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Patented Octlgz, 1946
2,409,948
UNITED STATES PATENT OFFICE
2,409,948
POLYMERIC MATERIALS
Elmore Louis Martin, Wilmington, Del., assignor
to E. I. du Pont de Nemours 8: Company, Wil
mington, Del., a corporation of Delaware
No‘ Drawing. Application March 1, 1945,
Serial No. 580,491
6 Claims.
'
(Cl. 260-86)
2
1
phate. The reactor is closed, evacuated, cooled
This invention relates to polymeric materials
and more particularly to polymers obtained from
in a solid carbon dioxide/methanol mixture, and
is further charged with 10 parts of vinyl chloride,
60 parts of vinyl ?uoride and 30 parts of tetra
?uoroethylene. The reactor is agitated and
halogenated ethylenes.
This invention has an an object new and use
ful compositions of matter. A further object is
the preparation of valuable high molecular
heated to 75° C. while maintainng an internal
pressure within the range of 3,000-32,000 lb./sq.
weight polymers comprising ?uorinated ethylenes.
in. by periodic injection into the reactor of deoxy
A still further object is the preparation of poly
genated water. The sum of the individual pres
mers comprising tetra?uoroethylene and vinyl
?uoride having greater solubility in organic sol 10 sure drops during the heating period of 9.1 hours
is 5400 lb. /sq. in. The'reactor. is cooled to room
vents and improved workability. Other objects
temperature, the unreacted portion of the gaseous
will appear hereinafter.
monomers bled o?, and the contents of the re
These objects are accomplished by polymerizing
action tube are discharged. There is obtained 42
ture of a perhaloethylene containing at least two 15 parts of a copolymer which contains 43.4% ?uo
rine and 8.67% chlorine which corresponds to a
?uorine atoms, vinyl ?uoride, and a hydrogen
tetra?uoroethylene/vinyl ?uoride/vinyl chloride
containing halogenated ethylene other than the
copolymer having a tetra?uoroethylene content
vinyl ?uoride.
of 25%, and a vinyl ?uoride content of 60% and a
I have found that polymers can be obtained
from the above mentioned ingredients which are 20 vinyl chloride content of 15%, or a mole ratio of
tetra?uoroethylene/vinyl ?uoride/vinyl chloride
of particular value in many industrial applications
of 1:5.4:1. Films cast from an acetone solution
by reason of their clarity and solubility in con
in the manner more fully described below a mix
(25% copolymer), have tensile strengths of 4850
junction with high tensile strength, non?am
lb./sq. in. at an elongation of 460%, a modulus of
mability, and other desirable properties
The invention is most advantageously carried 25 elasticity of 0.136>< 10° lb./sq. in., a tack tempera
ture (the temperature at which the ?lm shows
out when the mixture of copolymer ingredients is
a tendency to stick to a highly polished surface)
composed of tetra?uoroethylene, vinyl ?uoride,
of 115-120° C. and a temperature of zero tenacity
and vinyl chloride. The tetra?uoroethylene can,
of 135° C. The copolymer is non?ammable and
however, be replaced by other perhaloethylenes,
that is by other completely halogenated ethylene's 30 is soluble in acetone, methyl ethyl ketone, ethyl
acetate and halogenated hydrocarbons. It is
in which at least two of the halogen atoms are
insoluble in alcohols, ethers, and aliphatic and
The vinyl chloride can be replaced by
various hydrogen-containing halogenated ethyl
enes other than vinyl ?uoride. The vinyl ?uo
ride is speci?cally a necessary component in the 35
aromatic hydrocarbons.
Exmu2
, present copolymers.
A stainless steel pressure reactor is charged with
200 parts of deoxygenated water and 0.3 part
of benzoyl peroxide. The reactor is closed, evacu
ties of stiffness, melting point, tensile strength,
ated, cooled in a solid carbon dioxide/methanol
solubility and clarity, and sacri?c of one or more 40 mixture, and is then further charged with 25
of these properties, each of the mentioned copoly
parts of vinyl ?uoride, 45 parts of tetra?uoro
mer ingredients must be present in the composi
ethylene, and 30 parts of vinylidene ?uoride. The
tion to the extent of at least 5%. The polymer
reactor is then agitated and heated to 80° 0., the
ization reaction is conducted under superatmos
, pressure being maintained in the range of 2400
pheric pressure, generally autogenous pressure,
2600 lb./sq. in. by the periodic injection of de
and elevated temperature in the presence of a
oxygenated water. After heating for 10.2 hours
In order to obtain the'desired balance between
preservation to the greatest extent of the proper
small amount of a peroxy compound as catalyst;
the sum of the individual pressure drops is 1600
lb./sq. in. The reactor is then cooled and dis
charged. There is obtained 34 parts of a copoly
50 mer of tetra?uoroethylene/vinyl ?uoride/vinyli
.‘EXAMPLE 1
dene ?uoride which is soluble in acetone to the
extent of 23%. Films cast from an acetone solu
Av stainless steel high-pressure reactor is
‘tion have vtensile strengths of 5000 lbJsq. in. at
charged with 50 parts of tert.-butyl alcohol, 150
The invention is illustrated by the following
examples wherein parts are by weight.
