Thermal and Rheological Behavior of Reactive Blends from Metallocene Olefin Elastomers and Polypropylene
Domingues Junior, Nei S.; Forte, Maria M. C.; Riegel, Izabel C.
http://dx.doi.org/10.1590/S0104-14282012005000030
Polímeros: Ciência e Tecnologia, vol.22, n3, p.213-219, 2012
Abstract
Reactive blends of metallocene polyolefin elastomers (POE)/polypropylene (PP) with 60/40 composition were prepared with an organic peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, and a bis-azide derivative, diphenyloxid-4,4’-bis(sulfonylazide) (BSA). Ethylene-1-butene (EB) and ethylene-1-octene (EO) copolymers and elastomeric polypropylene (ePP) were used as the elastomeric phase. The effect of elastomeric phase on the thermal, rheological, morphological and mechanical properties of the thermoplastic vulcanizates (TPVs) or dynamic vulcanizates were studied. All TPVs depicted pseudoplastic behavior and blends cured with azide curative showed higher viscosities. The TPVs showed both dispersed and continuous phase morphology that depends on the elastomeric phase type revealing a limited degree of compatibility between PP and the elastomers EO or EB. On the other hand, the TPV PP/ePP showed a uniform morphology suggesting an improved compatibility. Substantial changes observed in physical properties were explained on the basis of blends’ morphology and dynamic vulcanization. The results confirm that the mechanical properties are more influenced by the elastomeric phase than by the curative agent. This study revealed a broad new range of opportunities for POE-based TPVs.
Keywords
Reactive blend, thermoplastic vulcanizates, metallocene polyolefin elastomers, rheology
References
1. Legge, N. R.; Holden, G.; Quirck, R. & Schroeder, H. E.
(eds.). – “Thermoplastic Elastomers”, Hanser publishers, New York
(1996).
2. Gessler, A. M. & Haslett, W. H. – “Process for preparing a vulcanized blend of crystalline polypropylene and chlorinated butyl rubber”, Patent US3.037.954 (1962).
3. Thomas, D. A. & Sperling, L. H. – “Interpenetrating Polymer Networks”, in: Interpenetrating Polymer Networks, S. Newman & D. R. Paul (eds.),: Academic Press, New York (1978).
4. Fisher, W. K. – “Thermoplastic blend of partially cured monoolefin copolymer rubber and polyolefin plastic”, Patent US3.758.643 (1973).
5. Gomes, A. C. O.; Soares, B. G.; Oliveira, M. G. & Paranhos, C. M. - Polimeros, 19, p.196 (2009).
6. Coran, A. Y.; Das, B. & Patel, R. P. – “Thermoplastic vulcanizates of olefin rubber and polyolefin resin”, Patent US4.130.535 (1978).
7. Coran, A. Y.; Chung, O. & Laokijcharoen, P. - Kaut. Gummi Kunst., 51, p.342 (1998).
8. Lopez-Manchado, M. A.; Arroyo, M. & Kenny, J. M. - Rubber Chem. Technol., 74, p.211 (2001).
9. Coran, A. Y. & Patel, R - Rubber Chem. Technol., 53, p.144 (1980).
10. Wang, Z.; Cheng, X. & Zhao, J. - Mater. Chem. Phys., 126, p.272 (2011). http://dx.doi.org/10.1016/j.matchemphys.2010.11.027
11. Chung, O. & Coran, A. Y. - Rubber Chem. Technol., 70, p.781. (1997). http://dx.doi.org/10.5254/1.3538460
12. Li, Z. & Kontopoulou, M. - Polym. Eng. Sci., 49, p.34 (2009). http:// dx.doi.org/10.1002/pen.21265
13. Pechurai, W.; Nakason, C. and Sahakaro, K. – Polym. Test., 27, p.621 (2008). http://dx.doi.org/10.1016/j.polymertesting.2008.04.001
