Crystallization and Crystalline Structure of Syndiotactic Polypropylene and Syndiotactic-Poly(1-Butene) Blend

Abstract

The crystallization and crystalline structure of syndiotactic-polypropylene (sPP) and syndiotactic-poly(1-butene) (sPB) blend containing 10 (Bl-10), 25 (Bl-25), 50 (Bl-50), 75 (Bl-75), and 90 (Bl-90) wt% of sPB, have been investigated by means of differential scanning calorimetry (DSC), FT-IR, and wide-angle X-ray diffraction (WAXD) analyses. The melt-crystallization behavior of the blend samples was studied by DSC on the cooling process at constant rates. Bl-50, Bl-75, and Bl-90 showed lower crystallization temperatures than the neat sPP. sPP in Bl-75 showed the lowest crystallization rate among the blend samples. Bl-90 showed a two-phase molten state, and sPP in Bl-90 crystallized via two-stepprocess. Time evolution of FT-IR spectroscopy at room temperature detected conformational transformation of the sPP polymer chain in the blend samples of Bl-50 and Bl-75. The absorption peaks intensity in the FT-IR spectra derived from the helical conformations in the crystalline phase decreased, and the planar zigzag conformations in the amorphous and mesophase phases decreased over the crystallization time. The time evolution of the WAXD profile of Bl-90 indicated that sPP in the blend accelerated the crystallization of sPB. The crystallized Bl-10, Bl-25, and Bl-50 samples showed diffraction peaks in WAXD profiles and melting endothermic peak in DSC profiles derived from only the sPP crystal. The crystallinity and melting temperature of sPP in the crystallized Bl-10, Bl-25, and Bl-50 samples were almost independent of the sPB content. Both the crystalline structure of sPP and sPB were detected in Bl-75 and Bl-90. Bl-75 showed the lowest crystallinity and melting temperature of sPP among the blend samples.

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Naga, N. , Takagi, Y. , Urakami, S. and Noguchi, K. (2014) Crystallization and Crystalline Structure of Syndiotactic Polypropylene and Syndiotactic-Poly(1-Butene) Blend. Open Journal of Polymer Chemistry, 4, 102-114. doi: 10.4236/ojpchem.2014.44012.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] Brintzinger, H.H., Fischer, D., Mülhaupt, R., Rieger, B. and Waymouth, R.M. (1995) Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts. Angewandte Chemie International Edition, 34, 1143-1170.
http://onlinelibrary.wiley.com/doi/10.1002/anie.199511431
http://dx.doi.org/10.1002/anie.199511431
[2] Ewen, J.A., Loria, R.L., Razavi, A. and Ferrara, J.D. (1988) Syndiospecific Propylene Polymerizations with Group IVB Metallocenes. Journal of the America Chemcal Society, 110, 6255-6256.
http://pubs.acs.org/doi/abs/10.1021/ja00226a056
[3] Asanuma, T., Nishimori, Y., Ito, M., Uchikawa, N. and Shiomura, T. (1991) Preparation of Syndiotactic Polyolefins by Using Metallocene Catalysts. Polymer Bulletin, 25, 567-570.
http://link.springer.com/article/10.1007%2FBF00293515
http://dx.doi.org/10.1007/BF00293515
[4] Lotz, B., Lovinger, A.J. and Cais, R.E. (1988) Crystal Structure and Morphology of Syndiotactic Polypropylene Single Crystals. Macromolecules, 21, 2375-2387.
http://dx.doi.org/10.1021/ma00186a013
[5] Lovinger, A.J., Lotz, B. and Davis, D.D. (1990) Interchain Packing and Unit Cell of Syndiotactic Polypropylene. Polymer, 31, 2253-2259.
http://www.sciencedirect.com/science/article/pii/003238619090310U http://dx.doi.org/10.1016/0032-3861(90)90310-U
[6] Lovinger, A.J., Davis, D.D. and Lotz, B. (1991) Temperature Dependence of Structure and Morphology of Syndiotactic Polypropylene and Epitaxial Relationships with Isotactic Polypropylene, Macromolecules, 24, 552-560.
http://pubs.acs.org/doi/abs/10.1021/ma00002a033
http://dx.doi.org/10.1021/ma00002a033
[7] De Rosa, C. and Corradini, P. (1993) Crystal Structure of Syndiotactic Polypropylene. Macromolecules, 26, 5711-5718.
