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Year 2018, Volume: 5 Issue: 3, 1095 - 1104, 01.09.2018
https://doi.org/10.18596/jotcsa.428666

Abstract

References

  • 1. Mehrotra RC, Bohra R, Gaur DP, Metal β-Diketonates and Allied Derivatives, Academic Press, London (1978).
  • 2. Fay RC, Lindmark AF. Nuclear magnetic resonance studies of inversion and diketonate R-group exchange in dialkoxybis (. beta.-diketonato) titanium (IV) complexes. Evidence for a twist mechanism. Journal of the American Chemical Society. 1983; 105(8): 2118-2127.
  • 3. Schubert U, Huesing N, Lorenz A. Hybrid inorganic-organic materials by sol-gel processing of organofunctional metal alkoxides. Chemistry of materials. 1995; 7(11): 2010-2027.
  • 4. Fleeting KA, O'Brien P, Otway DJ, White AJ, Williams DJ, Jones AC. Studies on Mixed β-Diketonate/Isopropoxide Compounds of Zirconium and Hafnium, the X-ray Single-Crystal Structures of [M2(OPri)6 (tmhd)2](M= Zr, Hf): Some Chemistry Important in the MOCVD of Oxides. Inorganic Chemistry. 1999; 38(7): 1432-1437.
  • 5. Hoebbel D, Reinert T, Schmidt H, Arpac E. On the hydrolytic stability of organic Ligands in Al-, Ti-and Zr-alkoxide complexes. Journal of sol-gel science and technology. 1997;10 (2): 115-126.
  • 6. Maurer C, Pittenauer E, Du VA, Allmaier G, Schubert U. Cyclic bis (β-diketonate)-and bis (β-ketoesterate)-bridged titanium and zirconium alkoxide derivatives. Dalton Transactions. 2012; 41(8): 2346-2353.
  • 7. Kurajica S, Skoric I, Mandic V. Ethyl acetoacetate ligand distribution in the course of titanium n-butoxide chelation. Materials Chemistry and Physics. 2014: 147(3): 1058-1067.
  • 8. Errington RJ, Ridland J, Clegg W, Coxall RA, Sherwood JM. β-Diketonate derivatives of titanium alkoxides: X-ray crystal structures and solution dynamics of the binuclear complexes [{Ti (OR)3 (dik)}2]. Polyhedron. 1998; 17(5): 659-674.
  • 9. Kickelbick G, Schubert U. An unusual ring structure of an oligomeric oxotitanium alkoxide carboxylate. European journal of inorganic chemistry. 1998; 1998(2): 159-161.
  • 10. Schubert U. Organically modified transition metal alkoxides: Chemical problems and structural issues on the way to materials syntheses. Accounts of chemical research. 2007; 40(9): 730-737.
  • 11. Yalcin G, Yildiz U, Kayan A. Preparation of Al, Ti, Zr-perfluoroheptanoate compounds and their use in ring opening polymerization. Applied Catalysis A: General. 2012; 423: 205-210.
  • 12. Mert, O., Kayan, A. Synthesis of silyliminophenolate zirconium compounds and their catalytic activity over lactide/epoxide. Applied Catalysis A: General. 2013; 464, 322-331.
  • 13. Umare PS, Tembe GL, Rao KV, Satpathy US, Trivedi B. Catalytic ring-opening polymerization of L-lactide by titanium biphenoxy-alkoxide initiators. Journal of Molecular Catalysis. 2007; 268(1-2): 235-243.
  • 14. Saridis E, Maroulas SD, Pitsikalis M. Ring-opening polymerization of L‐lactide using half‐titanocene complexes of the ATiCl2Nu type: Synthesis, characterization, and thermal properties. Journal of Polymer Science Part A: Polymer Chemistry. 2013; 51(5): 1162-1174.
  • 15. He JX, Duan YL, Kou X, Zhang YZ, Wang W, Yang Y, Huang Y. Dinuclear group 4 alkoxides: Excellent initiators for ring-opening polymerization of cyclic esters. Inorganic Chemistry Communications. 2015; 61: 144-148.
  • 16. D'Auria I, Lamberti M, Mazzeo M, Milione S, Roviello G, Pellecchia C. Coordination chemistry and reactivity of zinc complexes supported by a phosphido pincer ligand. Chemistry-A European Journal. 2012; 18(8), 2349-2360.
  • 17. Chisholm. MH, Gallucci JC, Zhen H, Huffman JC. Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand. Inorganic chemistry. 2001; 40(19): 5051-5054.
  • 18. Hubert-Pfalzgraf, LG, Cauro-Gamet L, Brethon A, Daniele S, Richard P. (2007). Lanthanide molecular oxohydroxides: Synthesis and characterisation of [Y4 (μ4- O)(μ-OEt)2 (μ, η2-AAA)2 (η2-AAA)3]2 (μ3-OH) 4 (μ3-OEt)2 (HAAA= allylacetatoacetate). Inorganic Chemistry Communications, 2007;10(2): 143-147.
  • 19. Kayan A. Preparation and characterization of TAMP/TIMP-Ti and Zr compounds and their catalytic activity over propylene oxide and Ɛ-caprolactone. Journal of the Turkish Chemical Society, Section A: Chemistry. 2017; 4(1): 59-80.
  • 20. Schubert U. Silica-based and transition metal-based inorganic-organic hybrid materials-A comparison. Journal of sol-gel science and technology, 2003; 26(1-3): 47-55.
  • 21. Faustini M, Nicole L, Ruiz-Hitzky E, Sanchez C. History of Organic–Inorganic Hybrid Materials: Prehistory, Art, Science, and Advanced Applications. Advanced Functional Materials. 2018.
  • 22. Chisholm MH. Trispyrazolylborate ligands as ancillary ligands in the development of single-site metal alkoxide catalysts for ring-opening polymerization of cyclic esters. Inorganica Chimica Acta. 2009; 362(12): 4284-4290.
  • 23. Mert O, Kayan A. Synthesis and characterization of substituted salicylate zirconium compounds and their catalytic activity over ε-caprolactone. Journal of Inclusion Phenomena and Macrocyclic Chemistry. 2014; 80(3-4): 409-416.
  • 24. Chmura AJ, Davidson MG, Jones MD, Lunn MD, Mahon MF. Group 4 complexes of amine bis (phenolate) s and their application for the ring opening polymerisation of cyclic esters. Dalton Transactions. 2006; (7): 887-889.
  • 25. Yildiz BC, Kayan A. Preparation of single-site tin (IV) compounds and their use in the polymerization of ε-caprolactone. Designed Monomers and Polymers. 2017; 20(1): 89-96.

