A description is given of highly stable polyurethane polymers prepared by reacting a polyether with a diisocyanate. Compounded stocks of these polymers may be shaped and cured in conventional equipment used in the rubber industry. The solutions are dispersed gels prepared from the polymers and may be used for forming supported or unsupported films for coating fabrics or solid surfaces, and for forming adhesive bonds between a wide variety of plastics, elastomers, fabrics, metals, wood, leather, ceramics and the like

Trischler, F. D.

English

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,UiA...-
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$ - - — --. . -
_ (NASA-Case-HFS-10506) POLYOBETHANES FBOW
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 FLDOBOALKYL PBOPYLEMEGLYCOL POLYETHEBS
Patent (Hhittaker Corp.), 2 p CSCL 07C
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United States Patent Office 3,463,762Patented Aug. 26, 1969
3,463,762
POLYURETHANES FROM FLUOROALKYL
PROPYLENEGLYCOL POLYETHERS
Fleyd D. Trischler, San Diego, Calif., assignor to Whit-
taker Corporation, Los Angeles, Calif., a corporation of
California
No Drawing. Filed Dec. 30, 1966, Ser. No. 606,036
Int. Cl. C08g 22/14
U.S. Cl. 260—77.5 11 Claims
10
ABSTRACT OF THE DISCLOSURE
This patent describes highly stable polyurethane poly-
mers prepared by reacting a polyether having the formula:
IH
wherein A is an alkylene group, B is a fluorine-containing
alkyl group, n is an integer from 1 to about 10 and m is
an integer from 1 to about 200, with a diisocyanate hav-
ing the formula:
OCN—A'—NCO
wherein A' is a divalent organic group. Compounded
stocks of these polymers may be shaped and cured in con-
ventional equipment used in the rubber industry. The so-
lutions are dispersed gels prepared from the polymers of
this invention and may be used for forming supported or
unsupported films for coating fabrics or solid surfaces, and
for forming adhesive bonds between a wide variety of
plastics, elastomers, fabrics, metals, wood, leather, ce-
ramics and the like.
15
cals and oxidizing agents, based upon fluorine-contain-
ing ethers and diisocyanates.
In another aspect of the present invention, it is an
object thereof to provide a new method for the prepara-
tion of novel fluorine-containing polyurethanes.
These and other objects and advantages of the present
invention will be apparent from the more detailed de-
scription which follows.
Briefly, the present invention comprises the novel poly-
urethanes having the following repeating unit:
Io-A-^FXA-o-Ll ' ° * *
L \ /Q \
prepared by reacting a fluorine-containing hydroxy termi-
nated polyether of the formula
This invention relates to a novel class of flilorine-con-
taining polyurethane polymers prepared by the reaction
of diisocyanates with fluorine-containing hydroxy-termi-
nated ethers.
In the printed literature there has been reference to the
synthesis of urethane polymers based on hydroxy-con-
taining ethers. However,'these ethers and the previously
reported polyurethane polymers based thereon do not pos-
sess any significant improvement in chemical and thermal
stability over the other commercially available polyure-
thane polymers. In general, the ordinary polyurethanes do
not possess a high degree of stability in the presence of
chemicals, solvents, strong acids and oxidizing agents.
In addition, the ordinary elastomeric polyurethanes are
subject to degradation at elevated temperature unless there
is added thereto a substantial amount of a stabilizer. Even
in the situation where stabilizers are employed, the poly-
urethane does not always exihibit good properties at ele-
vated temperature since many of the most readily avail-
able stabilizers tend to exude or otherwise fail at elevated
temperatures. Accordingly, it can be seen that there has
existed in the art a genuine need for a polyurethane poly-
mer possessing a high degree of resistance to the effects
of acid, strong oxidizing agents, chemicals, solvents and
elevated temperatures. This, the present invention pro-
vides to a very significant degree, and hence involves a
substantial advance in the state of the art.
Thus, it is a principal object of the present invention to
provide a novel class of polyurethane polymers.
More particularly, it is an object of the present inven-
tion to provide a novel class of polyurethane polymers
which are fluorine-containing and which are based upon