http://pubs.acs.org/doi/abs/10.1021/ma00073a028
http://dx.doi.org/10.1021/ma00073a028
[8] Chatani, Y., Maruyama, H., Noguchi, K., Asanuma, T. and Shiomura, T. (1990) Crystal Structure of the Planar Zigzag form of Syndiotactic Polypropylene. Journal of Polymer Science Part C: Polymer Letters, 28, 393-398.
http://onlinelibrary.wiley.com/doi/10.1002/pol.1990.140281301
http://dx.doi.org/10.1002/pol.1990.140281301
[9] Chatani, Y., Maruyama, H., Asanuma, T. and Shiomura, T. (1991) Structure of a New Crystalline Phase of Syndiotactic Polypropylene. Journal of Polymer Science Part B: Polymer Physics, 29, 1649-1652.
http://onlinelibrary.wiley.com/doi/10.1002/polb.1991.090291310
http://dx.doi.org/10.1002/polb.1991.090291310
[10] De Rosa, C., Auriemma, F. and Vinti, V. (1997) Disordered Polymorphic Modifications of Form I of Syndiotactic Polypropylene. Macromolecules, 30, 4137-4146.
http://pubs.acs.org/doi/abs/10.1021/ma961691f
http://dx.doi.org/10.1021/ma961691f
[11] De Rosa, C., Auriemma, F. and Vinti, V. (1998) On the Form II of Syndiotactic Polypropylene. Macromolecules, 31, 7430-7435. http://pubs.acs.org/doi/abs/10.1021/ma980789m
http://dx.doi.org/10.1021/ma980789m
[12] Zhang, J., Yang, D., Thierry, A.J., Wittmann, C. and Lotz, B. (2001) Isochiral Form II of Syndiotactic Polypropylene Produced by Epitaxial Crystallization. Macromolecules, 34, 6261-6267.
http://pubs.acs.org/doi/abs/10.1021/ma010758i
[13] Rastogi, S., La Camera, D., van der Burgt, F., Terry, A.E. and Cheng, S.Z.D. (2001) Polymorphism in Syndiotactic Polypropylene: Thermodynamic Stable Regions for Form I and Form II in Pressure—Temperature Phase Diagram. Macromolecules, 34, 7730-7736.
http://pubs.acs.org/doi/abs/10.1021/ma0109119
http://dx.doi.org/10.1021/ma0109119
[14] Guadagno, L., D’Aniello, C., Naddeo, C., Vittoria, V. and Meille, S.V. (2002) Elasticity of the Oriented Mesomorphic Form of Syndiotactic Polypropylene. Macromolecules, 35, 3921-3927. http://pubs.acs.org/doi/abs/10.1021/ma011825b
http://dx.doi.org/10.1021/ma011825b
[15] De Rosa, C., Venditto, V., Guerra, G., Pirozzi, B. and Corradini, P. (1991) Polymorphism and Chain Conformations in the Crystalline Forms of Syndiotactic Poly(1-Butene). Macromolecules, 24, 5645-5650.
http://pubs.acs.org/doi/abs/10.1021/ma00020a025
http://dx.doi.org/10.1021/ma00020a025
[16] De Rosa, C., Venditto, V., Guerra, G. and Corradini, P. (1992) Crystal Structure of the Form I of Syndiotactic Poly(1-Butene). Die Makromolekulare Chemie, 193, 1351-1358.
http://dx.doi.org/10.1002/macp.1992.021930611
http://onlinelibrary.wiley.com/doi/10.1002/macp.1992.021930611
[17] Zhang, B., Yang, D., De Rosa, C., Yan, S. and Petermann, J. (2001) Single Crystal Structure of Form I Syndiotactic Poly(Butene-1), Macromolecules, 34, 5221-5223.
http://pubs.acs.org/doi/abs/10.1021/ma010036r
http://dx.doi.org/10.1021/ma010036r
[18] Galimberti, M., Balbontin, G., Camurati, I. and Paganetto, G. (1994) Crystalline Syndiotactic Poly(1-Pentene). Macromolecular Rapid Communications, 15, 633-638.
http://dx.doi.org/10.1002/marc.1994.030150803
http://onlinelibrary.wiley.com/doi/10.1002/marc.1994.030150803
[19] De Rosa, C., Venditto, V., Guerra, G. and Corradini, P. (1992) Chain Conformation and Unit Cell in the Crystalline Phase of Syndiotactic Poly(4-Methyl-1-Pentene). Macromolecules, 25, 6938-6942.