Synthesis and characterization of Ti-/Zr-diphenylpropanedione complexes and their application in the ring opening polymerization of Ɛ-caprolactone

Year 2018, Volume: 5 Issue: 3, 1095 - 1104, 01.09.2018
https://doi.org/10.18596/jotcsa.428666

Abstract

The purpose has been to achieve a controlled ring-opening polymerization of ɛ-caprolactone, resulting in polymers with desirable properties such as high molecular weight, low polydispersity index, and highly regio-/stereo regular forms. Therefore, it is important to synthesize single site or reduced number of active site metal alkoxide compounds as catalysts. Ti(IV)/Zr(IV) diphenylpropanedione complexes were synthesized by reactions of titanium or zirconium alkoxides with diphenylpropanedione (dion)  ligand. The obtained complexes were characterized by nuclear magnetic resonance (1H-, 13C-NMR), high resolution mass (HRMS), Fourier transform infrared (FTIR) spectroscopies and elemental analysis. These compounds were tested as catalysts for the ring opening polymerization of Ɛ-caprolactone. The structure of poly-caprolactone (PCL) was analyzed by some spectroscopic techniques (NMR, FTIR) and gel permeation chromatography (GPC). In this work, all Ti-/Zr-complexes were effective over polymerization of Ɛ-caprolactone in solventless environment. Consequently, Ɛ-caprolactone polymers were obtained different average molecular weights between 7000-34000 Da with the PDI values of 1.14-1.60.

