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A series of rare earth phenolates substituted by alkyl groups for D,L-lactide ring-opening polymerization

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Abstract

Single component rare earth phenolates substituted by various alkyl groups have been prepared and the correlation between the aryloxides’ structure and catalytic activity in the ring-opening polymerization of D, L-lactide has also been investigated. The catalytic activity of all rare earth aryloxides, characteristics of the ring-opening polymerization as well as polymerization kinetics and mechanism were investigated. The results showed that both phenolates’ catalytic activities and polymerization characteristics changed regularly, keeping in good concordance with variations in substitutents’ number on phenol and structure of aryloxide ligands. The stronger ability of electron-donation of alkyl groups, the higher catalytic activity. Moreover, the more numbers of substituted alkyl on phenyl ring, the higher catalytic activity. The analyses of polymer ends revealed that the polymerization proceeded via a coordination-acyl-oxygen bond cleavage-insertion mechanism.

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References

  1. K E Uhrich, S M Cannizzaro, R S Langer, et al. Polymeric Systems for Controlled Drug Release[J]. Chem. Rev., 1999, 99(11): 3 181–3 189

    Article  CAS  Google Scholar 

  2. N Nimitsiriwat, E L Marshall, V C Gibson, et al. Unprecedented Reversible Migration of Amide to Schiff Base Ligands Attached to Tin: Latent Single-site Initiators for Lactide Polymerization[J]. J. Am. Chem. Soc., 2004, 126(42):13 598–13 599

    Article  CAS  Google Scholar 

  3. J C Wu, B H Huang, M L Hsueh, et al. Ring-opening Polymerization of Lactide Initiated by Magnesium and Zinc Alkoxides[J]. Polymer, 2005, 46(23): 9 784–9 792

    CAS  Google Scholar 

  4. B J O’Keefe, S M Monnier, M A Hillmyer, et al. Rapid and Controlled Polymerization of Lactide by Structurally Characterized Ferric Alkoxides[J]. J. Am. Chem. Soc., 2001, 123(2): 339–340

    Article  Google Scholar 

  5. X Y Wang, K R Liao, D P Guan, et al. Bulk Ring-opening Polymerization of Lactides Initiated by Ferric Alkoxides[J]. Macromolecules, 2005, 38(11): 4 611–4 617

    CAS  Google Scholar 

  6. B M Chamberlain, B A Jazdzewski, M Pink, et al. Controlled Polymerization of DL-Lactide and ɛ-Caprolactone by Structurally Well-defined Alkoxo-bridged Di- and Triyttrium(III) Complexes[J]. Macromolecules, 2000, 33(11):3 970–3 977

    Article  CAS  Google Scholar 

  7. K B Aubreeht, K Chang, M A Hillmyer, et al. Lactide Polymerization Activity of Alkoxide, Phenoxide, and Amide Derivatives of Yttrium(III) Arylamidinates[J]. J. Polym. Sci. Part A: Polym. Chem., 2001, 39(2): 284–293

    Article  Google Scholar 

  8. S K Russell, C L Gamble, K J Gibbins, et al. Stereoselective Controlled Polymerization of DL-Lactide with [Ti(trisphenolate)O-i-Pr]2 Initiators[J]. Maromolecules, 2005, 38(24): 10 336–10 340

    Article  CAS  Google Scholar 

  9. A J Chmura, M G Davidson, M D Jones, et al. Group 4 Complexes of Amine Bis(phenolate)s and Their Application for the Ring Opening Polymerisation of Cyclic Esters[J]. Dalton Trans., 2006, 7: 887–889

    Article  Google Scholar 

  10. L F Zhang, Z Q Shen, C P Yu, et al. Ring-opening Polymerization of D,L-Lactide by Rare Earth 2,6-Dimethylaryloxide[ J]. Polym. Int., 2004, 53(8): 1 013–1 016

    Article  CAS  Google Scholar 

  11. L Fan, Y B Xiong, K H Tu, et al. Ring-opening Polymerization of D,L-Lactide by Lanthanide Tris(2,4,6-trimethylphenolate): Characteristics and Kinetics[J]. Chin. J. Chem., 2005, 23(5): 613–616

    Article  CAS  Google Scholar 

  12. S Hirano, K T Suzuki. Exposure, Metabolism, and Toxicity of Rare Earths and Related Compounds[J]. Envir. Health Persp., 1996, 104: 85–95

    CAS  Google Scholar 

  13. P J Haley. The Pulmonary Toxicity of Stable and Radioactive Lanthanides[J]. Health Phys., 1991, 61: 809–820

    Article  CAS  Google Scholar 

  14. W M Stevels, M J K Ankone, P J Dijkstra, et al. A Versatile and Highly Efficient Catalyst System for the Preparation of Polyesters Based on Lanthanide Tris(2,2-di-tertbutylphenolate) s and Various Alcohols[J]. Macromolecules, 1996, 29(9): 3 332–3 333

    Article  CAS  Google Scholar 

  15. B M Chamberlain, Y P Sun, J R Hagadorn, et al. Discrete Yttrium (III) Complexed as Lactide Polymerization Catalysts[J]. Macromolecules, 1999, 32(7): 2 400–2 402