http://pubs.acs.org/doi/abs/10.1021/ma00051a034
http://dx.doi.org/10.1021/ma00051a034
[20] De Rosa, C., Venditto, V., Guerra, G. and Corradini, P. (1995) Crystal Structure of Syndiotactic Poly(4-Methyl-1-Pentene). Polymer, 36, 3619-3624.
http://www.sciencedirect.com/science/article/pii/003238619593762B
http://dx.doi.org/10.1016/0032-3861(95)93762-B
[21] Uozumi, T. and Soga, K. (1992) Copolymerization of Olefins with Kaminsky-Sinn-Type Catalysts. Die Makromolekulare Chemie, 193, 823-831.
http://onlinelibrary.wiley.com/doi/10.1002/macp.1992.021930401
http://dx.doi.org/10.1002/macp.1992.021930401
[22] Jüngling, S., Mülhaupt, R., Fischer, D. and Langhauser, F. (1995) Modified Syndiotactic Polypropene: Poly(Propeneco-Octene) and Blends with Atactic Oligopropene. Die Angewandte Makromolekulare Chemie, 229, 93-112.
http://onlinelibrary.wiley.com/doi/10.1002/apmc.1995.052290106
http://dx.doi.org/10.1002/apmc.1995.052290106
[23] Naga, N., Mizunuma, K., Sadatoshi, H. and Kakugo, M.(1997) Properties and Crystalline Structures of Syndiotactic Poly(Propylene-co-1-Butene). Macromolecules, 30, 2197-2200.
http://pubs.acs.org/doi/abs/10.1021/ma961438f
http://dx.doi.org/10.1021/ma961438f
[24] Thomann, R., Kressler, J. and Mülhaupt, R. (1997) Single Crystals of Syndiotactic Poly[Propene-co-(1-Octene)] and Syndiotactic Polypropene Crystallized in Bulk. Macromolecular Chemistry and Physics, 198, 1271-1279.
http://onlinelibrary.wiley.com/doi/10.1002/macp.1997.021980428
http://dx.doi.org/10.1002/macp.1997.021980428
[25] De Rosa, C., Auriemma, F., Vinti, V., Grassi, A. and Galimberti, M. (1998) Polymorphism of Syndiotactic Polypropylene in Copolymers of Propylene with Ethylene and 1-Butene. Polymer, 39, 6219-6226.
http://www.sciencedirect.com/science/article/pii/S0032386197101744
http://dx.doi.org/10.1016/S0032-3861(97)10174-4
[26] De Rosa, C., Talarico, G., Caporaso, L., Auriemma, F., Galimberti, M. and Fusco, O. (1998) Structural Characterization of Syndiotactic Copolymers of Propene with 1-Butene. Macromolecules, 31, 9109-9115.
http://pubs.acs.org/doi/abs/10.1021/ma981020c
http://dx.doi.org/10.1021/ma981020c
[27] Naga, N., Mizunuma, K., Sadatoshi, H. and Kakugo, M. (2000) Isothermal Crystallization of Syndiotactic Poly(Propylene-co-Olefin)s. Polymer, 41, 203-209.
http://www.sciencedirect.com/science/article/pii/S0032386199001639
http://dx.doi.org/10.1016/S0032-3861(99)00163-9
[28] De Rosa, C., Auriemma, F., Fanelli, E., Talarico, G. and Capitani, D. (2003) Structure of Copolymers of Syndiotactic Polypropylene with Ethylene. Macomolecules, 36, 1850-1864.
http://pubs.acs.org/doi/abs/10.1021/ma020981v
[29] Radulescu, A., Mathers, R.T., Coates, G.W., Richter, D. and Fetters, L.J. (2004) A SANS Study of the Self-Assembly in Solution of Syndiotactic Polypropylene Homopolymers, Syndiotactic Polypropylene-Block-Poly(Ethylene-co-Propylene) Diblock Copolymers and an Alternating Atactic-Isotactic Multisegment Polypropylene. Macromolecules, 37, 6962-6971. http://pubs.acs.org/doi/abs/10.1021/ma049426e
http://dx.doi.org/10.1021/ma049426e
[30] Arranz-Andrés, J., Guevara, J.L., Velilla, T., Quijada, R., Benavente, R., Pérez, E. and Cerrada, M.L. (2005) Syndiotactic Polypropylene and Its Copolymers with Alpha-Olefins. Effect of Composition and Length of Comonomer. Polymer, 46, 12287-12297.
