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Culture Documents
l | |l l l lNumber:
ml l l l l l l l l l l l l5,453,477
llllllll
453477A
[45]
Date of Patent:
PROCESS OF POLYMERIZING
2,705,706
CHLOROETRIFLUOROETHYLENE WITH
2,783,219
METABISULFITE
3640985
2,1972 Stevens
3,642,754
3,671,510
2/1972 Yatnka .
6/1972 Kornetani et a1. .
OTHER PUBLICATIONS
[22] Filed:
Mar. 7, 1994
[63]
[57]
ABSTRACT
. .
Int- Cl-6
[52]
-~ 526/230; 526/249
[58]
526/227
[56]
References Cited
Us. PATENT DOCUMENTS
absence of soaps.
2,569,524
2,689,241
10/1951
Hamilton .
12 Claims, No Drawings
5,453,477
1
PROCESS OF POLYMERIZING
CHLOROETRIFLUOROETHYLENE WITH
ALKYL HYDROPEROXIDE AND METAL
METABISULFITE
CROSSREFERENCE TO RELATED
APPLICATIONS
amounts of comonomers.
25
composition.
45
SUMMARY
50
useful peroxides which may ?nd use are one or more of the
65
copolymer.
5,453,477
3
5,000,000.
25
with the iron ions in the vessel walls so that the separate
40
(CH3)3COOH.
45
Na2S2O5.
60
5,453,477
5
tion of MBS.
As mentioned above, the presence of iron ions is needed
to be present in the reactor. When iron is added, it may be
in the form of ferrous sulfate, for example. In this case, it
IO
continuously to the reactor during the course of the reaction 25 have found that at relatively higher reaction temperatures, a
be used in the stead of or in addition to the TBH and MBS 30 to be the result of the production of more chains. In light of
these results, the inventors have found that control of the
described above. Further, the form of the reactor is not
reaction conditions to maintain a relatively higher reaction
critical to the practice of process taught herein.
35
55
5,453 ,477
7
inde?nitely.
is exerted upon the reactor vessel and its contents and such
a desired temperature is set and maintained throughout the
with a heat source or heat sink, to provide or withdrawn heat 20 and the reactor contents stirred to effect the agglomeration.
60
5,453,477
9
10
EXAMPLES
20
Reactor
templated.
The compositions formed from the reaction taught herein
following the process steps outlined may be used ultimately
Examples below.
25
50
55
5,453,477
11
12
Type:
Coagulan'ng Agent:
3
1C)
??eilfighzo
ffgglgf?zo
NaCl
sodium chloride
Hcl
hydmchlo?c acid
and characterized.
weight (Mn).
ticles in one batch. The collected particulates were subsequently washed on the centrifuge with two to four liters of
Puri?ed deionized water: and then dried Pen 3 glass tray in
a Circulating air even at a temperature of 1000 C- for a Period 35 mode. First, a test disc having a thickness of approximately
of 1418 hours3-4 millimeters was allowed to equilibrate at 240 C. for 5
Example Compositions
mec anrc
same as was described for the process utrlrzmg the four liter
mer VFZ were provided to the four liter reactor and pro_
reactor and a Jacketed temperature control System as well
cessed in accordance with the procedure described under the
The Production of PCTFE resins was generally in aeeor- 50 heading Polymerization Process Conditions - 4 Liter Reac
water were used, and a further distmctron was that the stirrer
accordance with the various process conditions were evalu
was Operated to rotate at 350 rpm in the 10 gallon teaetor- 55 ated, and the results of such evaluation is outlined on Table
2, following.
TABLE 1
4 liter reactor
Temp
Example:
1
2
TBH
MBS
Reaction
Pressure
CTFE (ml)
VFZ (g)*
Fe (g)
(deg. C.)
initial:
g/hr:
initial:
g/hr.
Time (hrs):
initial:
?nal:
320
410
15
20
0
0
40
40
0.035
0.035
0.016
0.016
0.038
0.04
0.17
0.017
8.5
8
156
156
118
74
5,453,477
13
14
TABLE l-continued
4 liter reactor
Temp
TBH
MBS
Reaction
Pressure
Example:
CfFE (ml)
VF2 (g)*
Fe (g)
(deg. C.)
initial:
g/lir:
initial:
g/hr.