‘
parts of deoxygenated water, 0.3 part of benzoyl
peroxide and 0.3 part of hydrated disodium phos
' an elongation of 440%, a modulus of elasticity of
55 0.101 x10a lbJsq. in.,,a tack temperature of 160
2,409,948
4
165° C., and a temperature of zero tenacity of 178°
C. The copolymer is nan?ammable and is soluble
used, the products are in general characterized
by lower molecular weights.
'The catalysts used in the practice of this in
vention are peroxy compounds, 1. e., those com
in acetone, methyl ethyl ketone, ethyl acetate, and
, halogenated hydrocarbons. It is insoluble in al
cohol, ether and aliphatic and aromatic-hydro
5 pounds which contain an -O—0_ linkage. Ex
carbons. -
amples of such catalysts are diacyl peroxides,
such as benzoyl peroxide and lauroyl peroxide,
polymers for a particular use is facilitated by
dialkyl peroxides, such as diethyi peroxide, and
the table inserted herein which shows the physi
inorganic peroxy compounds such as ammonium
cal properties of a number of these copolymers:
l0 persulfate, potassium persulfate, potassium per
Tame
' The ready selection of the most desirable co
Tetra‘
?uoro~
ethylene
Per cent
5‘
7
7
9
11
14
20
vm 1
?uor dc
Vin 1
chlor de
Tack
temp.
Temp- Modulus of
often
zero elssticltyX10‘
69
22
35
68
52
54
51
26
71
58
23
37
32
29
° 0.
45-50
40-45
35
70-75
40-45
50-55
35-40
° 0.
68
82
Lba/sq. in.
0. 062
0. 260
50
124
61
78
88
0. 219
0. 098
"‘. 032
0. 097
0. 134
21
48
31
60-65
...... _.
0. 030
23
25
33
36
36
55
60
40
37
43
22
15
180
135
. 100
90 ,
126
0. 145
0. 136
0. 002
0. 094
0. 147
55
25
27
21
20
85-90
115-120
50-55
40-45
80-85
130-135
172
2
38
70-75
126
60 .
27
Yield
Point
Ten.
Lbalaq. in. Liza/sq. in.
1, 850
2, 000
3, 120
' 3, 120
3, 420
2, 860
1, 720
2, 660 .
3, 550
3, 420
2, 900
1, B00
2, 700
3, 600
Elong.
Per cent
150
10
10
220 /
10
80
60
.
Excellent.
Hazy.
Good.
Excellent.
Fair.
Excellent.
Good.
1, 840 .
2, 550
380
3, 800
3, 800
1, 400
2, 640
3, 880
3, 850
4, 850
3, 410
2, 870
4, 710
10
460
420
350
400
0. 112
3, 480
7, 250
465
Fair.
0. 090
3, 160
3, 720
410
Good.
'
_
Clarity of
films
Fair.
D0.
Good.
Excellent.
' Suitable perhaloethylenes in addition to tetra
carbonate, potassium perphosphate, sodium per
?uoroethylene which contain at least two ?uorine 30 borate and hydrogen peroxide.
atoms include chlorotri?uoroethylene, bromotri
The polymerization is conducted generally at
?uoroethylene, 1,1-dichloro-2,2-di?uoroethylene
temperatures within the range of 40-200° C., de
and 1,2-dichloro-l,2-di?uoroethylene. Hydrogen
pending upon the type of catalysts used. With
containing halogenated ethylenes in addition to
diacyl peroxide catalysts, temperatures ranging
vinyl chloride and vinylidene ?uoride include
from 80-120° C., with persulfate catalysts 20-100°
vinyl bromide, vinylidene chloride, l-chloro-l
C., and with dialkyl peroxide catalysts 100-l50° C.
?uoroethylene, 1,1-di?uor0-2-chloroethylene and
tri?uoroethylene.
'
,
are generally used. The polymerization can ‘be
carried out at pressures above atmospheric, gen
erally within the range of 500—5000 lb./sq. in. and
The copolymers having the most valuable prop
erties are those obtained from mixtures consist 40 preferably within the range of 1500-4000 lb./sq.
ing of 20% to 50% tetra?uoroethylene, 25% to
in.
