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The effects of new aminosilane compounds as external donors on propylene polymerization

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Abstract

The new aminosilane compounds including Dimorpholindimethoxysilane (Donor-Pm), Di (1-methylpiperazine) dimethoxysilane (Donor-Pz) and Di (isopropylpiperazine) dimethoxysilane (Donor-Pi) were firstly synthesized and then employed as external donors for propylene polymerization with MgCl2-supported Ziegler-Natta catalyst, compared with dipiperidine dimethoxysilane (Donor-Py). The effects of the aminosilane external donors on the catalytic activity, hydrogen response, and molecular weight distribution, crystalline ability, thermal property, 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 these new aminosilane compounds were conducive to improving the isotacticity of polypropylene and the catalytic activity. The GPC results showed that the molecular weight distribution of polypropylene prepared respectively by Donor-Pz or Donor-Pi with two N atoms on each amino substituent group was broader more than 8.0, especially for Donor-Pi with the large alkyl-substituted group on each nitrogen atom, the molecular weight distribution of polypropylene was about 11.2, which was much broader than that of industrial polypropylene about 4 ~ 5. The DSC results indicated that the degrees of crystallinity of polypropylene prepared by the aminosilane external donors were higher, and the crystallization ability of polypropylene prepared by Donor-Pi was lower but closed to that of polypropylene prepared by Donor-Py. The SSA results indicated Donor-Py and Donor-Pi were conducive to improving the relative contents of the highest isotactic component of polypropylene, and the lamellae thicknesses results showed the sequence length of polypropylene prepared by Donor-Py and Donor-Pi were longer, and the isotactic sequence distribution of polypropylene prepared by Donor-Py and Donor-Pi were broader. The study results showed that the new aminosilane donor Donor-Pi was conducive to improving the stereo-regularity of polypropylene, especially revealing that it was a simple and an effective method to synthesize broad molecular weight distribution of polypropylene by using appropriate aminosilane external donor for propylene polymerization.

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References

  1. 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

    Article  CAS  Google Scholar 

  2. 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(8):1611–1623

    Article  CAS  Google Scholar 

  3. Zakirov MI, Kleiner VI, Adrov OI, Nifant’ev IE, Shklyaruk BF, Stroganov VS, Nedorezova PM, Klyamkina AN (2010) Effect of electron donors on polymerization of propylene in the presence of titanium-magnesium catalysts. Polym Sci Ser B 52(9–10):584–588

    Article  Google Scholar 

  4. Kim SY, Hiraoka Y, Taniike T, Terano M (2009) External donor induced direct contact effects on Mg (OC2H5)2-based Ziegler-Natta catalysts for propylene polymerization. Macromol Symp 285:115–120

    Article  CAS  Google Scholar 

  5. Vanka K, Singh G, Iyer D, Gupta VK (2010) DFT study of lewis base interactions with the MgCl2 surface in the Ziegler-Natta catalytic system: expanding the role of the donors. J Phys Chem C 114(37):15771–15781

    Article  CAS  Google Scholar 

  6. Osorio F, Fernandez J, Bracho N, Rajmankina T (2009) Effect of external donor and prepolymerization on the performance of Ziegler-Natta catalysts in propylene polymerization. Rev Tec De La Fac De Ing Univ Del Zulia 32(2):109–118

    CAS  Google Scholar 

  7. 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

    Article  CAS  Google Scholar 

  8. 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

    Article  CAS  Google Scholar 

  9. Ohnishi R, Konakazawa T (2004) Role of tert-butyl methyl ether (TBME) as an external donor in propene polymerization with dibutyl phthalate (DBP)-containing MgCl2-supported Ti catalysts activated with Al(i-C4H9)3. Macromol Chem Phys 205(14):1938–1947

    Article  CAS  Google Scholar 

  10. 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

    Article  CAS  Google Scholar 

  11. Lim SY, Choung SJ (1998) Effects of external electron donor on catalyst active sites in propylene polymerization. J Appl Polym Sci 67(10):1779–1787

    Article  CAS  Google Scholar 

  12. Shiono T, Hagihara H, Ikeda T, Soga K (1997) Control of molecular weight distribution of isotactic polypropylene obtained by a MgCl2-supported TiCl4 catalyst. Polymer 38(26):6409–6411