14. Caihong, L.; Xianbo, H. & Fangzhong, M. - Polym. Adv. Technol., 18, p.999 (2007).
15. Vennemann, N.; Bokamp, K. & Broker, D. - Macromol. Symp., 245‑246, p.641 (2006). http://dx.doi.org/10.1002/masy.200651391
16. Nakason, C.; Worlee, A. & Salaeh, S. – Polym. Test., 27, p.858 (2008). http://dx.doi.org/10.1016/j.polymertesting.2008.06.011
17. Cossa, M. M.; Costa, L. M. M.; Sirqueira, A. S.; Bretas, R. E. S.; Soares, B. G. & Gregório Filho, R. – Polimeros, 19, p.190 (2009).
18. Schellenberg, J. – Adv.Polym. Technol., 16, p.135 (1997). http:// dx.doi.org/10.1002/(SICI)1098-2329(199722)16:2%3C135::AID‑AD V6%3E3.0.CO;2-V
19. Silva, A. L. N.; Rocha, M. C. G.; Guimarães, M. J. O.C.; Lovisi, H.; Coutinho, F. M. B. & Santa Maria, L. C. - Polimeros, 11, p.135 (2001). http://dx.doi.org/10.1590/S0104-14282001000300013
20. Huang, H. J.; Xie, B. H.; Yang, W.; Shen, Y. X. & Yang, M. B. - J. of Macrom Sci - Part B, 49, p.231(2010).
21. Guimarães, M. J. O. C.; Coutinho, F. M. B.; Rocha, M. C. G.; Bretas, R. E. S. & Farah, M. – Polimeros, 13, p.135 (2003).
22. Chee, H. J.; Min, J. H.; Byung, Y. L. & Chang, H. C. – “Olefin-based crosslinked thermoplastic elastomers and a process of preparation thereof”, Patent US6.143.828 (2000).
23. Finerman, T. & Abdou-Sabet, S. – “Modification of thermolastic vulcanizates with a thermoplastic random copolymer of ethylene”, Patent US6.399.710 (2002).
24. Coates, G. W. & Waymouth, R. M. – Science, 267, p.217 (1995). PMid:17791342. http://dx.doi.org/10.1126/science.267.5195.217
25. Ternbrueggen, R. H.; Drumright, R. E. & Ho, T. H. – “Process for preparing thermoplastic vulcanizates”, Patent US6.277.916 (2001).
26. Chodak, I. - Prog. Polym. Sci., 20, p.1165 (1995). http://dx.doi. org/10.1016/0079-6700(95)98859-N
27. MacNally, T.; McShane, P.; Nally, G. M.; Murphy, W. R.; Cook, M. & Miller, A. – Polymer, 43, p.3785 (2002).
28. D’Orazio, L.; Mancarella, C.; Martuscelli, E.; Cecchin, G. & Corrieri, R. – Polymer, 40, p.2745 (1999).
29. Ferry, J. D. - “Viscoelastic Properties of Polymers”, Wiley and Sons, New York (1980).
30. Babu, R. R.; Singha, N. K. & Naskar, K. - J. Polym. Res., 18, p.31 (2011). http://dx.doi.org/10.1007/s10965-010-9388-2
31. Marinovic, T.; Susteric, Z.; Dimitrievski, I. & Veksli, Z. - Kaut. Gummi Kunst., 51, p.189 (1998).
32. Favis, B. D. – Can. J. Chem. Eng., 69, p.619 (1991). http://dx.doi. org/10.1002/cjce.5450690303
33. Tokita, N. - Rubber Chem. Technol., 50, p.292 (1977). http://dx.doi. org/10.5254/1.3535144
34. Wu, S. - Polym. Eng. Sci., 27, p.335 (1987). http://dx.doi.org/10.1002/ pen.760270506
35. Paul, D. R. - Adv. In Chem. Series, 211, p.3 (1985). http://dx.doi. org/10.1021/ba-1986-0211.ch001
36. Utracki, L. A. - “Polymer Alloys and Blends”, Hanser Publishers, New York 1989.
37. Eby, R. K.; Mareanukruoh, M.; Scavuzzo, R. J. & Preuschen, J. - Rubber Chem. Technol., 73, p.912 (2000).
38. Guimarães, M. J. O. C.; Coutinho, F. M. B.; Rocha, M. C. G.; Farah, M. & Bretas, R. E. S. – Polym. Test., 22, p.843 (2003).
