderhoff, J. W.; ElAasser, M. S. J. Colloid Interface Sei. 1992, 150, 549-558.
29. See the Supporting Information for a complete set of pore volume distribution plots.
30. For similar SEM images, see: (a) Footnote 8a. (b) Viklund, C.; Pontén, E.; Glad, B.; Irgum, K.; Hörstedt, P.; Svec, F. Chem. Mater. 1997, 9, 463-471.
31. Control experiments indicate that under these conditions the polymerization temperature did not have a large effect on the surface area of the resulting polymers.
32. For a DVB polymer morphology study addressing the length of polymerization, see: Nyhus, A. K.; Hagen, S.; Berge, A. J. Polym. Sei., Part A 1999, 37, 3973-3990.
33. Brunauer, S.; Emmett, P. H.; Teller, E. J. Am. Chem. Soc. 1938, 60, 309-319.
34. Barret, E. P.; Joyner, L. G.; Halenda, P. P. J. Am. Chem. Soc. 1951, 73, 373-380.