    Article  CAS  Google Scholar 

  13. Sacchi MC, Forlini F, Tritto I, Locatelli P, Morini G, Baruzzi G, Albizzati E (1995) Stereochemistry of the initiation step in Ziegler-Natta catalysts containing dialkyl propane diethers - a tool for distinguishing the role of internal and external donors. Macromol Symp 89:91–100

    Article  CAS  Google Scholar 

  14. Coutinho FMB, Santamaria LC (1991) Influence of internal and external electron-donors on the activity and stereospecificity of Ziegler-Natta catalysts. Eur Polym J 27(9):987–989

    Article  CAS  Google Scholar 

  15. 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(5):627–635

    Article  CAS  Google Scholar 

  16. Wang Q, Murayama N, Liu BP, Terano M (2005) Effects of electron donors on active sites distribution of MgCl2-supported Ziegler-Natta catalysts investigated by multiple active sites model. Macromol Chem Phys 206(9):961–966

    Article  CAS  Google Scholar 

  17. Pasquini N (2005) Polypropylene Handbook. Carl Hanser Verlag, Munich

    Google Scholar 

  18. Yao SG, Tanaka Y (2001) Theoretical consideration of the external donor of heterogeneous Ziegler-Natta catalysts using molecular mechanics, molecular dynamics, and QSAR analysis. Macromol Theory Simul 10(9):850–854

    Article  CAS  Google Scholar 

  19. Chadwick JC, Morini G, Balbontin G, Camurati I, Heere JJR, Mingozzi I, Testoni F (2001) Effects of internal and external donors on the regio-and stereoselectivity of active species in MgCl2-supported catalysts for propene polymerization. Macromol Chem Phys 202(10):1995–2002

    Article  CAS  Google Scholar 

  20. Harkonen M, Seppala JV, Vaananen T (1991) External alkoxysilane donors in Ziegler-Natta catalysis. Effects on poly (propylene) microstructure. Makromol Chem-Macromol Chem Phys 192(3):721–734

    Article  CAS  Google Scholar 

  21. 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

    Google Scholar 

  22. Li HY, Zhang LY, Hu YL (2010) Density functional theory study on the relationship between polymerization activity and substituent electronic effect of polyolefin catalysts. Chin J Catal 31(9):1127–1131

    CAS  Google Scholar 

  23. Cui NN, Zhang ZC, Li HY, Chen ST, Zhang XF, Ke YC, Hu YL (2005) Role of electron donor in the polymerization of propylene with MgCl2-supported catalysts. Acta Polym Sin 6:902–906

    Google Scholar 

  24. Ikeuchi H, Yano T, Ikai S, Sato H, Yamashita J (2003) Study on aminosilane compounds as external electron donors in isospecific propylene polymerization. J Mol Catal A Chem 193(1–2):207–215

    Article  CAS  Google Scholar 

  25. 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

    Article  CAS  Google Scholar 

  26. Sacchi MC, Forlini F, Tritto I, Mendichi R, Zannoni G, Noristi L (1992) Activation effect of alkoxysilane as external donors in MgCl2-supported Ziegler-Natta catalysts. Macromolecules 25(22):5914–5918

    Article  CAS  Google Scholar 

  27. Ren HG, Yang M, Li HY, Liu PG, Liu BY, Hu YL, Wang YJ (2011) Studies on aminosilane compounds as external electron donors in 1-butene polymerization. Acta Polym Sin 12:1412–1418

    Google Scholar 

  28. Moore EP (1996) Polypropylene Handbook: Polymerization, Characterization, Properties, Processing, Applications. Hanser Publishers

  29. Monasse B, Haudin J (1985) Growth transition and morphology change in polypropylene. Colloid Polym Sci 263(10):822–831

    Article  CAS  Google Scholar 

  30. Brandrup J, Immergut EH (1989) Polymer Handbook, 3rd edn. Wiley, New York

    Google Scholar 

  31. 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

    Article  CAS  Google Scholar 

  32. 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 B Polym Phys 31(10):1383–1393

