Polymers of ε-Caprolactone Using New Copper(II) and Zinc(II) Complexes as Initiators: Synthesis, Characterization and X-Ray Crystal Structures

被引:12
作者
Posada, Andres F. [1 ]
Macias, Mario A. [1 ]
Movilla, Santiago [1 ]
Pietro Miscione, Gian [1 ]
Perez, Leon D. [2 ]
Hurtado, John J. [1 ]
机构
[1] Univ Andes, Dept Quim, Carrera 1 18A-12, Bogota 111711, Colombia
[2] Univ Nacl Colombia, Grp Macromol, Dept Quim, Carrera 45 26-85,Edificio 451 449, Bogota 11001, Colombia
关键词
ring-opening polymerization; epsilon-caprolactone; bis(3,5-dimethylpyrazole) ligands; zinc(II) and copper(II) complexes; crystal structures; RING-OPENING POLYMERIZATION; CHROMIUM(III) COMPLEXES; EFFICIENT INITIATORS; LIGANDS SYNTHESIS; CU(II) COMPLEXES; BEARING; BLENDS;
D O I
10.3390/polym10111239
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Five of six new Zn(II) and Cu(II) complexes were active in the ring-opening polymerization (ROP) of epsilon-caprolactone (CL) under solvent-free conditions, producing polycaprolactones (PCLs) of high crystallinity with molecular weights between 22,900 and 38,700 g mol(-1) and decomposition temperatures above 260 degrees C. H-1 NMR analysis demonstrated that the PCLs obtained were mainly linear, having hydroxymethylene groups at the chain ends. The results obtained indicated a significant improvement in terms of the ratio of monomer: initiator compared to related Cu(II) and Zn(II) complexes. In addition, the structures of the complexes 1 and 4 were determined by single-crystal X-ray diffraction. The synthesis and full characterization of all complexes are described in this paper.
引用
收藏
页数:14
相关论文
共 43 条
[1]   ELECTRONEGATIVITY VALUES FROM THERMOCHEMICAL DATA [J].
ALLRED, AL .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1961, 17 (3-4) :215-221
[2]   Bis(3,5-dimethylpyrazole) copper(II) and zinc(II) complexes as efficient initiators for the ring opening polymerization of ε-caprolactone and D,L-lactide [J].
Appavoo, Divambal ;
Omondi, Bernard ;
Guzei, Ilia A. ;
van Wyk, Juanita L. ;
Zinyemba, Orpah ;
Darkwa, James .
POLYHEDRON, 2014, 69 :55-60
[3]   LIVING POLYMERIZATION AND SELECTIVE END FUNCTIONALIZATION OF EPSILON-CAPROLACTONE USING ZINC ALKOXIDES AS INITIATORS [J].
BARAKAT, I ;
DUBOIS, P ;
JEROME, R ;
TEYSSIE, P .
MACROMOLECULES, 1991, 24 (24) :6542-6545
[4]   Steric effects in controlling co-ordination environment in zinc 2-nitrobenzoate complexes [J].
Baruah, Abhilasha M. ;
Karmakar, Anirban ;
Baruah, Jubaraj B. .
INORGANICA CHIMICA ACTA, 2008, 361 (9-10) :2777-2784
[5]   Coordination Polymers Containing 1,3-Phenylenebis-((1H-1,2,4-triazol-1-yl)methanone) Ligand: Synthesis and ε-Caprolactone Polymerization Behavior [J].
Bello-Vieda, Nestor J. ;
Murcia, Ricardo A. ;
Munoz-Castro, Alvaro ;
Macias, Mario A. ;
Hurtado, John J. .
MOLECULES, 2017, 22 (11)
[6]   Heavy Halogen Atom Effect on 13C NMR Chemical Shifts in Monohalo Derivatives of Cyclohexane and Pyran. Experimental and Theoretical Study [J].
Cunha Neto, Alvaro ;
Ducati, Lucas C. ;
Rittner, Roberto ;
Tormena, Claudio F. ;
Contreras, Ruben H. ;
Frenking, Gernot .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2009, 5 (09) :2222-2228
[7]   Tetrahedral vs octahedral zinc complexes with ligands of biological interest: A DFT/CDM study [J].
Dudev, T ;
Lim, C .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (45) :11146-11153
[8]   METAL PYRAZOLATE POLYMERS .3. SYNTHESIS AND STUDY OF CU(I) AND CU(II) COMPLEXES OF 4-XDMPZ (WHERE X = H, CL, BR, I, AND CH3 FOR CU(I) AND X = H, CL, BR, AND CH3 FOR CU(II), DMPZ = 3,5-DIMETHYLPYRAZOLATE) [J].
EHLERT, MK ;
STORR, A ;
THOMPSON, RC .
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1992, 70 (04) :1121-1128
[9]   Crystallization kinetics of poly (ε-caprolactone) in miscible thermosetting polymer blends of epoxy resin and poly (ε-caprolactone) [J].
Guo, QP ;
Groeninckx, G .
POLYMER, 2001, 42 (21) :8647-8655
[10]   Synthesis, crystal structure, catalytic and anti-Trypanosoma cruzi activity of a new chromium(III) complex containing bis(3,5-dimethylpyrazol-1-yl)methane [J].
Hurtado, John ;
Ibarra, Laura ;
Yepes, David ;
Garcia-Huertas, Paola ;
Macias, Mario A. ;
Triana-Chavez, Omar ;
Nagles, Edgar ;
Suescun, Leopoldo ;
Munoz-Castro, Alvaro .
JOURNAL OF MOLECULAR STRUCTURE, 2017, 1146 :365-372