Abstract
The time dependent crystallization of a low isotactic polypropylene with statistically incorporated stereoerrors was investigated by the combination of differential scanning calorimetry (DSC), wideangle X-ray scattering (WAXS) and scanning force microscopy (SFM). Owing to Scanning force microscopy (SFM) and WAXS experiments the crystallization of the sample in mixed α/γ-form aggregates can be proposed. The nucleation and growth processes of crystallization in thin polypropylene films in real time were visualized with nanometer resolution by using SFM at variable temperature. During the isothermal crystallization from the melt initially crystals of the α-form were developed. These lamellae act as nuclei for the further crystallization of γ- and mixed α/γ-lamellae, which can be observed at longer crystallization times. Time dependent SFM and WAXS experiments showed that due to the low amount of crystallizable, regular sequences and its statistical distribution only slow crystallization rates can be observed. These results form the basis for a better understanding of the crystallization of low crystallinity polypropylenes. The investigations clearly show that the distribution of the regular isotactic segments influences the crystallization properties of propene based TEP's. This opens the possibility to tailor not only the mechanical but also the thermal properties of elastomeric polypropylenes by changing the polymer microstructure.
Similar content being viewed by others
Article PDF
References
L. Resconi, L. Cavallo, A. Fait, and F. Piemontesi, Chem. Rev., 100, 1253 (2000).
J. W. Collette, C. W. Tullock, R. N. MacDonald, W. H. Buck, A. C. L. Su, J. R. Harrell, R. Mulhaupt, and B. C. Anderson, Macromolecules, 22, 3851 (1989).
J. W. Collette, D. W. Ovenall, W. H. Buck, and R. C. Ferguson, Macromolecules, 22, 3858 (1989).
S. D. Ittel, J. Macromol. Sci. Chem., A27, 9 (1990).
D. T. Mallin, M. D. Rausch, Y. G. Lin, S. Dong, and J. C. W. Chien, J. Am. Chem. Soc., 112, 2030 (1990).
A. Bravakis, L. E. Bailey, M. Pigeon, and S. Collins, Macromolecules, 31, 1000 (1998).
G. W. Coates and R. M. Waymouth, Science, 267, 217 (1995).
M. D. Bruce, G. W. Coates, E. Hauptman, R. M. Waymouth, and J. W. Ziller, J. Am. Chem. Soc., 119, 11174 (1997).
G. Natta, G. Mazzanti, G. Crespi, and G. Moraglio, Chim. Ind., 39, 275 (1957).
G. Natta, U. S. Patent (1965).
“Thermoplastic Elastomers,” G. Holden, N. R. Legge, R. P. Quirk, and H. E. Schroeder, Ed., Hanser Gardner, 1996.
E. D. Carlson, M. T. Krejchi, C. D. Shah, T. Terakawa, R. M. Waymouth, and G. G. Fuller, Macromolecules, 31, 5343 (1998).
Y. Hu, E. D. Carlson, G. G. Fuller, and R. M. Waymouth, Macromolecules, 32, 3334 (1999).
R. Kravchenko, A. Masood, R. M. Waymouth, and C. L. Myers, J. Am. Chem. Soc., 120, 2039 (1998).
E. D. Carlson, G. G. Fuller, and R. M. Waymouth, Macromolecules, 32, 8100 (1999).
H. Schönherr, W. Wiyatno, J. Pople, C. W. Frank, G. G. Fuller, P. GA, and R. M. Waymouth, Macromolecles, 35, 2654 (2002).
G. J. Natta, J. Polym. Sci., 34, 531 (1959).
S. Bensason, J. Minick, A. Moet, S. Chum, A. Hiltner, and E. Baer, J. Polym. Sci., Part B: Polym. Phys., 34, 1301 (1996).
T. Ho and J. M. Martin, in “Metallocene-Based Polyolefins” J. Scheirs and W. Kaminsky, Ed., Wiley, Chichester, 2000, p 175.