http://www.sciencedirect.com/science/article/pii/S0032386105015430
http://dx.doi.org/10.1016/j.polymer.2005.10.078
[31] De Rosa, C. and Auriemma, F. (2006) Mechanical Properties of Syndiotactic Propylene-Ethylene Copolymers. Macromolecules, 39, 249-256. http://pubs.acs.org/doi/abs/10.1021/ma051228f
http://dx.doi.org/10.1021/ma051228f
[32] De Rosa, C. and Auriemma, F. (2006) Structure of Syndiotactic Propylene-Ethylene Copolymers: Effect of the Presence of Ethylene Units on the Structural Transitions during Plastic Deformation and Annealing of Syndiotactic Polypropylene. Polymer, 47, 2179-2188.
http://www.sciencedirect.com/science/article/pii/S0032386106000528
http://dx.doi.org/10.1016/j.polymer.2006.01.055
[33] Allegra, S.V. and Porzio, W. (1999) Isomorphous Polymer Pairs. In: Brandrup, J., Immergut, E.H. and Grulke, E.A., Eds., Polymer Handbook, 4th Edition, Wiley & Sons, Inc., New York, 399-407.
[34] Gorrasi, G., Vittoria, V. and Longo, P. (2001) Transport and Mechanical Properties of iPP-sPP Fibers. Journal of Applied Polymer Science, 80, 539-545.
http://dx.doi.org/10.1002/1097-4628(20010425)80:4<539::AID-APP1128>3.0.CO;2-3
http://onlinelibrary.wiley.com/doi/10.1002/1097-4628(20010425)80:4%3C539::AID-APP1128%3E3.0.CO;2-3
[35] Thomann, R., Kressler, J., Setz, S., Wang, C. and Mülhaupt, R. (1996) Morphology and Phase Behavior of Blends of Syndiotactic and Isotactic Polypropylene: 1. X-Ray Scattering, Light Microscopy, Atomic Force Microscopy and Scanning Electron Microscopy. Polymer, 37, 2627-2634.
http://www.sciencedirect.com/science/article/pii/003238619687621X
http://dx.doi.org/10.1016/0032-3861(96)87621-X
[36] Thomann, R., Kressler, J., Rudolf, B. and Mülhaupt, R. (1996) Morphology and Phase Behavior of Blends of Syndiotactic and Isotactic Polypropylene: 2. Differential Scanning Calorimetry, Light Transmission Measurements and PVT Measurements. Polymer, 37, 2635-2640.
http://www.sciencedirect.com/science/article/pii/0032386196876221
http://dx.doi.org/10.1016/0032-3861(96)87622-1
[37] Wang, Z.G., Phillips, R.A. and Hsiao, B.S. (2001) Morphology Development during Isothermal Crystallization. II. Isotactic and Syndiotactic Polypropylene Blends. Journal of Polymer Science Part B: Polymer Physics, 39, 1876-1888.
http://onlinelibrary.wiley.com/doi/10.1002/polb.1162
http://dx.doi.org/10.1002/polb.1162
[38] Zhang, X., Zhao, Y., Wang, Z., Zheng, C., Dong, X., Su, Z., Sun, P., Wang, D., Han, C.C. and Xu, D. (2005) Morphology and Mechanical Behavior of Isotactic Polypropylene (iPP)/Syndiotactic Polypropylene (sPP) Blends and Fibers. Polymer, 46, 5956-5965.
http://www.sciencedirect.com/science/article/pii/S0032386105005641
http://dx.doi.org/10.1016/j.polymer.2005.05.004
[39] Loos, J., Bonnet, M. and Petermann, J. (2000) Morphologies and Mechanical Properties of Syndiotactic Polypropylene (sPP)/Polyethylene (PE) Blends. Polymer, 41, 351-356.
http://www.sciencedirect.com/science/article/pii/S0032386199000920
http://dx.doi.org/10.1016/S0032-3861(99)00092-0
[40] Marquardt, J., Thomann, R., Thomann, Y., Heinmann, J. and Mülhaupt, R. (2001) Miscibility of Branched Ethene Homopolymers with Isoand Syndiotactic Polypropenes. Macromolecules, 34, 8669-8674.
http://pubs.acs.org/doi/abs/10.1021/ma010766z
http://dx.doi.org/10.1021/ma010766z
[41] Turner Jones, A. (1966) Cocrystallization in Copolymers of α-Olefins II—Butene-1 Copolymers and Polybutene Type II/I Crystal Phase Transition. Polymer, 7, 23-59.
