Abstract
A new aminosilane external donor named piperidine methyl dimethoxysilane (Donor-PMe) was firstly synthesized, and then was used as external donor on propylene polymerization with MgCl2-supported Ziegler-Natta catalyst. The effects of Donor-PMe on the catalytic activity, isotacticity, molecular weight distribution, isotactic sequence length, isotactic sequence distribution of polypropylene were studied by differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and self-nucleation and annealing (SSA), respectively. It was found that it was conducive to improving the activity and stereoregularity of catalyst when the new aminosilane Donor-PMe was used as external donor with MgCl2-supported Ziegler-Natta catalyst. The catalytic activity of the Ziegler-Natta catalyst and the isotacticity of PP prepared by Donor-PMe increased with the increase of Si/Ti ratio on propylene polymerization.The GPC results showed that the molecular weight distribution of polypropylene was about 6.7, which was broader than that of industrial homo-polypropylene about 3.0. The SSA results showed that the relative contents of the highest isotactic component and the lamellar thickness in the PP chain gradually increased with the increase of Si/Ti of Donor-PMe, indicating the isotactic sequence length of polypropylene got longer with the increase of Si/Ti ratio of Donor-PMe. Meanwhile, the lamellar thickness distribution of polypropylene became broader, revealing the isotactic sequence length distribution of polypropylene got broader, indicating there were more higher isotactic sequence length in PP chain.
Similar content being viewed by others
References
Qiao J, Guo M, Wang L, Liu D, Zhang X, Yu L, Song W, Liu Y (2011) Recent advances in polyolefin technology. Polym Chem 2:1611–1623
HIMONT Incorporated (1990) Components and catalysts for the polymerization of olefins. US patent 4971937
Zhang HX, Shin YJ, Lee DH, Yoon KB (2011) Preparation of ultra high molecular weight polyethylene with MgCl2/TiCl4 catalyst: effect of internal and external donor on molecular weight and molecular weight distribution. Polym Bull 66:627–635
Garoff T, Virkkunen V, Jaaskelainen P, Vestberg T (2003) A qualitative model for polymerisation of propylene with a MgCl2-supported TICl4 Ziegler-Natta catalyst. Eur Polymer J 39(8):1679–1685
Matsuoka H, Liu BP, Nakatani H, Terano M (2001) Variation in the isospecific active sites of internal donor-free MgCl2-supported Ziegler catalysts: Effect of external electron donors. Macromol Rapid Commun 22(5):326–328
Chang HF, Ren ST, Zheng T, Dang XF, Yang Y, Zhang LY, Li HY (2013) Studies on the influence of different substituted groups of the external donors on propylene polymerization. Acta Polym Sin 2:199–207
Dashti A, Ramazani SAA, Hiraoka Y, Kim SY, Taniike T, Terano M (2009) Kinetic and morphological investigation on the magnesium ethoxide-based Ziegler-Natta catalyst for propylene polymerization using typical external donors. Macromol Symp 285:52–57
Batt-Coutrot D, Wolf V, Malinge J, Saudemont T, Grison C, Coutrot P (2005) Study of dimethoxysilacycloalkanes as external donors in Ziegler-Natta stereospecific propylene polymerisation. Polym Bull 54(6):377–385
Proto A, Oliva L, Pellecchia C, Sivak AJ, Cullo LA (1990) Isotactic-specific polymerization of propene with supported catalysts in the presence of different modifiers. Macromolecules 23(11):2904–2907
Sacchi MC, Forlini F, Tritto I, Mendichi R, Zannoni G, Noristi L (1992) Activation effect of alkoxysilanes as external donors in magnesium chloride-supported Ziegler-Natta catalysts. Macromolecules 25(22):5914–5918
Wondimagegn T, Ziegler T (2012) The role of external alkoxysilane donors on stereoselectivity and molecular weight in MgCl2-supported Ziegler-Natta propylene polymerization: A density functional theory study. J Phys Chem C 116(1):1027–1033
Chang HF, Li HY, Zheng T, Zhou Q, Zhang LY, Hu YL (2014) The effects of new aminosilane compounds as external donors on propylene polymerization. J Polym Res 21:554
Fillon B, Wittmann JC, Lotz B, Thierry A (1993) Self-Nucleation and recrystallization of isotactic polypropylene (alpha-phase) investigated by differential scanning calorimetry. J Polym Sci, Part B: Polym Phys 31(10):1383–1393
Muller AJ, Hernandez ZH, Arnal ML, Sanchez JJ (1997) Successive self-nucleation/annealing (SSA): A novel technique to study molecular segregation during crystallization. Polym Bull 39(4):465–472
Lorenzo AT, Arnal ML, Muller AJ, Lin MC, Chen HL (2011) SAXS/DSC analysis of the lamellar thickness distribution on a SSA thermally fractionated model polyethylene. Macromol Chem Phys 212(18):2009–2016
Kang J, Yang F, Wu T, Li H, Liu D, Cao Y, Xiang M (2012) Investigation of the stereodefect distribution and conformational behavior of isotactic polypropylene polymerized with different Ziegler-Natta catalysts. J Appl Polym Sci 125(4):3076–3083