G. Holden, in “CRC Press,” J. Salamone, Ed., Boca Raton, 1996, p 8343.
E. M. Frick, S. Andrew, R. Zalusky, and M. A. Hillmyer, Biomacromolecules, 4, 216 (2003).
W. Gabrielse, M. Soliman, and K. Dijkstra, Macromolecules, 34, 1693 (2001).
S. Velankar and S. L. Cooper, Macromolecules, 33, 382 (2000).
M. Konrad, A. Knoll, G. Krausch, and R. Magerle, Macromolecules, 33, 5518 (2000).
N. Rehse, A. Knoll, R. Magerle, and G. Krausch, Macromolecules, 36, 3261 (2003).
C. De Rosa, F. Auriemma, M. Paolillo, L. Resconi, and I. Camurati, Macromolecule, 38, 9143 (2005).
R. G. Alamo, M.-H. Kim, M. J. Galante, J. R. Isasi, and L. Mandelkern, Macromolecules, 32, 4050 (1999).
J. C. Randall, R. G. Alamo, P. K. Agarwal, and C. J. Ruff, Macromolecules, 36, 1572 (2003).
B. Wunderlich, “Macromolecular Physics,” Academic press, New York, 1973, Vol. 1–3.
I. C. Sanchez and R. K. Eby, Macromolecules, 25, 638 (1975).
A. Alizadeh, L. Richardson, J. Xu, S. McCartney, H. Marand, Y. W. Cheung, and S. Chum, Macromolecules, 32, 6221 (1999).
B. Crist and D. N. Williams, J. Macromol. Sci., Part B: Phys., 39, 1 (2000).
D. Fischer and R. Mülhaupt, Macromol. Chem. Phys., 195, 1433 (1994).
C. De Rosa, F. Auriemma, T. Circelli, and R. M. Waymouth, Macromolecules, 35, 3622 (2002).
C. Averbuj, E. Tish, and M. S. Eisen, J. Am. Chem. Soc., 120, 8640 (1998).
M. Xie, Q. Wu, and S. Lin, Acta Polym. Sym., 1, 15 (1999).
K. Kimura, K. Takaishi, T. Matsukawa, T. Yoshimura, and H. Yamazaki, Chem. Lett., 571 (1998).
W. J. Gauthier and S. Collins, Macromolecules, 28, 3779 (1995).
G. H. Llinas, S.-H. Dong, D. T. Mallin, M. D. Rausch, Y.-G. Lin, H. H. Winter, and J. C. W. Chien, Macromolecules, 25, 1242 (1992).
J. C. W. Chien and M. D. Rausch, U. S. Patent 5.756.614 (1998).
R. M. Waymouth, G. W. Coates, and E. M. Hauptman, U. S. Patent 5.594.080 (1997).
S. A. Miller and J. E. Brecaw, Organometallics, 21, 934 (2002).
U. Dietrich, M. Hackmann, B. Rieger, M. Klinga, and M. Leskelä, J. Am. Chem. Soc., 121, 4338 (1999).
G. Müller and B. Rieger, Prog. Polym. Sci., 27, 815 (2002).
B. Rieger, C. Troll, and J. Preuschen, Macromolecules, 35, 5742 (2002).
X. Zhu, D. Yan, and Y. J. Fang, J. Phys. Chem. B., 105, 1246 (2001).
D. C. Bassett, in “Principles of Polymer Morphology,” Cambridge University Press, Cambridge, 1981.
G. R. Strobl, in “The physics of polymers,” Springer, Berlin, 1996.
R. Pearce and G. Vancso, Polymer, 39, 1237 (1998).
J. M. Schultz and M. J. Miles, J. Polym. Sci., Part B: Polym. Phys., 36, 2311 (1998).
J. K. Hobbs, T. J. McMaster, M. J. Miles, and P. J. Barham, Polymer, 39, 2437 (1998).
T. J. McMaster, J. K. Hobbs, P. J. Barham, and M. J. Miles, Probe Microsc., 1, 43 (1997).
L. Li, C.-M. Chan, K. L. Yeung, J.-X. Li, K.-M. Ng, and Y. Lei, Macromolecules, 34, 316 (2001).
Y. Kikkawa, Y. Inoue, H. Abe, T. Iwata, and Y. Doi, Polymer, 42, 2707 (2001).
W. Zhou, S. Z. D. Cheng, S. Puttharnarat, R. K. Eby, D. H. Reneker, B. Lotz, S. Magonov, E. T. Hsieh, R. G. Geerts, S. J. Palackal, G. R. Hawley, and M. B. Welch, Macromolecules, 33, 6861 (2000).
