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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Pyrazole and pyrazolyl copper and zinc complexes in ring opening polymerization of ε-caprolactone and D,L-lactide

Appavoo, Divambal 07 June 2012 (has links)
M.Sc. / Six pyrazole and pyrazolyl compounds, 3,5-dimethylpyrazole (L1), 3,5-diphenylpyrazole (L2), 3,5-di-tert-butylpyrazole (L3), bis(3,5-dimethylpyrazol-1-yl)methane (L4), bis(3,5-diphenylpyrazol-1-yl)methane (L5) and bis(1,2-bis{(3,5-dimethylpyrazol-1-yl)methyl}benzene (L6), were reacted with Zn(II) and Cu(II) benzoates to form pyrazole and pyrazolyl metal benzoates. The complexes are [Zn(C6H5COO)2(L1)2] (1), [Zn(3,5-NO2-C6H3COO)2(L1)2] (2), [Zn(4-OH-C6H4COO)2(L1)2] (3), [Zn(2-Cl-C6H4COO)2(L1)2] (4), [Zn(C6H5COO)2(L2)2] (5), [Zn(3,5-NO2-C6H3COO)2(L2)2] (6), [Zn(4-OH-C6H4COO)2(L2)2] (7), [Zn(2-Cl-C6H4COO)2(L2)2] (8), [Zn(3,5-NO2-C6H3COO)2L4] (9), [Zn(4-OH-C6H4COO)2L6] (10), [Zn2(C6H5COO)4L6]n (11), [Zn(3,5-NO2-C6H3COO)2L6] (12), [Zn(2-Cl-C6H4COO)2L6] (13), [Cu(C6H5COO)2(L1)2] (14), [Cu(3,5-NO2-C6H3COO)2(L1)2] (15), [Cu(4-OH-C6H4COO)2(L1)2] (16), [Cu(2-Cl-C6H4COO)2(L1)2] (17), [Cu(C6H5COO)2(C6H5COOH)]2 (18), [Cu(2-Cl-C6H4COO)2(L3)2] (19), [Cu(C6H5COO)2L4] (20), [Cu(2-Cl-C6H4COO)2L4] (21), [Cu(C6H5COO)2DMSO]2 (22), [Cu(C6H5COO)2L6]2 (23), [Cu(2-Cl-C6H4COO)2L6]2n (24), [Cu(4-OH-C6H4COO)2L6]2(25) and [Cu(3,5-NO2-C6H3COO)2L6]n (26). The molecular structures of the Zn(II) and Cu(II) complexes 6, 9, 11, 14, 17-19, 22-26 were determined by X-ray diffraction studies that revealed four types of geometries adopted by these complexes: (i) 4-coordinate tetrahedral (6, 9, 14), (ii) 6-coordinate octahedral (17), (iii) paddle wheel (18, 19, 22, 23, 25) and (iv) polymeric structures (11, 24, 26). Catalysis studies performed with selected complexes (1-4, 9-17, 23-26) revealed that they initiate the ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and D,L-lactide at elevated temperatures, and under solvent-free conditions and in toluene respectively. Polycaprolactone (PCL) and poly(D,L-lactide) (PLA) produced were of moderate molecular weights (858-4 757 Da for PCL and 602-3 185 Da for PLA) and polydispersity indices (1.36-2.16 for PCL and 1.42-2.35 for PLA). End group of the iv polymers, determined by MALDI-TOF MS, were benzoates, hydroxyl, methoxy groups and cyclic. From the 13C{1H} NMR spectra of polymers synthesized, the stereochemistry of PLA was predominantly isotactic.

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