39. Han, S. J.; Lohse, D. J. & Sperling, L. H. – J. App. Polym. Sci., 77, p.1478 (2000).
40. Kim, B. K. & Kim, K. J. Adv. – Polym.Technol., 12, p.263 (1993). http://dx.doi.org/10.1002/adv.1993.060120304
41. Rowland, M. E.; Turley, R. R. ; Hill, J. J.; Kale, L. T.; Kummer, K. G.; Lai, S. Y. & Chum, P. S. – “Rheology-modified polyolefins”, Patent US6.114.486 (2000).
2. Gessler, A. M. & Haslett, W. H. – “Process for preparing a vulcanized blend of crystalline polypropylene and chlorinated butyl rubber”, Patent US3.037.954 (1962).
3. Thomas, D. A. & Sperling, L. H. – “Interpenetrating Polymer Networks”, in: Interpenetrating Polymer Networks, S. Newman & D. R. Paul (eds.),: Academic Press, New York (1978).
4. Fisher, W. K. – “Thermoplastic blend of partially cured monoolefin copolymer rubber and polyolefin plastic”, Patent US3.758.643 (1973).
5. Gomes, A. C. O.; Soares, B. G.; Oliveira, M. G. & Paranhos, C. M. - Polimeros, 19, p.196 (2009).
6. Coran, A. Y.; Das, B. & Patel, R. P. – “Thermoplastic vulcanizates of olefin rubber and polyolefin resin”, Patent US4.130.535 (1978).
7. Coran, A. Y.; Chung, O. & Laokijcharoen, P. - Kaut. Gummi Kunst., 51, p.342 (1998).
8. Lopez-Manchado, M. A.; Arroyo, M. & Kenny, J. M. - Rubber Chem. Technol., 74, p.211 (2001).
9. Coran, A. Y. & Patel, R - Rubber Chem. Technol., 53, p.144 (1980).
10. Wang, Z.; Cheng, X. & Zhao, J. - Mater. Chem. Phys., 126, p.272 (2011). http://dx.doi.org/10.1016/j.matchemphys.2010.11.027
11. Chung, O. & Coran, A. Y. - Rubber Chem. Technol., 70, p.781. (1997). http://dx.doi.org/10.5254/1.3538460
12. Li, Z. & Kontopoulou, M. - Polym. Eng. Sci., 49, p.34 (2009). http:// dx.doi.org/10.1002/pen.21265
13. Pechurai, W.; Nakason, C. and Sahakaro, K. – Polym. Test., 27, p.621 (2008). http://dx.doi.org/10.1016/j.polymertesting.2008.04.001
14. Caihong, L.; Xianbo, H. & Fangzhong, M. - Polym. Adv. Technol., 18, p.999 (2007).
15. Vennemann, N.; Bokamp, K. & Broker, D. - Macromol. Symp., 245‑246, p.641 (2006). http://dx.doi.org/10.1002/masy.200651391
16. Nakason, C.; Worlee, A. & Salaeh, S. – Polym. Test., 27, p.858 (2008). http://dx.doi.org/10.1016/j.polymertesting.2008.06.011
17. Cossa, M. M.; Costa, L. M. M.; Sirqueira, A. S.; Bretas, R. E. S.; Soares, B. G. & Gregório Filho, R. – Polimeros, 19, p.190 (2009).
