Caracterização Viscosimétrica de Nanocompósitos Híbridos PS/POSS
Viscometric Characterization of PS/POSS Hybrid Nanocomposites
Canto, Leonardo B.; Oliveira, Ricardo V. B.; Mauler, Raquel S.; Repenning, Gustavo B.; Bianchi, Otávio
http://dx.doi.org/10.1590/S0104-14282012005000022
Polímeros: Ciência e Tecnologia, vol.22, n2, p.125-133, 2012
Resumo
Nanocompósitos híbridos de poliestireno (PS) e poliedros oligoméricos silsesquioxanos (POSS) com diferentes composições e graus de hibridização foram obtidos por processamento reativo no estado fundido utilizando-se peróxido de dicumila (DCP) como iniciador, na presença ou não de estireno como agente de transferência de radical. Os materiais foram caracterizados viscosimetricamente por cromatografia de permeação em gel (GPC) usando detecção tripla por espalhamento de luz, viscosimetria e índice de refração. As amostras PS/POSS processadas com estireno apresentaram maiores valores de massa molar ponderal média (Mw) e menores valores de polidispersão (Mw/Mn), devido ao maior grau de conversão da reação de hibridização do PS-POSS (28-40%) e do menor grau de degradação (cisão) das cadeias do PS, quando comparadas com amostras PS/POSS processadas sem estireno nas quais o grau de conversão ficou em torno de 24-28%. Para os sistemas PS e PS/POSS em solução com THF, os parâmetros da equação de Mark-Houwink-Sakurada (MHS), α ≅ 0,7 e log K ≅ –3,5 a –3,9 e os valores dos parâmetros de interação polímero-solvente, χij ≅ 0,49, não apresentaram diferenças significativas com relação aos tamanhos moleculares. Por outro lado, essas diferenças de tamanhos moleculares foram caracterizadas por uma função cumulativa da fração mássica de cadeias em função da distância média quadrática entre pontas de cadeia ( 2 1/2 ) < r >0 .
Palavras-chave
PS, POSS, nanocompósitos híbridos, viscosimetria
Abstract
Polystyrene (PS) and polyhedral oligomeric silsesquioxanes (POSS) hybrid nanocomposites with different compositions were obtained by reactive melt processing using dicumyl peroxide (DCP) as initiator in the presence or absence of styrene as radical transfer agent. The materials were characterized by viscosimetry by means of gel permeation chromatography (GPC) using triple-detector: light scattering, viscometer and refractive index. PS/POSS samples processed with styrene showed higher weight average molecular weights (Mw) and lower polydispersity indexes (Mw/Mn), as a result of higher PS-POSS conversion (28-40%) and lower PS degradation, as compared to the PS/POSS samples processed without styrene in which the degree of conversion was lower (24-28%). For the PS/POSS solutions in THF, the parameters of the Mark-Houwink-Sakurada equation, α ≅ 0.7 and log K ≅ –3.5 to –3.9, and the values of polymer-solvent interaction parameter, χij ≅ 0.49, were not changed with respect to changes in molecular size. On the other hand, these changes were characterized by a cumulative function of the mass fraction of chains as a function of the root mean square end to end distance ( 2 1/2 ) < r >0 .
Keywords
PS, POSS, hybrid nanocomposites, viscosimetry
References
1. Baldi, F.; Bignotti, F.; Fina, A.; Tabuani, D. & Ricco, T. - J. Appl.
Polym. Sci., 105, p.935 (2007). http://dx.doi.org/10.1002/app.26142
2. Carniato, F.; Fina, A.; Tabuani, D. & Boccaleri, E. - Nanotechnology, 19, p.1 (2008).
3. Joshi, M.; Butola, B. S.; Simon, G. & Kukaleva, N. - Macromolecules, 39, p.1839 (2006). http://dx.doi.org/10.1021/ma051357w
4. Misra, R.; Alidedeoglu, A. H.; Jarrett, W. L. & Morgan, S. E. - Polymer, 50, p.2906 (2009). http://dx.doi.org/10.1016/j.polymer.2009.03.057
5. Pielichowski, K.; Njuguna, J.; Janowski, B. & Pielichowski, J. - “Polyhedral Oligomeric Silsesquioxanes (POSS) - containing nanohybrid polymers”, in: Supramolecular Polymers Polymeric Betains Oligomers, Springer-Verlag Berlin, Berlin (2006).
