Research Article
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Year 2018, , 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, , 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

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.