On the hydrolytic stability of organic ligands in Al-, Ti- and Zr-alkoxide complexes

被引:84
作者
Hoebbel, D [1 ]
Reinert, T [1 ]
Schmidt, H [1 ]
Arpac, E [1 ]
机构
[1] AKDENIZ UNIV,TR-07200 ANTALYA,TURKEY
关键词
metal alkoxide complexes; beta-keto ligands; hydrolysis; particle size; IR; C-13; NMR;
D O I
10.1023/A:1018305811088
中图分类号
TQ174 [陶瓷工业]; TB3 [工程材料学];
学科分类号
0805 ; 080502 ;
摘要
The complexation degrees of Al-, Ti- and Zr-butoxide (M) with unsaturated and saturated beta-diketones (3-allylpentane-2.4-dione-APD, acetylacetone-ACAC) and beta-ketoesters (methacryloxyethyl-acetoacetate-MEAA, allylacetoacetate-AAA, ethylacetoacetate-EAA) as organic ligands (L) were examined by IR and C-13 NMR spectroscopy and were found to be L:M greater than or equal to 1.5. The hydrolytic stability of the ligands of the metal alkoxide complexes (L:M = 1) during hydrolysis/condensation reactions at the molar ratio h (H2O:OR) = 0.5-2.0 decreases with increasing H2O:complex ratio. Furthermore, the ligand stability depends on the type of metal in the complexes and decreases in the order Al- > Zr- > Ti-butoxide complexes at h = 1. The ACAC ligand likewise shows in the Al-, Ti- and Zr-butoxide complexes a high hydrolytic stability (95-100%) at h = 1 within 7 days. The Ti- and Zr-butoxide complexes with beta-ketoesters as ligand show at h = 1 a release to a different extent e.g., up to 60% in the case of the MEAA-ligand in the Ti-butoxide complex after 2 days. Tn general, the hydrolytic stability of the ligands in the Ti-butoxide complexes (L:M = 1, h = 1) decreases in the order ACAC > APD > AAA > EAA greater than or equal to MEAA. The hydrolysis/condensation reaction of complexes having a weak ligand stability leads to larger particle sizes in the sols than those with stable ACAC ligands. The results contribute to a more controlled synthesis of sols and of new inorganic-organic hybrid polymers via the sol-gel process.
引用
收藏
页码:115 / 126
页数:12
相关论文
共 39 条
[1]  
[Anonymous], BETTER CERAMICS CHEM
[2]  
[Anonymous], ULTRASTRUCTURE PROCE
[3]   ALUMINUM SEC-BUTOXIDE MODIFIED WITH ETHYLACETOACETATE - AN ATTRACTIVE PRECURSOR FOR THE SOL-GEL SYNTHESIS OF CERAMICS [J].
BABONNEAU, F ;
COURY, L ;
LIVAGE, J .
JOURNAL OF NON-CRYSTALLINE SOLIDS, 1990, 121 (1-3) :153-157
[4]   Organically substituted titanium alkoxides with unsaturated organic groups [J].
BarglikChory, C ;
Schubert, U .
JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, 1995, 5 (02) :135-142
[5]  
BARGLIKCHORY C, 1993, P 1 EUR WORKSH HYBR, P261
[6]  
BLANCHARD J, 1995, NEW J CHEM, V19, P929
[7]  
BUHLER H, 1991, THESIS U WURZBURG GE
[8]   The Role of Complexing Ligands in the Formation of Non-Aggregated Nanoparticles of Zirconia [J].
Chatry, M. ;
Henry, M. ;
In, M. ;
Sanchez, C. ;
Livage, J. .
JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, 1994, 1 (03) :233-240
[9]   HYDROLYSIS OF TITANIUM ALKOXIDES - MODIFICATION OF THE MOLECULAR PRECURSOR BY ACETIC-ACID [J].
DOEUFF, S ;
HENRY, M ;
SANCHEZ, C ;
LIVAGE, J .
JOURNAL OF NON-CRYSTALLINE SOLIDS, 1987, 89 (1-2) :206-216
[10]   STUDIES IN CHEMOTHERAPY .13. ANTIMALARIALS - HALOGENATED SULFANILAMIDOHETEROCYCLES [J].
ENGLISH, JP ;
CLARK, JH ;
CLAPP, JW ;
SEEGER, D ;
EBEL, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1946, 68 (03) :453-458