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Iranian Polymer Journal

, Volume 27, Issue 5, pp 319–327 | Cite as

Ring-opening polymerization of l-lactide catalyzed by a novel molybdenum-based catalytic system

  • Jing Hua
  • Qingqing Lv
  • Zhaobo Wang
  • Kai Liu
  • Jun Ling
Original Research
  • 130 Downloads

Abstract

As a transparent material that can be completely biodegradable, poly(l-lactide) (PL-LA) has recently received considerable attention. In this study, it our first efforts to fabricate l-lactide (L-LA) by a novel molybdenum-based catalytic system consisting of molybdenum pentachloride (MoCl5) as the main catalyst and m-cresol substituted alkyl aluminum Al(OPhCH3)(i-Bu)2 as the co-catalyst. The effects of different types of phosphorus ligands, Al:Mo molar ratios, catalyst contents,catalyst components (separate catalysis of m-cresol aluminum and cocatalysis of Al/Mo system) and polymerization temperature were investigated. The Tg and Tm of the resulting poly(l-lactide) (PL-LA) were characterized by differential scanning calorimetry (DSC), and the molecular weight and molecular weight distribution were determined by gel permeation chromatography (GPC). The GPC results showed that the molecular weight of the PL-LA was higher than that 104 g/mol and the molecular weight distribution was narrow. The structures of PL-LA was detected by 1H NMR spectroscopy (1H NMR) and X-ray diffraction (XRD) validation, which demonstrated that a moalr ratio of Mo/Al/l-lactide = 1:30:1000 showed the higher conversion rate and molecular weight. In comparison to the separate catalysis of m-cresol aluminum, the molecular weight of PL-LA prepared by the cocatalysis of Al/Mo system was slightly improved, and the molecular chains were relatively regular and the crystallinity was higher.

Keywords

Molybdenum-based catalytic system Coordination polymerization l-Lactide Poly(l-lactide) Ring-opening polymerization 

Notes

Acknowledgements

The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: The work is supported by the Natural Science Foundation of Shandong Province, China (no. ZR 2016 EMM03).