    Article  CAS  Google Scholar 

  33. 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

    Article  CAS  Google Scholar 

  34. 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

    Article  CAS  Google Scholar 

  35. Song SJ, Wu PY, Feng JC, Ye MX, Yang YL (2009) Influence of pre-shearing on the crystallization of an impact-resistant polypropylene copolymer. Polymer 50(1):286–295

    Article  CAS  Google Scholar 

  36. Pérez CJ, Carella JM (2007) Early detection of degradation in a semi-crystalline polyolefin by a successive self-nucleation and annealing technique. Polym Degrad Stab 92(7):1213–1218

    Article  Google Scholar 

  37. 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

    Article  CAS  Google Scholar 

  38. Müller AJ, Arnal ML (2005) Thermal fractionation of polymers. Prog Polym Sci 30(5):559–603

    Article  Google Scholar 

  39. 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

    Article  CAS  Google Scholar 

  40. 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

    Article  Google Scholar 

  41. 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

    Article  CAS  Google Scholar 

  42. 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 (8). DOI 10.1007/s10965-013-0207-4

  43. 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

    Article  CAS  Google Scholar 

  44. Müller AJ, Lorenzo AT, Arnal ML (2009) Recent Advances and Applications of “Successive Self‐Nucleation and Annealing”(SSA) High Speed Thermal Fractionation. In. Wiley Online Library, pp 207-214

  45. 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

    Article  CAS  Google Scholar 

  46. Liu DM, 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 (5). DOI:10.1007/s10965-013-0126-4

  47. Durmus A, Yalcinyuva T (2009) Effects of additives on non-isothermal crystallization kinetics and morphology of isotactic polypropylene. J Polym Res 16(5):489–498

    Article  CAS  Google Scholar 

  48. Kang J, Yang F, Wu T, Li HL, Liu DM, 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

    Article  CAS  Google Scholar 

  49. Kang J, Cao Y, Li HL, Li JP, Chen SH, Yang F, Xiang M (2012) Influence of the stereo-defect distribution on the crystallization behavior of Ziegler-Natta isotactic polypropylene. J Polym Res 19(12):1–11

    Article  CAS  Google Scholar 

  50. Kang J, Yang F, Wu T, Li HL, 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(2):425–434

    Article  CAS  Google Scholar 

  51. Kang J, Gai JG, Li JP, Chen SH, Peng HM, Wang B, Cao Y, Li HL, Chen JY, Yang F, Xiang M (2013) Dynamic crystallization and melting behavior of beta-nucleated isotactic polypropylene polymerized with different Ziegler-Natta catalysts. J Polym Res. 20 (2). DOI:10.1007/s10965-012-0070-8

  52. 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 Polym J 39(8):1679–1685

    Article  CAS  Google Scholar 

  53. Gedde UW (1995) Polymer physics. Chapman & Hall, London

    Google Scholar 

  54. Iijima M, Strobl G (2000) Isothermal crystallization and melting of isotactic polypropylene analyzed by time- and temperature-dependent small-angle X-ray scattering experiments. Macromolecules 33(14):5204–5214

    Article  CAS  Google Scholar 

  55. 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

    Article  CAS  Google Scholar 

  56. Wlochowicz A, Eder M (1984) Distribution of lamella thicknesses in isothermally crystallized polypropylene and polyethylene by differential scanning calorimetry. Polymer 25(9):1268–1270

    Article  CAS  Google Scholar 

  57. Keating M, Lee IH, Wong CS (1996) Thermal fractionation of ethylene polymers in packaging applications. Thermochim Acta 284(1):47–56

    Article  CAS  Google Scholar 

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Acknowledgements

The authors express thanks for the supports of the National Science Foundation of China (No. 51073170).

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Hefei Chang, Tao Zheng, Qian Zhou & Liaoyun Zhang

  2. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Huayi Li & Youliang Hu

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  1. Hefei Chang
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  2. Huayi Li
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Correspondence to Huayi Li or Liaoyun Zhang.

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Chang, H., Li, H., Zheng, T. et al. The effects of new aminosilane compounds as external donors on propylene polymerization. J Polym Res 21, 554 (2014). https://doi.org/10.1007/s10965-014-0554-9

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