6. Janssen, L. P. B. - “Reactive Extrusion Systems”, Marcel Dekker, Inc., New York (2004). http://dx.doi.org/10.1201/9780203014172
7. Xanthos, M. - “Reactive Extrusion: Principles and Practice”, Hanser Publishers, Munich (1992).
8. Passaglia, E.; Coiai, S.; Ricci, L. & Ciardelli, F. - Macromol. Symp., 218 (2004).
9. Zhou, Z.; Cui, L.; Zhang, Y.; Zhang, Y. & Yin, N. - Eur. Polym. J., 44, p.3057 (2008). http://dx.doi.org/10.1016/j.eurpolymj.2008.05.036
10. Monticelli, O.; Fina, A.; Ullah, A. & Waghmare, P. - Macromolecules, 42, p.6614 (2009). http://dx.doi.org/10.1021/ma900969b
11. Passaglia, E.; Coiai, S. & Augier, S. - Prog. Polym. Sci., 34, p.911 (2009). http://dx.doi.org/10.1016/j.progpolymsci.2009.04.008
12. Greene, S. V. - “SEC with On-Line Triple Detection: Light Scattering,Viscometry, and Refractive Index”, in: Encyclopedia of Chromatography, J. Cazes (ed.), Marcel Dekker, Inc., New York (2002).
13. Jackson, C. & Barth, H. G. - “Molecular Weight Sensitive Detectors for Size Exclusion Chromatography”, in: Handbook of Size Exclusion Chromatography and Related Techniques Second Edition, Revised and Expanded, cap.22, C-S. Wu (ed.), New York (2004).
14. Kurata, M. & Tsunashima, Y. - “Viscosity - Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules”, in: Polymer Handbook, J. Brandup, E. H. Immergut, E. A. Grulke (eds.), John Wiley & Sons, New York (2003).
15. Ouano, A. C. – J. Polym. Sci. Part A-1: Polym. Chem., 10, p.2169 (1972). http://dx.doi.org/10.1002/pol.1972.150100727
16. Menges, M. & Schmidt-Naake, G. - Angew. Makromol. Chem., 258, p.51 (1998). http://dx.doi.org/10.1002/(SICI)1522- 9505(19980801)258:1%3C51::AID-APMC51%3E3.0.CO;2-T
17. Tribe, K.; Saunders, G. & Meißner, R. - Macromol. Symp., 236, p.228 (2006). http://dx.doi.org/10.1002/masy.200690059
18. Hong, L. Z. & Liu, G. J. - Macromolecules, 43, p.3941 (2010). http:// dx.doi.org/10.1021/ma100353t
19. Çatiker, E. & Güner, A. – Polym. Bul., 41, p.223 (1998).
20. Cecopieri-Gómez, M. L. & Palacios-Alquisira, J. - J. Braz. Chem. Soc., 16, p.426 (2005).
21. Lee, J. S.; Kim, S. C. & Lee, H. K. - Macromol. Res., 16, p.631 (2008). http://dx.doi.org/10.1007/BF03218572
22. Stockmayer, W. H. & Fixman, M. – J. Polym. Sci. Part C: Polym. Symp., 1, p.137 (1963).
23. Michielsen, S. - “Specific Refractive Index Increments of Polymers in Dilute Solution”, in: Polymer Handbook, J. Brandup, E. H. Immergut, E. A. Grulke (eds.), John Wiley & Sons, New York (2003).