References

  1. 1.
    Von Schenck H, Ryner M, Albertsson A-C, Svensson M (2002) Ring-opening polymerization of lactones and lactides with Sn(IV) and Al(III) initiators. Macromolecules 35:1556–1562CrossRefGoogle Scholar
  2. 2.
    Liu K, Lv QQ, Hua J (2017) Study on damping properties of HVBR/EVM blends prepared by in situ polymerization. Polym Test 60:321–325CrossRefGoogle Scholar
  3. 3.
    Zhao W, Wang Y, Liu X, Chen X, Cui D (2012) Synthesis of isotactic-heterotactic stereo block (hard-soft) poly(lactide) with tacticity control through immortal coordination polymerization. Chem Asian J 7:2403–2410CrossRefGoogle Scholar
  4. 4.
    Ma H, Okuda J (2005) Kinetics and mechanism of l-lactide polymerization by rare earth metal silylamido complexes: effect of alcohol addition. Macromolecules 38:2665–2673CrossRefGoogle Scholar
  5. 5.
    Deng XM, Yuan ML, Xiong CD, Li XH (1999) Polymerization of lactides and lactones. II. Ring-opening polymerization of ε-caprolactone and DL-lactide by organoacid rare earth compounds. J Appl Polym Sci 71:1941–1948CrossRefGoogle Scholar
  6. 6.
    Li W, Zhang Z, Yao Y, Zhang Y, Shen Q (2012) control of conformations of piperazidine-bridged bis(phenolato) groups: syntheses and structures of bimetallic and monometallic lanthanide amides and their application in the polymerization of lactides. Organometallics 31:3499–3511CrossRefGoogle Scholar
  7. 7.
    Long P, Huang X, Jing L, Wu Y, Zheng N (2000) Novel single and double-layer and three-dimensional structures of rare-earth metal coordination polymers: the effect of lanthanide contraction and acidity control in crystal structure formation. Angew Chem Int Ed 39:527–530CrossRefGoogle Scholar
  8. 8.
    Zhang J, Qiu J, Yao Y, Zhang Y, Wang Y, Shen Q (2012) Synthesis and characterization of lanthanide amides bearing aminophenoxy ligands and their catalytic activity for the polymerization of lactides. Organometallics 31:3138–3148CrossRefGoogle Scholar
  9. 9.
    Liu J, Ling J, Li X, Shen Z (2009) Monomer insertion mechanism of ring-opening polymerization of ɛ-caprolactone with yttrium alkoxide intermediate: a DFT study. J Mol Catal A: Chem 300:59–64CrossRefGoogle Scholar
  10. 10.
    Amgoune A, Thomas C, Carpentier J (2009) Controlled ring-opening polymerization of lactide by group 3 metal complexes. Pure Appl Chem 79:2013–2030CrossRefGoogle Scholar
  11. 11.
    Sauer A, Kapelski A, Fliedel C, Dagorne S, Kol M, Okuda J (2013) Structurally well-defined group 4 metal complexes as initiators for the ring-opening polymerization of lactide monomers. Dalton Trans 42:9007–9023CrossRefGoogle Scholar
  12. 12.
    Kido J, Okamoto Y (2002) Organo lanthanide metal complexes for electroluminescent materials. Chem Rev 102:2357–2368CrossRefGoogle Scholar
  13. 13.
    Zhang M, Ni X, Shen Z (2014) Synthesis of bimetallic bis(phenolate) N-heterocyclic carbene lanthanide complexes and their applications in the ring-opening polymerization of l-lactide. Organometallics 33:6861–6867CrossRefGoogle Scholar
  14. 14.
    Alhashmialameer D, Ikpo N, Collins J, Dawe LN, Hattenhauer K, Kerton FM (2015) Ring-opening polymerization of rac-lactide mediated by tetrametallic lithium and sodium diamino-bis(phenolate) complexes. Dalton Trans 44:20216–20231CrossRefGoogle Scholar
  15. 15.
    Wang L, Roşca SC, Poirier V, Sinbandhit S, Dorcet V, Roisnel T, Carpentier JF, Sarazin Y (2014) Stable divalent germanium, tin and lead amino(ether)-phenolate monomeric complexes: structural features, inclusion heterobimetallic complexes, and ROP catalysis. Dalton Trans 43:4268–4286CrossRefGoogle Scholar
  16. 16.
    Dı́az E, Valenciano R, Landa P, Arana JL, González J (2002) Viscometric study of complexes of poly(vinyl pyrrolidone) with Co2+. Polym Test 21:247–251CrossRefGoogle Scholar
  17. 17.
    Ahuja R, Kundu S, Goldman AS, Brookhart Vicente BC, Scott SL (2008) Catalytic ring expansion, contraction, and metathesis-polymerization of cycloalkanes. Chem Commun 2:253–255CrossRefGoogle Scholar
  18. 18.
    Cotton FA, Frenz BA (1974) Conformation of fused cycloalkanes in organometallic complexes. II. The structure of bis(tricyclo[6.3.0.0 2,7]undeca-3,5-diene)dicarbonylmolybdenum, (C11H14)2 Mo(CO)2. Acta Cryst B30:1772–1776CrossRefGoogle Scholar
  19. 19.
    Tian W, Xu H, Tian J, Xu L, Hua J (2009) Synthesis of high vinyl polybutadiene rubber catalyzed by MoCl5/tributyl phosphate/Al(OPhCH3)(i-Bu)2. Chin Synth Rub Ind 32:75Google Scholar
  20. 20.
    Malcolmson SJ, Meek SJ, Sattely ES, Schrock RR, Hoveyda AH (2008) Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis. Nature 456:933–937CrossRefGoogle Scholar
  21. 21.
