151 / 390
obvious that AlCl
3
is the dominant species in the high boilers. Broad signals in
27
Al-NMR
indicate low symmetry and broad signals were found for both the species at 117 ppm and AlCl
3
.
Furthermore, reference measurements of methylaluminum chlorides showed that no such
compound is present in the mixture. So the species causing the signal at 117 ppm remained
unidentified, but since it has to be formed by reaction of the two aluminum species present in
the product mixture, it most probably is closely related to AlCl
3
, possibly Al
2
Cl
7
-
.
In the disilane columns of the distillation the concentration of aluminum in the high boiling
residues which are discharged as waste from the last distillation columns rises further to about
4500 ppm. Two more aluminum species at 40 ppm and 96 ppm can be found in NMR spectra
of the residue (Figure 8). As can be seen, a major fraction of the aluminum species in the
mixture still consists of AlCl
3
.
Figure 6:
27
Al-NMR of the direct synthesis product mixture (Al concentration ~200 ppm,
broad hump from 20 – 120 ppm caused by probe and cavity of the NMR spectrometer
Figure 7:
27
Al-NMR of the high boilings of the distillation process (Al
concentration ~1700 ppm), broad hump from 20 – 120 ppm caused by probe and
cavity of the NMR spectrometer
140
120
100
80
60
40
20
0
-20
-40
ppm
MiniSpec -CopyrightCorporateAnalyticsWackerChemieAG
CurrentDataParameters
NAME 2641997D-LIMS
EXPNO
10
PROCNO
1
F2 -AcquisitionParameters
Date
17.06.2014
Time
07.16.00
INSTRUM
spect
PROBHD 5mmPABBOBB-
PULPROG
zg
TD
16384
SOLVENT
CDCl3
NS
1024
DS
4
SWH
52083,333 Hz
FIDRES
3,178914 Hz
AQ
0,1572864 sec
RG
574.7
DW
9,600 usec
DE
7,00 usec
TE
683,2 K
D1
1,00000000 sec
========CHANNEL f1========
NUC1
27Al
P1
6,30 usec
PL1
0,00 db
SFO1
130,3183240 MHz
F2 -Processingparameters
SI
32768
SF
130,318329 MHz
WDW
EM
SSB
0
LB
1,00 Hz
GB
0
PC
1,40
1DNMR plotparameters
CX
28,22 cm
CY
16,16 cm
F1P
159,040 ppm
F1
0,00 Hz
F2P
-40,159 ppm
F2
0,00 Hz
PPMCM
7,06001 ppm/cm
HZCM
0,00000 Hz/cm
Integrale
160
140
120
100
80
60
40
20
0
-20
ppm
MiniSpec -CopyrightCorporateAnalyticsWackerChemieAG
CurrentDataParameters
NAME 2648478D-LIMS
EXPNO
10
PROCNO
1
F2 -AcquisitionParameters
Date
03.07.2014
Time
08.52.25
INSTRUM
spect
PROBHD 5mmPABBOBB-
PULPROG
zg
TD
16384
SOLVENT
CDCl3
NS
1024
DS
4
SWH
52083,333 Hz
FIDRES
3,178914 Hz
AQ
0,1572864 sec
RG
645.1
DW
9,600 usec
DE
7,00 usec
TE
298,2 K
D1
1,00000000 sec
========CHANNEL f1========
NUC1
27Al
P1
6,30 usec
PL1
0,00 db
SFO1
130,3183240 MHz
F2 -Processingparameters
SI
32768
SF
130,318329 MHz
WDW
EM
SSB
0
LB
1,00 Hz
GB
0
PC
1,40
1DNMR plotparameters
CX
28,22 cm
CY
16,16 cm
F1P
163,044 ppm
F1
0,00 Hz
F2P
-39,909 ppm
F2
0,00 Hz
PPMCM
7,19305 ppm/cm
HZCM
0,00000 Hz/cm
Integrale
AlCl
3
AlCl
3
143