24. Malawer, E. G. & Senak, L. - “Introduction to Size Exclusion Chromatography”, in: Handbook of Size Exclusion Chromatography and Related Techniques Second Edition, Revised and Expanded, cap.22, C-S. Wu (ed.), Marcel Dekker Inc., New York (2004).
25. Sun, S. F. - “Physical chemistry of macromolecules : basic principles and issues”, John Wiley & Sons, Hoboken (2004). http://dx.doi. org/10.1002/0471623571
26. Florea, M. - J. Chromatogr. A, 878, p.1 (2000). http://dx.doi. org/10.1016/S0021-9673(00)00265-X
27. Teraoka, I. - “Polymer Solution An Introdution to Physical Properties”, John Wiley & Sons, Inc., New York (2002).
28. Delpech, M. C.; Coutinho, F. M. B.; Sousa, K. G. M. & Cruz, R. C. - Polímeros, 17, p.294 (2007). http://dx.doi.org/10.1590/S0104- 14282007000400008
29. Wall, F. T. & Hiller, L. A. - Annu. Rev. Phys. Chem., 5, p.267 (1954). http://dx.doi.org/10.1146/annurev.pc.05.100154.001411
30. Flory, P. J. - “Principles of Polymer Chemistry”, Cornell University Press, Ithaca (1953).
31. Wypych, G. - “Handbook of Solvents”, Chem Tec Publishing, Toronto (2001).
32. Pyun, J. & Matyjaszewski, K. - Macromolecules, 33, p.217 (2000). http://dx.doi.org/10.1021/ma9910787
33. Hirai, T.; Leolukman, M.; Jin, S.; Goseki, R.; Ishida, Y.; Kakimoto, M.‑a.; Hayakawa, T.; Ree, M. & Gopalan, P. - Macromolecules, 42, p.8835 (2009). http://dx.doi.org/10.1021/ma9018944
34. Bevington, J. C. & Huckerby, T. N. – Eur. Polym. J., 42, p.1433 (2006). http://dx.doi.org/10.1016/j.eurpolymj.2005.12.011
35. Zhang, H-X.; Lee, H-Y.; Shin, Y-J.; Yoon, K-B.; Noh, S-K. & Lee, D-H. – Polym. Int., 57, p.1351 (2008). http://dx.doi.org/10.1002/pi.2480
36. Moad, G. - Prog. Polym. Sci., 24, p.81 (1999). http://dx.doi. org/10.1016/S0079-6700(98)00017-3
37. Denisov, E. T.; Denisova, T. G. & Pokidova, T. S. - “Handbook of free radical initiators”, John Wiley & Sons, Inc., Hoboken (2003). http:// dx.doi.org/10.1002/0471721476
38. Nachtigall, S. M. B.; Stedile, F. C.; Felix, A. H. O. & Mauler, R. S. - J. Appl. Polym. Sci., 72, p.1313 (1999). http://dx.doi. org/10.1002/(SICI)1097-4628(19990606)72:10%3C1313::AIDAPP11% 3E3.3.CO;2-4
39. Nachtigall, S. n. M. B.; Felix, A. H. O.; Ojeda, T. & Mauler, R. S. - Polímeros, 8, p.69 (1998). http://dx.doi.org/10.1590/S0104- 14281998000400010
40. Faravelli, T.; Pinciroli, M.; Pisano, F.; Bozzano, G.; Dente, M. & Ranzi, E. – J. Anal. Appl. Pyrol., 60, p.103 (2001). http://dx.doi. org/10.1016/S0165-2370(00)00159-5
41. Li, Y.; Xie, X.-M. & Guo, B.-H. - Polymer, 42, p.3419 (2001). http:// dx.doi.org/10.1016/S0032-3861(00)00767-9
42. Bettini, S. H. P. & Ruvolo, A. C. - J. Appl. Polym. Sci., 107, p.1430 (2008). http://dx.doi.org/10.1002/app.27201
43. Huber, K.; Bantle, S.; Lutz, P. & Burchard, W. - Macromolecules, 18, p.1461 (1985). http://dx.doi.org/10.1021/ma00149a017
44. Fujita, H. - Macromolecules, 21, p.179 (1988). http://dx.doi. org/10.1021/ma00179a036
45. Morris, R. L.; Amelar, S. & Lodge, T. P. – J. Chem. Phys., 89, p.6523 (1988). http://dx.doi.org/10.1063/1.455372
46. Von Meerwall, E. D.; Amelar, S.; Smeltzly, M. A. & Lodge, T. P. - Macromolecules, 22, p.295 (1989). http://dx.doi.org/10.1021/ ma00191a054
