DID YOU KNOW? DTIC has over 3.5 million final reports on DoD funded research, development, test, and evaluation activities available to our registered users. Click
HERE to register or log in.
Accession Number:
ADA280532
Title:
Tert-Butylalumoxanes: Synthetic Analogs for Methylalumoxane (MAO) and New Catalytic Routes to Polyolefins and Polyketones
Descriptive Note:
Technical rept.
Corporate Author:
HARVARD UNIV CAMBRIDGE MA DEPT OF CHEMISTRY
Report Date:
1994-06-16
Pagination or Media Count:
47.0
Abstract:
The hydrolysis of AltBu3 in toluene using the hydrated salt, A12SO43.14H20, results in the formation of the dimeric hydroxide TBu 2Almu-OH2 1 and Al4tBu7mu 3-02mu-OH2 as the major and minor products, respectively. Compound 1 may also be prepared by the addition of water to a refluxing toluene solution of A1tBu3. Compound 1 is remarkably stable to thermolysis and is converted slowly to a mixture of alumoxane species. Dissolution of compound 1 in MeCN or THF yields the hydrogen-bound trimeric complexes TBu2A1mu-OH3.nMeCN n 13, 2 and TBu2 Almu-OH3.2THF, respectively. The large scale synthesis of alumoxanes from the low temperature thermolysis of the trimeric hydroxide. TBu2A1mu-OH3, allows for the isolation of the penta-aluminum compound Al5tBu7mu-3-02mu-OH2 4 and the heptameric alumoxane TBuAlmu 3-O7 5. The structure of compound 4 is consistent with the condensation of TBu2 Almu-OH3 with TBu2Almu-OH2. Thermolysis of 4 yields an alumina gel. The structural relationship of 4 with respect to the structures reported for non-alkyl alumoxanes and alumina gels is discussed. Reaction of TBu2Gamu-OH3 with AltBu3 in toluene yields the octameric alumoxane GatBu3 and TBuA1mu3-08 6, as the major isolable products. Mass spectrometry indicates the incorporation of low levels of gallium 8 into samples of 6 made by this route. The molecular structures of compounds 2, 4 and 6 have been determined by X-ray crystallograhy.
Distribution Statement:
APPROVED FOR PUBLIC RELEASE