Fan YD, Zhang CY, Xue YH, Zhang XQ, Ji XL, Bo SQ (2011) Microstructure of two polypropylene homopolymers with improved impact properties. Polymer 52(2):557–563
Chang HF, Zhang Y, Ren ST, Dang XF, Zhang LY, Li HY, Hu YL (2012) Study on the sequence length distribution of polypropylene by the successive self-nucleation and annealing (SSA) calorimetric technique. Polym Chem 3(10):2909–2919
Zheng H, Zeng F, Chen Z, Kang J, Chen J, Cao Y, Xiang M (2017) Exploring the roles of molecular structure on the β-crystallization of polypropylene random copolymer. J Polym Res 24:225
Pérez CJ, Carella JM (2007) Early detection of degradation in a semicrystalline polyolefin by a successive self-nucleation and annealing technique. Polym Degrad Stab 92(7):1213–1218
Lorenzo AT, Arnal ML, Sanchez JJ, Muller AJ (2006) Effect of annealing time on the self-nucleation behavior of semicrystalline polymers. J Polym Sci B Polym Phys 44(12):1738–1750
Müller AJ, Arnal ML (2005) Thermal fractionation of polymers. Prog Polym Sci 30(5):559–603
Kang J, Chen Z, Zhou T, Yang F, Chen J, Cao Y, Xiang M (2014) Dynamic crystallization and melting behavior of β-nucleated isotactic polypropylene with different melt structures. J Polym Res 21:384
Virkkunen V, Laari P, Pitkänen P, Sundholm F (2004) Tacticity distribution of isotactic polypropylene prepared with heterogeneous Ziegler-Natta catalyst. 2. Application and analysis of SSA data for polypropylene. Polymer 45(14):4623–4631
Muller AJ, Arnal ML, Spinelli AL, Canizales E, Puig CC, Wang H (2003) Morphology and crystallization kinetics of melt miscible polyolefin blends. Macromol Chem Phys 204(12):1497–1513
Ding C, Zhang G, Gu J, Cao F, Zheng X (2017) Application of the correct design of successive self-nucleation and annealing (SSA) to study the stereo-defects and its distribution of homo- and co-polypropylene. RSC Adv 7:24870–24877
Arnal ML, Balsamo V, Ronca G, Sanchez A, Muller AJ, Canizales E, de Navarro CU (2000) Applications of successive self-nucleation and annealing (SSA) to polymer characterization. J Therm Anal Calorim 59(1–2):451–470
Chang HF, Li HY, Zheng T, Zhang LY, Yuan W, Li L, Huang H, Hu YL (2013) Characterization of the effects of the C/N mixed external donors on the stereo-defects distribution of polypropylene by successive self-nucleating and annealing and 13C-NMR techniques. J Polym Res 20:207
Kang J, Yang F, Wu T, Li H, Cao Y, Xiang M (2012) Polymerization control and fast characterization of the stereo-defect distribution of heterogeneous Ziegler-Natta isotactic polypropylene. Eur Polym J 48:425–434
Pijpers TFJ, Mathot VBF, Goderis B, Scherrenberg RL, van der Vegte EW (2002) High-speed calorimetry for the study of the kinetics of (De) vitrification, crystallization, and melting of macromolecules. Macromolecules 35(9):3601–3613
Xue YH, Fan YD, Bo SQ, Ji XL (2011) Characterization of the microstructure of impact polypropylene alloys by preparative temperature rising elution fractionation. Eur Polym J 47(8):1646–1653
Suarez I, Caballero MJ, Coto B (2011) Characterization of ethylene/propylene copolymers by means of a GPC-4D technique. Eur Polym J 47(2):171–178
Müller AJ, Michell RM, Pérez RA, Lorenzo AT (2015) Successive Self-nucleation and Annealing (SSA): Correct design of thermal protocol and applications. Eur Polym J 65:132–154
Liu D, Kang J, Xiang M, Cao Y (2013) Effect of annealing on phase structure and mechanical behaviors of polypropylene hard elastic films. J Polym Res 20:126
Song SJ, Wu PY, Feng JC, Ye MX, Yang YL (2009) Influence of preshearing on the crystallization of an impact-resistant polypropylene copolymer. Polymer 50(1):286–295
Gedde UW (1995) Polymer physics. Chapman & Hall, London
Iijima M, Strobl G (2000) Isothermal crystallization and melting of isotactic polypropylene analyzed by time- and temperaturedependent small-angle X-ray scattering experiments. Macromolecules 33(14):5204–5214
Bond EB, Spruiell JE, Lin JS (1999) A WAXD/SAXS/DSC study on the melting behavior of Ziegler-Natta and metallocene catalyzed isotactic polypropylene. J Polym Sci B: Polym Phys 37(21):3050–3064
Wlochowicz A, Eder M (1984) Distribution of lamella thicknesses in isothermally crystallized polypropylene and polyethylene by differential scanning calorimetry. Polymer 25(9):1268–1270
Keating M, Lee IH, Wong CS (1996) Thermal fractionation of ethylene polymers in packaging applications. Thermochim Acta 284(1):47–56
Funding
National Natural Science Foundation of China, Grant No. 22209053, Cong Ding
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflicts of Interest
The authors declare no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Chang, H., Li, H., Li, C. et al. The effects of a new aminosilane external donor on propylene polymerization with MgCl2-supported Ziegler-Natta catalyst. J Polym Res 31, 35 (2024). https://doi.org/10.1007/s10965-024-03869-w
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10965-024-03869-w