L. G. M. Beekmans and G. J. Vancso, Polymer, 41, 8975 (2000).
G. J. Vancso, G. Liu, J. KargerKocsis, and J. Varga, Colloid Polym. Sci., 38, 491 (1999).
J. K. Hobbs, A. D. L. Humphris, and M. J. Miles, Macromolecules, 34, 5508 (2001).
H. Schönherr and C. W. Frank, Macromolecules, 36, 1188 (2003).
H. Schönherr and C. W. Frank, Macromolecules, 36, 1199 (2003).
H. Schönherr, C. J. Waymouth, and C. W. Frank, Macromolecules, 36, 2412 (2003).
A. Boger, B. Heise, C. Troll, O. Marti, and B. Rieger, Eur. Polym. J., 43, 634 (2007).
Q. Zhong, D. Inniss, K. Kjoller, and V. Elings, Surf. Sci., 290, 688 (1993).
T. J. Morkved and H. M. Jaeger, Europhys. Lett., 40, 643 (1997).
J. P. Cleveland, B. Anczykowski, A. E. Schmid, and V. B. Elings, Appl. Phys. Lett., 72, 2613 (1998).
J. Tamayo and R. Garcia, Appl. Phys. Lett., 73, 2926 (1998).
W. W. Scott and B. Bhushan, Ultramicroscopy, 97, 151 (2003).
G. Bar, Y. Thomann, R. Brandsch, H.-J. Cantow, and M.-H. Whangbo, Langmuir, 13, 3807 (1997).
B. Wunderlich, in “Macromolecular Physics,” Academic Press, New York, 1976, Vol. II.
S. Brückner, S. V. Meille, V. Petraccone, and B. Pirozzi, Prog. Polym. Sci., 16, 361 (1991).
S. V. Meille, S. Brückner, and W. Porzio, Macromolecules, 23, 4114 (1990).
R. G. Alamo, J. A. Blanco, P. K. Agarwal, and J. C. Randall, Macromolecules, 36, 1559 (2003).
C. De Rosa, F. Auriemma, A. Di Capua, L. Resconi, S. Guidotti, I. Camurati, I. E. Nifant'ev, and Laishevtsev, J. Am. Chem. Soc., 126, 17040 (2004).
D. Fischer and R. Mülhaupt, Macromol. Chem. Phys., 195, 1433 (1994).
C. De Rosa, F. Auriemma, and L. Resconi, Macromolecules, 38, 10080 (2005).
D. C. Bassett and R. H. Olley, Polymer, 25, 935 (1984).
R. H. Olley and D. C. Bassett, Polymer, 30, 399 (1989).
B. Lotz and J. C. Wittmann, J. Polym. Sci., Part B: Polym. Phys., 24, 1541 (1986).
B. Lotz, S. Graff, C. Straupe, and J. C. Wittmann, Polymer, 32, 2902 (1991).
R. Thomann, C. Wang, J. Kressler, and R. Müllhaupt, Macromolecules, 29, 8425 (1996).
R. Thomann, J. Kressler, B. Pudolf, and R. Mülhaupt, Polymer, 37, 2635 (1996).
R. Thomann, J. Kressler, S. Setz, R. Wang, and R. Müllhaupt, Polymer, 37, 2627 (1996).
C. De Rosa, F. Auriemma, and C. Perretta, Macromolecules, 37, 6843 (2004).
A. R. Siedle, PCT 1999.
W. Wiyatno, J. Pople, A. P. Gast, R. M. Waymouth, and G. G. Fuller, Macromolecles, 35, 8488 (2002).
C. De Rosa, F. Auriemma, T. Circelli, and R. M. Waymouth, Macromolecules, 35, 3622 (2002).
F. Auriemma and C. De Rosa, Macromolecules, 35, 9057 (2002).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hild, S., Boger, A., Troll, C. et al. Nucleation and Crystallization of Low Isotatic Polypropylenes with Statistically Distributed Stereoerrors. Polym J 41, 993–1004 (2009). https://doi.org/10.1295/polymj.PJ2008131
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2008131