75% vinyl ?uoride, and 5% to 30% of the hy
The products of this invention are character
drogen-containing halogenated ethylene other
ized by good solubility and excellent clarity. They
than the vinyl ?uoride. Within this range the , are further characterized by having the valuable
proportions best for particular purposes will vary
45 combination of ‘properties which include good
somewhat. Thus where stiffness is a considera
tensile strength, relatively high softening tem
tion the preferred compositions contain 20%-45%
tetra?uoroethylene, 50%-75% vinyl ?uoride, and
5% .to 30% of the other hydrogen-containing
a
perature, high modulus of elasticity, low water ab
sorption' and non?amma-bility. Copolymers of
this invention are therefore particularly suitable
halogenated ethylene. For applications where
tack temperature is of ?rst importance, the best 50 for use as a base for photographic and X-ray
?lms and in coating compositions, wrapping ?lms
results are obtained with compositions contain
and industrial ?bers. They can be molded into
ing 20%-50% tetra?uoroethylene, 25%-75%
various shaped articles and can be extruded in
vinyl ?uoride and 5%-20% of the .other hydroe
the form of ?bers, ?lms, etc. These copolymers
gen-containing halogenated ethylene. Where the
tensile strength is of primary importance, com 55 are also valuable for coating wire in the manu
facture of electrically insulated conductors. For
positions containing 20%-50% of the tetra?uoro
many
of these purposes the polymer may be com
ethylene, 45 %-70% of vinyl ?uoride and 5%-.25%
bined with or prepared in the presence of plasti
of the hydrogen-containing halogenated ethylene‘
are the preferred. For applications where tack
cizers, stabilizers, ?llers, pigments, dyes, softeners,
60 natural resins or synthetic resins.
‘
, temperature, stiffness and tenacity are of ?rst im-. portance, compositions containing 20%-45% .of 5 ' , As many widely different embodiments of this
tetra?uoroethylene, 50%-70% of vinyl ?uoride,
and 5%-2o% vof the hydrogen-containing halo
invention may be- made without departing from
. the spirit and scope thereof, it is to be understood ,
genated ethylene are used because these composi- 65 that this invention is not to be limited to the
speci?c embodiments thereof, except as de?ned
in the appended claims.
ture and tenacity values.
Iclaim:
.Although the examples illustrate the polymerlQ
1. A composition of matter comprising the co
zation of a monomeric mixture in the presence’ of
water, it is possible to carry out the reaction in , polymerization product of a mixture of a per
an organic solvent instead of water. In general, 70 haloethylene containing at least two ?uorine
tions possess the higher stiffness, tack tempera
- _ it is preferred to carry out the polymerization in
the presence of water or water-organic solvent
, mixtures inasmuch as better results can be ob
atoms, vinyl ?uoride, and a hydrogen-containing
halogenated ethylene other than vinyl ?uoride,
'said mixture containing each of said nerhalo
ethylene, vinyl ?uoride and hydrogen-containing
. tained. since when organic solvents‘ alone are 75 halogenated ethylene other than vinyl ?uoride in
2,409, 948
‘ 5
a
an amount of at least 5% by weight, the halogen
contained in said perhaloethylene and in said hy
drogen-containing halogenated ethylene being
,_ selected from the group consisting of chlorine,
bromine, and ?uorine.
.
2. A composition of matter comprising the co
polymerization product of a mixture of tetra
6
said perhaloethylene, vinyl ?uoride and hydro
gen-containing halogenated ethylene other than
vinyl ?uoride in an amount of at least 5% by
weight, the halogen contained in said perhalo
ethylene and in said hydrogen-containing halo
c genated ethylene being selected from the group
consisting of chlorine, bromine, and ?uorine.
?uoroethylene, vinyl ?uoride, and a hydrogen
5. A process for obtaining copolymers which
containing halogenated ethylene other than vinyl
comprises heating in the presence of a peroxy
?uoride, said mixture containing each of said 10 catalyst at 40° C. to 200° C. under autogenous
tetra?uoroethylene, vinyl ?uoride and hydrogen
pressure a mixture of tetra?uoroethylene, vinyl
containing halogenated ethylene other than vinyl
?uoride, and a hydrogen-containing halogenated
?uoride i an amount of at, least 5% by weight,
ethylene other than vinyl ?uoride, said mixture
the halogen contained in said perhaloethylene
containing each of said tetra?uoroethylene, vinyl
and in said hydrogen-containing halogenated
?uoride, and hydrogen-containing halogenated '
ethylene being selected from the group consist
ethylene other than vinyl ?uoride in amount of
at least 5% by weight, the halogen contained in
ing of chlorine, bromine, and ?uorine.
,
3. A composition of matter comprising the co
polymerization product of a mixture of tetra
said perhaloethylene and in said hydrogen-con
taining halogenated ethylenebeing" selected from
?uoroethylene, vinyl ?uoride, and vinyl chloride, 20 the group consisting of chlorine, bromine, and
said mixture containing each of said tetra?uoro
?uorine.
ethylene, vinyl ?uoride, and vinyl chloride in
6. A process for obtaining copolymers which
,
comprises heating in the presence of a peroxy
4. A process for obtaining copolymers which
catalyst at 40° C. to 200° C. under autogenous
comprises heating at 40°-200° C. under autoge 25 pressure a mixture of tetra?uoroethylene, vinyl
nous pressure in the presence of a peroxy catalyst
?uoride, and vinyl chloride, said mixture con
a mixture of a perhaloethylene containing at least
taining each of said tetra?uoroethylene, vinyl
two ?uorine atoms, vinyl ?uoride, and a hydro
?uoride, and vinyl chloride in amount of at least
amount of at least 5% by weight.
gen-containing halogenated ethylene other than
vinyl ?uoride,-said mixture containing each of
5% by weight.
EIMORE LOUIS MARTIN.
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