194
H.-D. Quan et al. / Journal of Fluorine Chemistry 128 (2007) 190–195
The other set of apparatus for preparation of HFC-245fa
consisted of two mass flow controllers (one for CTFP and the
other for AHF) and the reactor used in the first step.
(Section 3.3.1). The remainder of the procedure for preparing the
catalyst was also as previously described (Section 3.3.1).
The product stream was scrubbed through a water bath at
60 8C to remove excess amounts of HF, passed through a drier
filled with CaCl2, and finally analyzed by a SHIMADZU GC-14
B on-line. The capillary column was Pora plot Q with 0.32 mm
i.d. and 25 m length from J & W Scientific Inc. The operating
conditions of gas chromatography (GC) were as follows—(a)
preparation of CTFP from PCP: column temperature, 150 8C;
detector temperature, 200 8C; injector temperature, 200 8C;
carrier gas, ꢀ5 cm3 He/min; sample size, 0.05 cm3. (b)
Preparation of HFC-245fa from CTFP. The column was
programmed as follows: initial temperature, 80 8C for 10 min;
increasing the temperature at the rate of 20 8C/min to a final
temperature of 200 8C for 10 min; detector temperature 200 8C;
carrier gas, ꢀ5 cm3 He/min; sample size 1.0 cm3.
3.3.5. Preparation of CTFP from PCP
Preparation of CTFP from PCP was started by feeding PCP
into the reactor via a vaporizer at 150 8C through a Masterflex
(Cole-Parmer Instrument Co.) metering pump. AHF was drawn
to vapor phase in the above vaporizer. The mixture of PCP and
AHF passed through the reactor, which was packed with 10 cm3
of catalyst at the required temperature. The product stream
from the reactor was scrubbed, dried and passed through the GC
on-line. The results are listed in Tables 1 and 2.
3.3.6. Preparation of HFC-245fa from CTFP
Preparation of HFC-245fa from CTFP was as follows: A
certain amount of AHF and CTFP were fed into a pre-mixture at
80 8C, then passed through a reactor packed with 10 cm3 of
catalyst at the required temperature. The product stream from
the reactor was scrubbed, dried and passed through the GC on-
line. The results are listed in Tables 3–6.
3.3. Fluorination of 1,1,1,3,3-pentachloropropane and the
preparation of process catalyst
3.3.1. Porous aluminum fluoride-based catalyst (PAF)
3.4. Analytic results of intermediates and HFC-345fa
Porous aluminum fluoride-based catalyst (PAF), with 92 m2/g
surface area, was prepared by reaction with AlF3Á3H2O [16].
Then 25 g of SbCl5 was dropped gradually into 25 g of the above
PAF under a nitrogen atmosphere. The SbCl5/PAF was charged
into an Inconel reactor that was 300 mm in length and 12 mm in
diameter, and dried at 100 8C for 3 h in the presence of nitrogen.
Then AHF diluted by nitrogen was passed through the reactor at
200 8C (the diluted gas is a 1:1 mixture of N2:AHF at 100 cm3/
min) for 2 h, pure AHF 200 cm3/min for 3 h. Finally the
remainder of AHF in the reactor was purged by nitrogen for 10 h.
3.4.1. Trans-CF3CH CHCl
Boiling point, 51 8C/760 mmHg. Spectral data, MS peaks m/
e: 61 CHCHCl; 69 CF3; 82 CF3CH; 95 CF3CH CH; 111
+
+
+
+
+CF2CH CHCl, 130 CF3CH CHCl. NMR chemical shifts:
+
F1(3)d-64.09 m; H2(1)d-6.93 d,q; H3(1)d-6.10 m.
3.4.2. Cis-CF3CH CHCl
Boiling point 21 8C/760 mmHg. Spectral data, MS peaks m/
e: 61 CHCHCl; 69 CF3; 82 CF3CH; 95 CF3CH CH; 111
+
+
+
+
+
+CF2CH CHCl, 130 CF3CH CHCl. NMR chemical shifts:
3.3.2. Porous calcium fluoride-based catalyst (PCF)
Porous calcium fluoride-based catalyst (PCF), with 60 m2/g
surface area, was prepared from the reaction of soda-lime and
AHF [16]. Then 25 g of SbCl5 was dropped gradually into 25 g
of the above PCF under a nitrogen atmosphere. The SbCl5/PCF
was charged into a reactor as previously described (Section
3.3.1). The remainder of the procedure for preparing this
catalyst was also as previously described (Section 3.3.1).
F1(3)d-60.56 d; H2(1)d-6.59 d; H3(1)d-6.10 m.
3.4.3. Trans-CF3CH CHF
Boiling point À16 8C [23]. Spectra data, MS peak m/e: 45
+CH CHF, 69 +CF3, 95 +CF2CH CHF, 114 +CF3CH CH.
NMR chemical shifts:
F1(3)d-62.60 m, H2 (1)d-5.67 m, H3(1)d-7.19 d,d,q, F4(1)d-
120.4 d.
3.3.3. Porous magnesium fluoride-based catalyst (PMF)
Porous magnesium fluoride-based catalyst (PMF), with
about 9.0 m2/g surface area, was prepared from commercial
MgF2. Then about 25 g of SbCl5 was dropped gradually into
25 g of PMF under a nitrogen atmosphere. The SbCl5/PMF was
charged into a reactor as previously described (Section 3.3.1).
The remainder of the procedure for preparing this catalyst was
also as previously described (Section 3.3.1).
3.4.4. CF3CH2CHF2
Spectra data of CF3CH2CHF2: IR: 3001(w), 2359(w),
1307(vs), 1208(vs), 1146(vs). MS peak m/e: 51 +CHF2; 64
+CHCHF2; 69 CF3; 115 CF3CH2CHF; 133 CF3CH2CHF.
NMR chemical shifts:
+
+
+
F1(3)d-63.86 m, H2(2)d-2.72 m, H3(1)d-6.07(t,t), F4(2)d-
116.38 (d,m).
3.3.4. Porous chromium fluoride-based catalyst (PCrF)
Porous chromium fluoride-based catalyst (PCrF), with
90.0 m2/g surface area, was prepared from the reaction of
porous chromia and AHF. Then about 25 g of SbCl5 was dropped
gradually into 25 g of PCrF under a nitrogen atmosphere. The
SbCl5/PCrF was charged into a reactor as previously described
Acknowledgements
We gratefully thank NEDO Research Project ‘‘Innovation
Technology for the Synthesis of Alternative Compounds Which
Reduce Global Warming’’ Project no.: P01070.