    Article  CAS  Google Scholar 

  16. Z Q Shen, Y Q Shen, Y F Zhang, et al. Ring Opening Polymerization of ɛ-Caprolactone by Rare Earth Alkoxide-CCl4 Systems[J]. Polym. J., 1995, 27: 59–64

    Article  CAS  Google Scholar 

  17. Z Q Shen, X H Chen, Y Q Shen, et al. Ring-opening Polymerization of ɛ-Caprolactone by Rare Earth Coordination Catalysts. I. Characteristics, Kinetics, and Mechanism of ɛ-Caprolactone Polymerization with Nd(acac)3·3H2O-AlET3 System[J]. J. Polym. Sci. Part A: Polym. Chem., 1994, 32(4): 597–603

    Article  CAS  Google Scholar 

  18. J Ling, Z Q Shen, Q H Huang. Novel Single Rare Earth Aryloxide Initiators for Ring-opening Polymerization of 2,2-dimethyltrimethylene Carbonate[J]. Macromolecules, 2001, 34(22): 7 613–7 616

    Article  CAS  Google Scholar 

  19. C P Yu, L F Zhang, K H Tu, et al. Ring-opening of D,LLactide by the Single Component Rare Earth Tris(4-tertbutylphenolate) s[J]. Polym. Bull., 2004, 52(5): 329–337

    Article  CAS  Google Scholar 

  20. J Ling, J G Shen, T E Hogen-Esch. A Density Functional Theory Study of the Mechanisms of Scandium-alkoxide Initiated Coordination-insertion Ring-opening Polymerization of Cyclic Esters[J]. Polymer, 2009, 50(15): 3 575–3 581

    Article  CAS  Google Scholar 

  21. J Z Liu, J Ling, X Li, et al. Monomer Insertion Mechanism of Ring-opening Polymerization of ɛ-Caprolactone with Yttrium Alkoxide Intermediate: A DFT Study[J]. J. Mol. Catal. A: Chem., 2009, 300(1–2): 59–64

    Article  CAS  Google Scholar 

  22. R K Kulkarni, E G Moore, A F Hegyeli. Biodegradable Poly(lactic acid) Polymers[J]. J. Biomed. Mater. Res., 1971, 5: 169–181

    Article  CAS  Google Scholar 

  23. M D Taylor, C P Carter. Preparation of Anhydrous Lanthanide Halides Especially Iodides[J]. J. Inorg. Nucl. Chem., 1962, 24(4): 387–391

    Article  CAS  Google Scholar 

  24. P B Hitchcock, M F Lappert, A Singh. Three- and Four-coordinate, Hydrocarbon-soluble-aryloxides of Scandium, Yttrium, and the Lanthanoids X-ray Crystal Structure of Tris(2,6-di-t-butyl-4-methylphenoxo)scandium[J]. J. Chem. Soc. Chem. Commun., 1983, (24): 1 499–1 501

    Google Scholar 

  25. I Palard, A Soum, S M Guillaume. Unprecedented Polymerization of ɛ-Caprolactone Initiated by a Single-Site Lanthanide Borohydride Complex, [Sm(η-C5Me5)2(BH4)(thf)]: Mechanistic Insights[J]. Chem. Eur. J., 2004, 10(16): 4 054–4 062

    Article  CAS  Google Scholar 

  26. S Agarwal, C Mast, K Dehnicke, et al. Rare Earth Metal Initiated Ring-opening Polymerization of Lactones[J]. Macromol. Rapid Commun., 2000, 21: 195–212

    Article  CAS  Google Scholar 

  27. F M Kerton, A C Whitwood, C E Willions. A Highthroughput Approach to Lanthanide Complexes and Their Rapid Screening in the Ring Opening Polymerisation of Caprolactone[J]. Dalton Trans., 2004, 15: 2 237–2 244

    Google Scholar 

  28. H Ma, T P Spaniol, J Okuda. Rare Earth Metal Complexes Supported by 1,ω-Dithiaalkanediyl-bridged Bis(phenolato) Ligands: Synthesis, Characterization and Ring-opening Polymerization Catalysis of L-Lactide[J]. J. Chem. Soc.Dalton Trans., 2003, 24: 4 770–4 480

    Google Scholar 

  29. K Dehnicke, A Greiner. Unusual Complex Chemistry of Rare-earth Elements: Large Ionic Radii-small Coordination Numbers[J]. Angew Chem. Int. Ed., 2003, 42: 1 340–1 354

    Article  CAS  Google Scholar 

  30. W J Evans, H Katsumata. Polymerization of ɛ-Caprolactone by Divalent Samarium Complexes[J]. Macromolecules, 1994, 27(8): 2 330–2 332

    Article  CAS  Google Scholar 

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Correspondence to Lifang Zhang  (张丽芳).

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Funded by the Natural Science Foundation of Shanxi Province (No. 2006011069) and the Opening Foundation of Key Laboratory of Shanxi Province (No. 2009011059-7)

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Wang, Y., Niu, Y., Zhang, L. et al. A series of rare earth phenolates substituted by alkyl groups for D,L-lactide ring-opening polymerization. J. Wuhan Univ. Technol.-Mat. Sci. Edit. 26, 939–944 (2011). https://doi.org/10.1007/s11595-011-0341-y

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  • DOI: https://doi.org/10.1007/s11595-011-0341-y

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