http://www.sciencedirect.com/science/article/pii/S0032386166800150
http://dx.doi.org/10.1016/S0032-3861(66)80015-0
[42] Hewett, W.A. and Weir, F.E. (1963) Dynamic Properties of Homo-and Copolymers of 4-Methyl-1-Pentene. Journal of Polymer Science Part A: General Papers, 1, 1239-1244.
http://onlinelibrary.wiley.com/doi/10.1002/pol.1963.100010414
http://dx.doi.org/10.1002/pol.1963.100010414
[43] Gohil, R.M. and Petermann, J. (1980) Mixed Crystals in Polymer Blends: Polypropylene-Polybutene-1 System. Journal of Macromolecular Science, Part B: Physics, 18, 217-232.
http://www.tandfonline.com/doi/abs/10.1080/00222348008241379?journalCode=lmsb20#.VAfp6pUcR9M
http://dx.doi.org/10.1080/00222348008241379
[44] Supaphol, P. (2000) Nonisothermal Bulk Crystallization and Subsequent Melting Behavior of Syndiotactic Polypropylenes: Crystallization from the Melt State. Journal of Appllied Polymer Science, 78, 338-354.
http://dx.doi.org/10.1002/1097-4628(20001010)78:2<338::AID-APP140>3.0.CO;2-Y
http://onlinelibrary.wiley.com/doi/10.1002/1097-4628(20001010)78:2%3C338::AID-APP140%3E3.0.CO;2-Y
[45] Ozawa, T. (1971) Kinetics of Non-Isothermal Crystallization. Polymer, 12, 150-158.
http://www.sciencedirect.com/science/article/pii/0032386171900413
http://dx.doi.org/10.1016/0032-3861(71)90041-3
[46] Sevengney, M.S., Parthasarthy, G., Kannan, R.M., Thurman, D.W. and Fernandez-Ballester, L. (2003) Deformation-Induced Morphology Changes and Orientation Behavior in Syndiotactic Polypropylene. Macromolecules, 36, 6472-6483. http://pubs.acs.org/doi/abs/10.1021/ma025774%2B
http://dx.doi.org/10.1021/ma025774+
[47] Sevengney, M.S., Kannan, R.M., Siedle, A.R., Naik, R. and Naik, V.M. (2006) Vibrational Spectroscopic Investigation of Stereoregularity Effects on Syndiotactic Polypropylene Structure and Morphology. Vibration Spectroscopy, 40, 246-256. http://www.sciencedirect.com/science/article/pii/S0924203105001396
[48] Sevengney, M.S., Kannan, R.M., Siedle, A.R. and Percha, P.A. (2005) FTIR Spectroscopic Investigation of Thermal Effects in Semi-Syndiotactic Polypropylene. Journal Polymer Science Part B: Polymer Physics, 43, 439-461.
http://onlinelibrary.wiley.com/doi/10.1002/polb.20334
http://dx.doi.org/10.1002/polb.20334
[49] Zheng, K., Liu, R., Chang, H., Shen, D. and Huang, Y. (2009) In Situ FTIR Spectroscopic Study of the Conformational Change of Syndiotactic Polypropylene during the Isothermal Crystallization. Polymer, 50, 5782-5786.
http://www.sciencedirect.com/science/article/pii/S0032386109008829
http://dx.doi.org/10.1016/j.polymer.2009.10.017
[50] Guadagno, L., D’Aniello, C., Naddeo, C. and Vittoria, V. (2000) Polymorphism of Oriented Syndiotactic Polypropylene. Macromolecules, 33, 6023-6030. http://pubs.acs.org/doi/abs/10.1021/ma0005973
http://dx.doi.org/10.1021/ma0005973
[51] Guadagno, L., D’Aniello, C., Naddeo, C. and Vittoria, V. (2001) Structure and Physical Properties of Syndiotactic Polypropylene Oriented from Different Polymorphs. Macromolecules, 34, 2512-2521.
http://pubs.acs.org/doi/abs/10.1021/ma0019398
http://dx.doi.org/10.1021/ma0019398
[52] De Rosa, C., de Ballesteros, O.R., Santoro, M. and Auriemma, F. (2003) Influence of the Quenching Temperature on the Crystallization of the Trans-Planar Mesomorphic Form of Syndiotactic Polypropylene. Polymer, 44, 6267-6272.
http://www.sciencedirect.com/science/journal/00323861/44/20
http://dx.doi.org/10.1016/S0032-3861(03)00569-X

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