47. Levenberg, K. - Quart. Appl. Math. , 2, p.164 (1944).
48. Marquardt, D. W. - J. Soc. Ind. Appl. Math., 11, p.431 (1963). http:// dx.doi.org/10.1137/0111030
49. Wagner, H. L. - J. Phys. Chem. Ref. Data, 14, p.1101 (1985). http:// dx.doi.org/10.1063/1.555740
50. Weber, V.; Duval, M.; Ederlé, Y. & Mathis, C. - Carbon, 36, p.839 (1998). http://dx.doi.org/10.1016/S0008-6223(98)00015-3
51. Orwoll, R. A. & Arnold, P. A. - “Polymer - Solvent Interaction Parameter c”, in: Physical Properties of Polymers Handbook, J. E. Mark (ed.), Springer, New York (2007).
52. Spyriouni, T.; Tzoumanekas, C.; Theodorou, D.; Muller-Plathe, F. & Milano, G. - Macromolecules, 40, p.3876 (2007). http://dx.doi. org/10.1021/ma0700983
53. Terao, K.; Hokajo, T.; Nakamura, Y. & Norisuye, T. - Macromolecules, 32, p.3690 (1999). http://dx.doi.org/10.1021/ma990091o
2. Carniato, F.; Fina, A.; Tabuani, D. & Boccaleri, E. - Nanotechnology, 19, p.1 (2008).
3. Joshi, M.; Butola, B. S.; Simon, G. & Kukaleva, N. - Macromolecules, 39, p.1839 (2006). http://dx.doi.org/10.1021/ma051357w
4. Misra, R.; Alidedeoglu, A. H.; Jarrett, W. L. & Morgan, S. E. - Polymer, 50, p.2906 (2009). http://dx.doi.org/10.1016/j.polymer.2009.03.057
5. Pielichowski, K.; Njuguna, J.; Janowski, B. & Pielichowski, J. - “Polyhedral Oligomeric Silsesquioxanes (POSS) - containing nanohybrid polymers”, in: Supramolecular Polymers Polymeric Betains Oligomers, Springer-Verlag Berlin, Berlin (2006).
6. Janssen, L. P. B. - “Reactive Extrusion Systems”, Marcel Dekker, Inc., New York (2004). http://dx.doi.org/10.1201/9780203014172
7. Xanthos, M. - “Reactive Extrusion: Principles and Practice”, Hanser Publishers, Munich (1992).
8. Passaglia, E.; Coiai, S.; Ricci, L. & Ciardelli, F. - Macromol. Symp., 218 (2004).
9. Zhou, Z.; Cui, L.; Zhang, Y.; Zhang, Y. & Yin, N. - Eur. Polym. J., 44, p.3057 (2008). http://dx.doi.org/10.1016/j.eurpolymj.2008.05.036
10. Monticelli, O.; Fina, A.; Ullah, A. & Waghmare, P. - Macromolecules, 42, p.6614 (2009). http://dx.doi.org/10.1021/ma900969b
11. Passaglia, E.; Coiai, S. & Augier, S. - Prog. Polym. Sci., 34, p.911 (2009). http://dx.doi.org/10.1016/j.progpolymsci.2009.04.008
12. Greene, S. V. - “SEC with On-Line Triple Detection: Light Scattering,Viscometry, and Refractive Index”, in: Encyclopedia of Chromatography, J. Cazes (ed.), Marcel Dekker, Inc., New York (2002).