References

  • 1. Mehrotra RC, Bohra R, Gaur DP, Metal β-Diketonates and Allied Derivatives, Academic Press, London (1978).
  • 2. Fay RC, Lindmark AF. Nuclear magnetic resonance studies of inversion and diketonate R-group exchange in dialkoxybis (. beta.-diketonato) titanium (IV) complexes. Evidence for a twist mechanism. Journal of the American Chemical Society. 1983; 105(8): 2118-2127.
  • 3. Schubert U, Huesing N, Lorenz A. Hybrid inorganic-organic materials by sol-gel processing of organofunctional metal alkoxides. Chemistry of materials. 1995; 7(11): 2010-2027.
  • 4. Fleeting KA, O'Brien P, Otway DJ, White AJ, Williams DJ, Jones AC. Studies on Mixed β-Diketonate/Isopropoxide Compounds of Zirconium and Hafnium, the X-ray Single-Crystal Structures of [M2(OPri)6 (tmhd)2](M= Zr, Hf): Some Chemistry Important in the MOCVD of Oxides. Inorganic Chemistry. 1999; 38(7): 1432-1437.
  • 5. Hoebbel D, Reinert T, Schmidt H, Arpac E. On the hydrolytic stability of organic Ligands in Al-, Ti-and Zr-alkoxide complexes. Journal of sol-gel science and technology. 1997;10 (2): 115-126.
  • 6. Maurer C, Pittenauer E, Du VA, Allmaier G, Schubert U. Cyclic bis (β-diketonate)-and bis (β-ketoesterate)-bridged titanium and zirconium alkoxide derivatives. Dalton Transactions. 2012; 41(8): 2346-2353.
  • 7. Kurajica S, Skoric I, Mandic V. Ethyl acetoacetate ligand distribution in the course of titanium n-butoxide chelation. Materials Chemistry and Physics. 2014: 147(3): 1058-1067.
  • 8. Errington RJ, Ridland J, Clegg W, Coxall RA, Sherwood JM. β-Diketonate derivatives of titanium alkoxides: X-ray crystal structures and solution dynamics of the binuclear complexes [{Ti (OR)3 (dik)}2]. Polyhedron. 1998; 17(5): 659-674.
  • 9. Kickelbick G, Schubert U. An unusual ring structure of an oligomeric oxotitanium alkoxide carboxylate. European journal of inorganic chemistry. 1998; 1998(2): 159-161.
  • 10. Schubert U. Organically modified transition metal alkoxides: Chemical problems and structural issues on the way to materials syntheses. Accounts of chemical research. 2007; 40(9): 730-737.
  • 11. Yalcin G, Yildiz U, Kayan A. Preparation of Al, Ti, Zr-perfluoroheptanoate compounds and their use in ring opening polymerization. Applied Catalysis A: General. 2012; 423: 205-210.
  • 12. Mert, O., Kayan, A. Synthesis of silyliminophenolate zirconium compounds and their catalytic activity over lactide/epoxide. Applied Catalysis A: General. 2013; 464, 322-331.
  • 13. Umare PS, Tembe GL, Rao KV, Satpathy US, Trivedi B. Catalytic ring-opening polymerization of L-lactide by titanium biphenoxy-alkoxide initiators. Journal of Molecular Catalysis. 2007; 268(1-2): 235-243.
  • 14. Saridis E, Maroulas SD, Pitsikalis M. Ring-opening polymerization of L‐lactide using half‐titanocene complexes of the ATiCl2Nu type: Synthesis, characterization, and thermal properties. Journal of Polymer Science Part A: Polymer Chemistry. 2013; 51(5): 1162-1174.
  • 15. He JX, Duan YL, Kou X, Zhang YZ, Wang W, Yang Y, Huang Y. Dinuclear group 4 alkoxides: Excellent initiators for ring-opening polymerization of cyclic esters. Inorganic Chemistry Communications. 2015; 61: 144-148.
  • 16. D'Auria I, Lamberti M, Mazzeo M, Milione S, Roviello G, Pellecchia C. Coordination chemistry and reactivity of zinc complexes supported by a phosphido pincer ligand. Chemistry-A European Journal. 2012; 18(8), 2349-2360.
  • 17. Chisholm. MH, Gallucci JC, Zhen H, Huffman JC. Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand. Inorganic chemistry. 2001; 40(19): 5051-5054.
  • 18. Hubert-Pfalzgraf, LG, Cauro-Gamet L, Brethon A, Daniele S, Richard P. (2007). Lanthanide molecular oxohydroxides: Synthesis and characterisation of [Y4 (μ4- O)(μ-OEt)2 (μ, η2-AAA)2 (η2-AAA)3]2 (μ3-OH) 4 (μ3-OEt)2 (HAAA= allylacetatoacetate). Inorganic Chemistry Communications, 2007;10(2): 143-147.
  • 19. Kayan A. Preparation and characterization of TAMP/TIMP-Ti and Zr compounds and their catalytic activity over propylene oxide and Ɛ-caprolactone. Journal of the Turkish Chemical Society, Section A: Chemistry. 2017; 4(1): 59-80.
  • 20. Schubert U. Silica-based and transition metal-based inorganic-organic hybrid materials-A comparison. Journal of sol-gel science and technology, 2003; 26(1-3): 47-55.
  • 21. Faustini M, Nicole L, Ruiz-Hitzky E, Sanchez C. History of Organic–Inorganic Hybrid Materials: Prehistory, Art, Science, and Advanced Applications. Advanced Functional Materials. 2018.
  • 22. Chisholm MH. Trispyrazolylborate ligands as ancillary ligands in the development of single-site metal alkoxide catalysts for ring-opening polymerization of cyclic esters. Inorganica Chimica Acta. 2009; 362(12): 4284-4290.
  • 23. Mert O, Kayan A. Synthesis and characterization of substituted salicylate zirconium compounds and their catalytic activity over ε-caprolactone. Journal of Inclusion Phenomena and Macrocyclic Chemistry. 2014; 80(3-4): 409-416.
  • 24. Chmura AJ, Davidson MG, Jones MD, Lunn MD, Mahon MF. Group 4 complexes of amine bis (phenolate) s and their application for the ring opening polymerisation of cyclic esters. Dalton Transactions. 2006; (7): 887-889.
  • 25. Yildiz BC, Kayan A. Preparation of single-site tin (IV) compounds and their use in the polymerization of ε-caprolactone. Designed Monomers and Polymers. 2017; 20(1): 89-96.
There are 25 citations in total.

Details

Primary Language English
Subjects Chemical Engineering
Journal Section Articles
Authors

Yagmur Gökalp This is me

Asgar Kayan 0000-0002-9996-5245

Publication Date September 1, 2018
Submission Date May 30, 2018
Acceptance Date September 6, 2018
Published in Issue Year 2018 Volume: 5 Issue: 3

Cite

Vancouver Gökalp Y, Kayan A. Synthesis and characterization of Ti-/Zr-diphenylpropanedione complexes and their application in the ring opening polymerization of Ɛ-caprolactone. JOTCSA. 2018;5(3):1095-104.