期刊
RSC ADVANCES
卷 11, 期 22, 页码 13475-13485出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ra00339a
关键词
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资金
- University of Johannesburg
- National Research Foundation (South Africa)
- Spanish MINECO [CTQ2017-87201-P]
- Generalidad Valenciana [Prometeo/2019/076]
In this study, four copper complexes were synthesized and characterized, showing the ability to catalyze the ring opening polymerization of ε-caprolactone and d,l-lactide to obtain polymers with low molecular weights and polydispersity indices. The end group analysis revealed the presence of benzoate, hydroxyl, methoxy, and cyclic end groups in the polymers.
1,2-Bis{(3,5-dimethylpyrazol-1-yl)methyl}benzene (L) reacts with [Cu(OAc)(2)] and C6H5COOH, 4-OH-C6H4COOH, 2-Cl-C6H4COOH and (3,5-NO2)(2)-C6H3COOH to afford the copper complexes [Cu-2(C6H5COO)(4)(L)(2)] (1), [Cu-2(4-OH-C6H4COO)(4)(L)(2)] (2), [Cu-2(2-Cl-C6H4COO)(4)(L)(2)](n) (3) and [Cu{(3,5-NO2)(2)-C6H3COO}(2)L](n) (4) which are characterised by IR, mass spectrometry, elemental analyses, and X-ray crystallography. The structural data revealed two geometries that are adopted by the complexes: (i) paddle wheel in 1, 2 center dot 7H(2)O, 3 and (ii) regular chains in 3 and 4. Magnetic studies show strong antiferromagnetic couplings in the paddle wheel complexes and a weak antiferromagnetic coupling in the monometallic chain one. Catalysis studies performed with these complexes (1-4) showed that they initiate ring opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) under solvent-free conditions and d,l-lactide in toluene at elevated temperatures. Polycaprolactone (PCL) and poly(d,l-lactide) (PLA) obtained from the polymerization reactions are of low molecular weights (858 for PCL and 602 Da for PLA for initiator 1) and polydispersity indices (typically 2.16 for PCL and 1.64 for PLA with 1 as the initiator). End group analysis of the polymers, determined by MALDI-ToF MS, indicates that the polymers have benzoate, hydroxyl, methoxy and cyclic end groups.
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