    Maruta Y, Abiko A (2014) Random copolymerization of ε-caprolactone and l-lactide with molybdenum complexes. Polym Bull 71:989–999CrossRefGoogle Scholar
  22. 22.
    Geng J, Sun Y, Hua J (2016) 1,2- and 3,4-rich polyisoprene synthesized by Mo(VI)-based catalyst with phosphorus ligand. Polym Sci Ser B 58:495–502CrossRefGoogle Scholar
  23. 23.
    Tian W, Tian J, Geng J, Hua J, Xu L (2009) Effect of tributyl phosphate on molybdenum-based catalyst system catalyzed polymerization of butadiene. Chin Synth Rub Ind 32:196–200Google Scholar
  24. 24.
    Düz B, Elbistan CK, Ece A, Sevin F (2009) Application of carbon arc-generated Mo- and W-based catalyst systems to the ROMP of norbornene. Appl Organometal Chem 23:359–364CrossRefGoogle Scholar
  25. 25.
    Hua J, Li X, Li Y-S, Xu L, Li Y-X (2007) Atom transfer radical polymerization of butadiene using MoO2Cl2/PPh3 as the catalyst. J Appl Polym Sci 104:3517–3522CrossRefGoogle Scholar
  26. 26.
    Dawans F, Teyssie P (1969) Process and catalytic compositions for obtaining amorphous 1,2-Polybutadiene and the products thereof. US patent 3,451,987AGoogle Scholar
  27. 27.
    Chow WS, Lok SK (2009) Thermal properties of poly(lactic acid)/organo-montmorillonite nanocomposites. J Therm Anal Calorim 95:627–632CrossRefGoogle Scholar
  28. 28.
    Ji YY, Kim Y, Ko YS (2013) Ring-opening polymerization behavior of l -lactide catalyzed by aluminum alkyl catalysts. J Ind Eng Chem 19:1137–1143CrossRefGoogle Scholar
  29. 29.
    Naga N, Mizunuma K (1998) Chain transfer reaction by trialkylaluminum(AIR3) in the stereospecific polymerization of propylene with metallocene-AIR3/Ph3CB(C6F5)4. Polymer 39:5059–5067CrossRefGoogle Scholar
  30. 30.
    Kretschmer WP, Meetsma A, Hessen B, Schmalz T, Qayyum S, Kempe R (2006) Reversible chain transfer between organoyttrium cations and aluminum: synthesis of aluminum-terminated polyethylene with extremely narrow molecular-weight distribution. Chem Eur J 12:8969–8978CrossRefGoogle Scholar
  31. 31.
    Furukawa T, Sato H, Murakami R, Zhang J, Duan Y-X, Noda I, Ochiai S, Ozaki Y (2005) Structure, dispersibility, and crystallinity of poly(hydroxybutyrate)/poly(l-lactic acid) blends studied by FT-IR microspectroscopy and differential scanning calorimetry. Macromolecules 38:6445–6454CrossRefGoogle Scholar
  32. 32.
    Vogel C, Hoffmann GG, Siesler HW (2009) Rheo-optical FT-IR spectroscopy of poly(3-hydroxybutyrate)/poly(lactic acid) blend films. Vib Spectrosc 49:284–287CrossRefGoogle Scholar
  33. 33.
    Vogel C, Wessel E, Siesler HW (2008) FT-IR spectroscopic imaging of anisotropic poly(3-hydroxybutyrate)/poly(lactic acid) blends with polarized radiation. Macromolecules 41:2975–2977CrossRefGoogle Scholar
  34. 34.
    Koval’Aková M, Olčák D, Hronský V, Vrábel P, Fričová O, Chodák I, Alexy P, Sučik G (2016) Morphology and molecular mobility of plasticized polylactic acid studied using solidstate 13C- and 1H-NMR spectroscopy. J Appl Polym Sci 133:43517.  https://doi.org/10.1002/app.43517 Google Scholar
  35. 35.
    Espartero JL, Rashkov I, Li SM, Manolova N, Vert M (1996) NMR analysis of low molecular weight poly(lactic acid)s. Macromolecules 29:3535–3539CrossRefGoogle Scholar
  36. 36.
    Nyce GW, Glauser T, Connor EF, Möck A, Waymouth RW, Hedrick JL (2003) In situ generation of carbenes: a general and versatile platform for organocatalytic living polymerization. J Am Chem Soc 125:3046–3056CrossRefGoogle Scholar
  37. 37.
    Pan P, Liang Z, Zhu B, Dong T, Inoue Y (2009) Blending effects on polymorphic crystallization of poly(l-lactide). Macromolecules 42:3374–3380CrossRefGoogle Scholar
  38. 38.
    Silverajah VS, Ibrahim NA, Zainuddin N, Yunus WM, Hassan HA (2012) Mechanical, thermal and morphological properties of poly(lactic acid)/epoxidized palm olein blend. Molecules 17:11729–11747CrossRefGoogle Scholar
  39. 39.
    Pan P, Kai W, Zhu B, Dong T, Inoue Y (2007) Polymorphous crystallization and multiple melting behavior of poly(l-lactide): molecular weight dependence. Macromolecules 40:6898–6905CrossRefGoogle Scholar
  40. 40.
    Huh KM, Bae YH (1999) Synthesis and characterization of poly(ethylene glycol)/poly(l-lactic acid) alternating multiblock copolymers. Polymer 40:6147–6155CrossRefGoogle Scholar

Copyright information

© Iran Polymer and Petrochemical Institute 2018

Authors and Affiliations

  1. 1.Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-plasticsQingdao University of Science and TechnologyQingdaoPeople’s Republic of China
  2. 2.College of Material Science and EngineeringQingdao University of Science and TechnologyQingdaoPeople’s Republic of China

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