18. Schellenberg, J. – Adv.Polym. Technol., 16, p.135 (1997). http:// dx.doi.org/10.1002/(SICI)1098-2329(199722)16:2%3C135::AID‑AD V6%3E3.0.CO;2-V
19. Silva, A. L. N.; Rocha, M. C. G.; Guimarães, M. J. O.C.; Lovisi, H.; Coutinho, F. M. B. & Santa Maria, L. C. - Polimeros, 11, p.135 (2001). http://dx.doi.org/10.1590/S0104-14282001000300013
20. Huang, H. J.; Xie, B. H.; Yang, W.; Shen, Y. X. & Yang, M. B. - J. of Macrom Sci - Part B, 49, p.231(2010).
21. Guimarães, M. J. O. C.; Coutinho, F. M. B.; Rocha, M. C. G.; Bretas, R. E. S. & Farah, M. – Polimeros, 13, p.135 (2003).
22. Chee, H. J.; Min, J. H.; Byung, Y. L. & Chang, H. C. – “Olefin-based crosslinked thermoplastic elastomers and a process of preparation thereof”, Patent US6.143.828 (2000).
23. Finerman, T. & Abdou-Sabet, S. – “Modification of thermolastic vulcanizates with a thermoplastic random copolymer of ethylene”, Patent US6.399.710 (2002).
24. Coates, G. W. & Waymouth, R. M. – Science, 267, p.217 (1995). PMid:17791342. http://dx.doi.org/10.1126/science.267.5195.217
25. Ternbrueggen, R. H.; Drumright, R. E. & Ho, T. H. – “Process for preparing thermoplastic vulcanizates”, Patent US6.277.916 (2001).
26. Chodak, I. - Prog. Polym. Sci., 20, p.1165 (1995). http://dx.doi. org/10.1016/0079-6700(95)98859-N
27. MacNally, T.; McShane, P.; Nally, G. M.; Murphy, W. R.; Cook, M. & Miller, A. – Polymer, 43, p.3785 (2002).
28. D’Orazio, L.; Mancarella, C.; Martuscelli, E.; Cecchin, G. & Corrieri, R. – Polymer, 40, p.2745 (1999).
29. Ferry, J. D. - “Viscoelastic Properties of Polymers”, Wiley and Sons, New York (1980).
30. Babu, R. R.; Singha, N. K. & Naskar, K. - J. Polym. Res., 18, p.31 (2011). http://dx.doi.org/10.1007/s10965-010-9388-2
31. Marinovic, T.; Susteric, Z.; Dimitrievski, I. & Veksli, Z. - Kaut. Gummi Kunst., 51, p.189 (1998).
32. Favis, B. D. – Can. J. Chem. Eng., 69, p.619 (1991). http://dx.doi. org/10.1002/cjce.5450690303
33. Tokita, N. - Rubber Chem. Technol., 50, p.292 (1977). http://dx.doi. org/10.5254/1.3535144
34. Wu, S. - Polym. Eng. Sci., 27, p.335 (1987). http://dx.doi.org/10.1002/ pen.760270506
35. Paul, D. R. - Adv. In Chem. Series, 211, p.3 (1985). http://dx.doi. org/10.1021/ba-1986-0211.ch001
36. Utracki, L. A. - “Polymer Alloys and Blends”, Hanser Publishers, New York 1989.
37. Eby, R. K.; Mareanukruoh, M.; Scavuzzo, R. J. & Preuschen, J. - Rubber Chem. Technol., 73, p.912 (2000).
38. Guimarães, M. J. O. C.; Coutinho, F. M. B.; Rocha, M. C. G.; Farah, M. & Bretas, R. E. S. – Polym. Test., 22, p.843 (2003).
39. Han, S. J.; Lohse, D. J. & Sperling, L. H. – J. App. Polym. Sci., 77, p.1478 (2000).
40. Kim, B. K. & Kim, K. J. Adv. – Polym.Technol., 12, p.263 (1993). http://dx.doi.org/10.1002/adv.1993.060120304
41. Rowland, M. E.; Turley, R. R. ; Hill, J. J.; Kale, L. T.; Kummer, K. G.; Lai, S. Y. & Chum, P. S. – “Rheology-modified polyolefins”, Patent US6.114.486 (2000).
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