13. Jackson, C. & Barth, H. G. - “Molecular Weight Sensitive Detectors for Size Exclusion Chromatography”, in: Handbook of Size Exclusion Chromatography and Related Techniques Second Edition, Revised and Expanded, cap.22, C-S. Wu (ed.), New York (2004).
14. Kurata, M. & Tsunashima, Y. - “Viscosity - Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules”, in: Polymer Handbook, J. Brandup, E. H. Immergut, E. A. Grulke (eds.), John Wiley & Sons, New York (2003).
15. Ouano, A. C. – J. Polym. Sci. Part A-1: Polym. Chem., 10, p.2169 (1972). http://dx.doi.org/10.1002/pol.1972.150100727
16. Menges, M. & Schmidt-Naake, G. - Angew. Makromol. Chem., 258, p.51 (1998). http://dx.doi.org/10.1002/(SICI)1522- 9505(19980801)258:1%3C51::AID-APMC51%3E3.0.CO;2-T
17. Tribe, K.; Saunders, G. & Meißner, R. - Macromol. Symp., 236, p.228 (2006). http://dx.doi.org/10.1002/masy.200690059
18. Hong, L. Z. & Liu, G. J. - Macromolecules, 43, p.3941 (2010). http:// dx.doi.org/10.1021/ma100353t
19. Çatiker, E. & Güner, A. – Polym. Bul., 41, p.223 (1998).
20. Cecopieri-Gómez, M. L. & Palacios-Alquisira, J. - J. Braz. Chem. Soc., 16, p.426 (2005).
21. Lee, J. S.; Kim, S. C. & Lee, H. K. - Macromol. Res., 16, p.631 (2008). http://dx.doi.org/10.1007/BF03218572
22. Stockmayer, W. H. & Fixman, M. – J. Polym. Sci. Part C: Polym. Symp., 1, p.137 (1963).
23. Michielsen, S. - “Specific Refractive Index Increments of Polymers in Dilute Solution”, in: Polymer Handbook, J. Brandup, E. H. Immergut, E. A. Grulke (eds.), John Wiley & Sons, New York (2003).
24. Malawer, E. G. & Senak, L. - “Introduction to Size Exclusion Chromatography”, in: Handbook of Size Exclusion Chromatography and Related Techniques Second Edition, Revised and Expanded, cap.22, C-S. Wu (ed.), Marcel Dekker Inc., New York (2004).
25. Sun, S. F. - “Physical chemistry of macromolecules : basic principles and issues”, John Wiley & Sons, Hoboken (2004). http://dx.doi. org/10.1002/0471623571
26. Florea, M. - J. Chromatogr. A, 878, p.1 (2000). http://dx.doi. org/10.1016/S0021-9673(00)00265-X
27. Teraoka, I. - “Polymer Solution An Introdution to Physical Properties”, John Wiley & Sons, Inc., New York (2002).
28. Delpech, M. C.; Coutinho, F. M. B.; Sousa, K. G. M. & Cruz, R. C. - Polímeros, 17, p.294 (2007). http://dx.doi.org/10.1590/S0104- 14282007000400008
29. Wall, F. T. & Hiller, L. A. - Annu. Rev. Phys. Chem., 5, p.267 (1954). http://dx.doi.org/10.1146/annurev.pc.05.100154.001411