Time (hrs):
initial:
?nal:
3
4
5
6
7
8
9
10
11
12
13
14
320
320
320
320
320
320
320
320
320
200
200
320
15
15
15
15
15
15
15
0
15
10
10
0
0
0
0
0
0.06
0.06
0
0
0
0
0
0
50
40
30
40
50
55
55
20
50
50
50
10
0.084
0.084
0.06
0.06
0.06
0.06
0.06
0.06
0.105
0.105
0.105
0.05
0.034
0.034
0.034
0.034
0.034
0.034
0.034
0.034
0.05
0.05
0.03
0.017
0.00
0.08
0.064
0.37
0.037
0.036
0.036
0.042
0.042
0.042
0.035
0.058
0.058
0.058
0.02
5.5
5.75
6.8
8.5
8
8.5
10
13.5
6.8
4
6
26
198
156
120
156
198
219
219
77
200
194
188
59
187
80
42
0.064
0.21
0.21
0.21
0.074
0.12
0.12
0.12
0.055
118
171
56
51
67
65
62
62
59
TABLE 2
4 liter reactor
Example:
1
2
Coagulant
Polymer
Intrinsic
type:
recovered (g):
Viscosity:
-~
327
446
1.08
1.13
Ash cont.:
Mw +
(ppm) (1 X 10
Mn 4+
3):
(l x 10
<35
<35
461
510
124
140
Hete.*+
3):
Index:
3.7
3.6
Melt Viscosity
(1 x 10
5 Pa Sec):
6.5
8.7
210
0.64
71
360
160
2.25
NaCl
373
0.87
10,000
370
90
- 4.11
5a
5b
B
A
126
172
1.17
1.18
309
62
600
590
210
180
2.86
3.28
B
B
B
B
B
B
HCl
C
C
315
295
395
435
395
425
276
425
350
1.1
0.79
0.58
0.61
0.83
0.79
0.68
0.83
1.16
73
126
112
73
109
600
390
310
340
450
450
375
400
530
310
135
80
110
225
190
180
170
230
1.94
2.89
3.9
3.1
2
2.37
2.1
2.4
2.3
7.9
2
0.5
0.73
2.4
2.3
0.73
5.7
19.4
6
7
8
9
10
11
12
13
14
<35
210
283
tion Product. The polymer produced in the reactor was 55 according to the guidelines given above in the four-liter
divided into two portions, and evaluated and reported as
reactor; the resultant polymer product was evaluated and the
samples labeled 5a and 5b. The results of the evaluation
evaluation results are outlined on Table 2.
are outlined on Table 2.
5,453,477
15
16
below.
'
cake was washed with one liter of purified water plus two ml
conc. H2504, one liter of puri?ed water, two liters of
puri?ed water plus four grams of sodium bicarbonate, and
then six liters of puri?ed water. The polymer was dried
overnight at 95 C_ in a circulating air oven. A white
y y
wppl _ _
1 2c 31m
'
b1
reaction causing a temperature rise to 46 C. and a pressure 20 F0 y(c hoiom utgoet 1y ?ne) or a cog) ymprsl C 0mm '
increase to 185 psi. The polymerization temperature was
through the reactor jacket. At 1.1 hours and 3.5 hours, after
observing a 10 psi drop in reactor pressure, additional
monomers, 345 kg chlorotri?uomethylene plus 110 g 25
compnses'
_ _
10 gallon reactor
Temp
TBH
MBS
Reaction
Pressure (psi)
Example:
CTFE (kg)
VF2 (g)*
(deg. C.)
initial:
g/hr:
initial;
g/hr.
Time (hrs):
initial:
?nal:
15
16
17
6.82
7.32
7.28
25
0
0
41
10
10
1.05
0.52
0.36
0.1
0.2
0.01
1.22
0.61
0.43
0.12
0.29
0.11
5
23
30
174
52
54
70
38
54
TABLE 4
10 gallon reactor
Example:
15a
15b
15c
16
17
coagulant
Polymer
Intrinsic
Ash cont.:
type:
recovered (g)
Viscosity:
(ppm)
(1 X 10
Mw +
C
D
B
C
B
454
405
459
414
371
1.3
1.26
1.3
0.93
1.1
84
51
44
<35
<25
570
580
580
550
550
Mn +1-
3)
(1 x 10
190
190
220
130
120
l-lete.*+
3)
Index:
3
3.1
2.64
6.9
709
5,453,477
18
17
(b) charging to said reactor vessel said redox initiator
system and maintaining a controlled temperature
initiator system.
roethylene.
10. The process according to claim 1 wherein said reac
chlorotri?uoroethylene
and
25
30
35
40
50
55
60
65