obvious that AlCl3 is the dominant species in the high boilers. Broad signals in 27Al-NMR
indicate low symmetry and broad signals were found for both the species at 117 ppm and AlCl3.
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 AlCl3, possibly Al2Cl7-.
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 AlCl3.
Current Data Parameters
NAME
2641997D-LIMS
EXPNO
10
PROCNO
1
F2 - Acquisition Parameters
Date
17.06.2014
Time
07.16.00
INSTRUM
spect
PROBHD 5 mm PABBO BBPULPROG
zg
TD
16384
SOLVENT
CDCl3
NS
1024
DS
4
SWH
52083,333
FIDRES
3,178914
AQ
0,1572864
RG
574.7
DW
9,600
DE
7,00
TE
683,2
D1
1,00000000
Hz
Hz
sec
usec
usec
K
sec
======== CHANNEL f1 ========
NUC1
27Al
P1
6,30 usec
PL1
0,00 db
SFO1
130,3183240 MHz
AlCl3
MHz
Hz
cm
cm
ppm
Hz
ppm
Hz
ppm/cm
Hz/cm
Integrale
F2 - Processing parameters
SI
32768
SF
130,318329
WDW
EM
SSB
0
LB
1,00
GB
0
PC
1,40
1D NMR plot parameters
CX
28,22
CY
16,16
F1P
159,040
F1
0,00
F2P
-40,159
F2
0,00
PPMCM
7,06001
HZCM
0,00000
140
120
100
80
60
ppm
40
20
0
-20
-40
MiniSpec - Copyright Corporate Analytics Wacker Chemie AG
Figure 6: 2 7 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
Current Data Parameters
NAME
2648478D-LIMS
EXPNO
10
PROCNO
1
F2 - Acquisition Parameters
Date
03.07.2014
Time
08.52.25
INSTRUM
spect
PROBHD 5 mm PABBO BBPULPROG
zg
TD
16384
SOLVENT
CDCl3
NS
1024
DS
4
SWH
52083,333
FIDRES
3,178914
AQ
0,1572864
RG
645.1
DW
9,600
DE
7,00
TE
298,2
D1
1,00000000
Hz
Hz
sec
AlCl3
usec
usec
K
sec
======== CHANNEL f1 ========
NUC1
27Al
P1
6,30 usec
PL1
0,00 db
SFO1
130,3183240 MHz
MHz
Hz
cm
cm
ppm
Hz
ppm
Hz
ppm/cm
Hz/cm
Integrale
F2 - Processing parameters
SI
32768
SF
130,318329
WDW
EM
SSB
0
LB
1,00
GB
0
PC
1,40
1D NMR plot parameters
CX
28,22
CY
16,16
F1P
163,044
F1
0,00
F2P
-39,909
F2
0,00
PPMCM
7,19305
HZCM
0,00000
160
140
120
100
80
60
ppm
40
20
0
-20
MiniSpec - Copyright Corporate Analytics Wacker Chemie AG
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
143