30. Flory, P. J. - “Principles of Polymer Chemistry”, Cornell University Press, Ithaca (1953).
31. Wypych, G. - “Handbook of Solvents”, Chem Tec Publishing, Toronto (2001).
32. Pyun, J. & Matyjaszewski, K. - Macromolecules, 33, p.217 (2000). http://dx.doi.org/10.1021/ma9910787
33. Hirai, T.; Leolukman, M.; Jin, S.; Goseki, R.; Ishida, Y.; Kakimoto, M.‑a.; Hayakawa, T.; Ree, M. & Gopalan, P. - Macromolecules, 42, p.8835 (2009). http://dx.doi.org/10.1021/ma9018944
34. Bevington, J. C. & Huckerby, T. N. – Eur. Polym. J., 42, p.1433 (2006). http://dx.doi.org/10.1016/j.eurpolymj.2005.12.011
35. Zhang, H-X.; Lee, H-Y.; Shin, Y-J.; Yoon, K-B.; Noh, S-K. & Lee, D-H. – Polym. Int., 57, p.1351 (2008). http://dx.doi.org/10.1002/pi.2480
36. Moad, G. - Prog. Polym. Sci., 24, p.81 (1999). http://dx.doi. org/10.1016/S0079-6700(98)00017-3
37. Denisov, E. T.; Denisova, T. G. & Pokidova, T. S. - “Handbook of free radical initiators”, John Wiley & Sons, Inc., Hoboken (2003). http:// dx.doi.org/10.1002/0471721476
38. Nachtigall, S. M. B.; Stedile, F. C.; Felix, A. H. O. & Mauler, R. S. - J. Appl. Polym. Sci., 72, p.1313 (1999). http://dx.doi. org/10.1002/(SICI)1097-4628(19990606)72:10%3C1313::AIDAPP11% 3E3.3.CO;2-4
39. Nachtigall, S. n. M. B.; Felix, A. H. O.; Ojeda, T. & Mauler, R. S. - Polímeros, 8, p.69 (1998). http://dx.doi.org/10.1590/S0104- 14281998000400010
40. Faravelli, T.; Pinciroli, M.; Pisano, F.; Bozzano, G.; Dente, M. & Ranzi, E. – J. Anal. Appl. Pyrol., 60, p.103 (2001). http://dx.doi. org/10.1016/S0165-2370(00)00159-5
41. Li, Y.; Xie, X.-M. & Guo, B.-H. - Polymer, 42, p.3419 (2001). http:// dx.doi.org/10.1016/S0032-3861(00)00767-9
42. Bettini, S. H. P. & Ruvolo, A. C. - J. Appl. Polym. Sci., 107, p.1430 (2008). http://dx.doi.org/10.1002/app.27201
43. Huber, K.; Bantle, S.; Lutz, P. & Burchard, W. - Macromolecules, 18, p.1461 (1985). http://dx.doi.org/10.1021/ma00149a017
44. Fujita, H. - Macromolecules, 21, p.179 (1988). http://dx.doi. org/10.1021/ma00179a036
45. Morris, R. L.; Amelar, S. & Lodge, T. P. – J. Chem. Phys., 89, p.6523 (1988). http://dx.doi.org/10.1063/1.455372
46. Von Meerwall, E. D.; Amelar, S.; Smeltzly, M. A. & Lodge, T. P. - Macromolecules, 22, p.295 (1989). http://dx.doi.org/10.1021/ ma00191a054
47. Levenberg, K. - Quart. Appl. Math. , 2, p.164 (1944).
48. Marquardt, D. W. - J. Soc. Ind. Appl. Math., 11, p.431 (1963). http:// dx.doi.org/10.1137/0111030
49. Wagner, H. L. - J. Phys. Chem. Ref. Data, 14, p.1101 (1985). http:// dx.doi.org/10.1063/1.555740
50. Weber, V.; Duval, M.; Ederlé, Y. & Mathis, C. - Carbon, 36, p.839 (1998). http://dx.doi.org/10.1016/S0008-6223(98)00015-3
51. Orwoll, R. A. & Arnold, P. A. - “Polymer - Solvent Interaction Parameter c”, in: Physical Properties of Polymers Handbook, J. E. Mark (ed.), Springer, New York (2007).
52. Spyriouni, T.; Tzoumanekas, C.; Theodorou, D.; Muller-Plathe, F. & Milano, G. - Macromolecules, 40, p.3876 (2007). http://dx.doi. org/10.1021/ma0700983
53. Terao, K.; Hokajo, T.; Nakamura, Y. & Norisuye, T. - Macromolecules, 32, p.3690 (1999). http://dx.doi.org/10.1021/ma990091o
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