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EXAMPLE 32 50
sodium formate were used. The reaction was conducted
In the same autoclave in Example 1 were charged 44 for one hour at 140 C.
grams (1 mole) of ethylene oxide, 27 grams (1.5 moles) The reaction mixture was analyzed by the same
of water, 1.2 grams (0.02 mole) of acetic acid and 4.1 method as in Example 1. The conversion rate of ethyl
grams (0.05 moles) of sodium acetate, and heated to 55 ene oxide was 100%. The reaction product was com
140 C. under stirring. The reaction was carried out for posed of 94.3% of ethylene glycol by weight, 5.5% of
an hour at this temperature. diethylene glycol by weight and 0.2% of triethylene
The reaction mixture was analyzed by the same pro glycol by weight.
cedure as in Example 1. The conversion ratio of ethyl EXAMPLE 34
ene oxide was 100%. The reaction product was com- 60
posed of 93.6% of ethylene glycol by weight, 6.1% of In the same autoclave in Example 1 were charged 58
diethylene glycol by weight and 0.3% of triethylene grams (1 mole) of propylene oxide, 36 grams (2 moles)
glycol by weight. of water, 1.9 grams (0.03 mole) of acetic acid and 3.57
EXAMPLE 33 grams (0.03 mole) of trimethylamine acetate. Said auto
65 clave was set in an electric furnace and heated under
As in Experiment 32, 44 grams (1 mole) of ethylene stirring to an internal temperature of 160 C. and the
oxide, 18 grams (1 mole) of water, 0.92 grams (0.02 reaction was conducted for one hour at this tempera
mole) of formic acid and 2.72 grams (0.04 mole) of ture.
4,937,393
13 14
The internal pressure of the reactor was risen to a COMPARATIVE EXAMPLE 13
maximum of 15 kg/cm2G and then reduced with the
progress of hydration reaction to a final pressure of 4.5 The procedure similar to that of Example 34 was
kg/cm2G at the end of reaction. repeated to carry out the hydration reaction of propy
The autoclave was cooled to the room temperature 5 lene oxide except that 1.8 grams (0.03 mole) of acetic
and a part of the reaction mixture was collected and acid were used without trimethylamine acetate. The
analyzed by the same method as Example 1. The results results are illustrated in Table 3.
are illustrated in Table 3.
in Table COMPARATIVE EXAMPLE 14
EXAMPLES 35-45 10 The procedure similar to that of Example 40 was
The same autoclave in Example 1 was used. Reaction repeated to carry out the hydration reaction of propy
conditions such as quantity of raw materials, kind and lene oxide except that 3.08 grams (0.04 mole) of ammo
quantity of the catalyst and reaction temperature were nium acetate were used without acetic acid. The results
varied as illustrated in Table 3 to perform the hydration are illustrated in Table 3.
reaction of propylene oxide. The results are illustrated 15
in Table 3. EXAMPLE 46
In the same autoclave in Example 1 were charged 44
COMPARATIVE EXAMPLE 11 grams (1 mole) of ethylene oxide, 27 grams (1.5 moles)
The procedure similar to that of Example 34 was of water, 0.3 grams (0.005 mole) of acetic acid, and 5.95
repeated without any catalyst to carry out the hydration 20 grams (0.05 mole) of trimethylamine acetate, and heated
reaction of propylene oxide. The results are illustrated under stirring to 140 C. The reaction was conducted
in Table 3. for an hour at this temperature.
The reaction mixture was analyzed by the same
COMPARATIVE EXAMPLE 12 method as in Example 1. The conversion ratio of ethyl
The procedure similar to that of Example 34 was 25 ene oxide was 100%. The reaction product was com
repeated to carry out the hydration reaction of propy- posed of 93.9% of ethylene glycol by weight, 5.9% of
lene oxide except that 3.57 grams (0.03 mole) of trimeth- diethylene glycol by weight and 0.2% of triethylene
ylamine acetate were used without acetic acid. The glycol by weight.
results are illustrated in Table 3.
TABLE 3
Material Catalyst
H2O A A) -- (B Product
PO (B) PO Reaction PG DPG TPG
Example PO H2O (mole (A) Acid (B) Salt mole % Temperature Time Conversion (% (% (%
No. (g) (g) ratio)" (g) mole (g) mole ratio mole (C) (hr) (% mole) wt) wt) wt)
34 58 36 2 Acetic Ac TEA 00 6 160 100 9.5 7.6 0.9
1.8 (0.03 3.57 (0.03 100
35 58 36 2 Acetic Ac TEA 20 6 160 l 100 93.1 6.4 0.5
0.6 (0.01 5.95 0.05) 100
36 58 36 2 Acetic Ac TEA 100 2 160 1. 100 92.7 6.8 0.5
6.0 (0.1) 2.38 (0.02 20
37 58 i8 Acetic Ac TBA 40 7 160 100 92.3 7.1 0.6
1.2 (0.02 12.25 0.05) 100
38 58 54 3 Acetic Ac AN 20 6 60 1 100 93.7 6.0 0.3
0.6 (0.01 7.65 (0.05)
39 58 54 3 Acetic Ac PY 20 6 160 1 100 94.0 5.7 0.3
0.6 (0.01) 6.95 (0.05)
40 58. 36 2 Acetic Ac NH4 50 6 60 1. 00 90.8 8.2 .0
1.2 (0.02 3.08 (0.04) 100
41 58. 18 1 Formic Ben TMA 100 6 140 1 100 94.3 5.4 0.3
1.38 (0.03) 5.43 (0.03 1.
42 58. 18 1 Formic For TMA 25 5 140 100 94.7 5. 0.2
0.46 (0.01) 4.2 (0.04) 00
43 58. 18 1 Propionic Pro TMA 6 160 1 100 92.5 7.0 0.5
2.96 (0.04 3.5 (0.02) 50
44 58. 18 1 Cl-Acetic CAcTMA l 6 60 100 92.9 6.7 0.4
3.78 (0.04 3.91 (0.02) 50
45 58 8 1 Formic Lau TMA 40 7 160 1. 100 91.0 7.9 1,
0.92 (0.02 12.95 (0.05) 100
Compar 58 36 2 - - - 160 1 96.5 59.3 304 10.3
11
4,937,393
15 16
TABLE 3-continued
Material Catalyst
H2O (A) A. B Product
PO (B) PO Reaction PG DPG TPG
Example PO H2O (mole (A) Acid (B) Salt mole % Temperature Time Conversion (% (% (%
No. (g) (g) ratio) (g) mole (g) mole ratio mole (°C) (hr) (% mole) wt) wt) wt)
Compar 58 36 2 AcTBA O 3. 60 99.5 74.7 23.2 2.1
2 3.57 003 100
Compar 58 36 2 Acetic 00 3 160 100 60.2 29.4 10.4
13 1.8 (0.03 O
Compar 58 36 2 O Ac NH4 O 4. 160 1 00 79.5 17.1 3.4
14 3.08.0.04 100
Note:
PO . . . propylene oxide
H2O. . . water
PG . . . propylene glycol
DPG . . . dipropylene glycol
TPG ... tripropylene glycol
Cl-Acetic. ... monochloroacetic acid
AcTEA. . . triethylamine acetate
Ac TBA. . . tributylamine acetate
AcAN. . . aniline acetate
Ac PY. . . pyridine acetate
AcNH, ... ammonium acetate
Ben TMA. . . trimethylamine benzoate
For TMA. . . trimethylamine formate
Pro TMA. . . trimethylamine propionate
CAcTMA. . . trimethylamine monochloroacetate
Lau TMA. . . trimethylamine laurate
65