hydroxy-terminated fluorine-containing ethers.
Even more specifically, it is an object of the present
invention to provide a novel class of polyurethane poly-
mers which are resistant to acids, alkali, solvents, chemi-
HO—A «"*
/B
\ / m
20 with a fluorine-containing diisocyanate of the formula
OCN—A'—NCO
wherein in the above formulae A is an alkylene radical
preferably containing 1 to about 5 carbon atoms such as
25 methylene, ethylene, propylene, or butylene, B is a fluo-
rine containing alkyl radical containing 1 to about 5
carbon atoms, A' is a divalent organic group such as, an
aromatic hydrocarbon group, aliphatic hydrocarbon
group, a halohydrocarbon group, or hetero-interrupted
30 aromatic groups such as those having the formula
(X), (X). (X),
40
wherein A" is oxygen, sulfur, imino, alkylene, or alkylated
alkylene, the X is halogen, hydrogen, or alkyl, and n, a,
45 b and c are integers from 1 to about 10, m is an integer
from 1 to about 200, x is an integer from 1 to about
500, and z is an integer from 1 to 4. Preferably A' is
phenylene chlorophenylene, fluorophenylene, alkylated
phenylene and the like. In general, A' contains from 2
50 to about 20 carbon atoms.
Typically, B is monofluoromethyl, perfluoromethyl,
perfluorobutyl, and the like.
Preferably, the polyurethanes of the present inven-
tion are prepared by reacting a stoichiometric amount up
55 to a stoichimetric excess of the diisocyanate with the
hydroxy-containing polyethers. Where the diisocyanate is
utilized in a stoichiometric excess, there results an iso-
cyanate terminated polyurethane prepolymer. Such poly-
mer may be cured or chain extended with an active hy-
60 drogen-containing compound such as a diol, triol, water,
amine, or thiol. Accordingly, the present invention en-
compasses the discovery of such cross-linked and chain
extended polyurethane polymers.
The following examples are presented solely to illus-
65 trate the invention and should not be regarded as limiting
in any way. In the examples, the parts and percentages
are by weight unless otherwise indicated.
EXAMPLE I
70 The hydroxy terminated poly(trifluoropropyleneglycol)
mono(hydroxyhexafluoropentyl)ether having a molecu-
lar weight of 970 (8.0 g., 0.00825 mole) was added to
3,463,
3
tetrafluoro-p-phenylene diisocyanate (2.9 g., 0.0124
mole) at 60°-70° C. with mixing. The polymerization
was carried out at 80°-90° C. for 165 minutes, then post-
cured at 165° C. for Vi hour. The film was exposed to
moist air for 20 minutes, then postcured at 165° C. for
Vz hour. The final polymer was a tough, clear elastic
film capable of being used in coatings, laminates, adhe-
sives, etc.
EXAMPLE II
The hydroxyl terminated poly(trifluoropropylenegly-
col)mono(hydroxyhexafluoropentyl)ether having a mo-
lecular weight of 2150 (10.8 g., 0.005 mole) and tolylene-
2.4-diisocyanate (1.1 g., 0.006 mole) were mixed at 80°-
150° C. in a Vz hour period, followed by a postcure at
105° C. for \l/2 hours to yield a highly elastomeric tough
polymer.
This invention also includes the formation of prepoly-
mers for use as coatings or adhesives. Isocyanate-termi-
nated prepolymers can be prepared by using a greater
than stoichiometric amount of diisocyanate. This pre-
polymer is subsequently advanced with active hydrogen
containing compounds such as diamines, diols, dithiols,
etc. Hydroxyl-terminated prepolymers can be prepared
by using a greater than stoichiometric amount of diol.
This prepolymer is subsequently advanced with addition-
al diisocyanate.
The properties of these polymers may be varied by
suitable compounding. The amount and type of com
pounding agent to be incorporated in the stock is de-
pendent upon the use for which the polymer is intended.
The compounding agents ordinarily used in the rubber
industry with either natural or synthetic rubber are use-
ful with the products of this invention. These include
carbon black, clay, silica, talc, zinc, and magnesium ox-
ides, calcium and magnesium carbonate, titanium diox-
ide, and plasticizers. Inorganic and organic coloring
agents may be incorporated to give well defined colors.
Conventional rubber processing machinery such as rubber
mills or Werner-Pfleiderer or Banbury mixers may be
used. The 'resulting compounded stocks may be shaped
and cured in conventional equipment used in the rubber
industry. The solutions or dispersed gels prepared from
the polymers of this invention may be used for forming
supported or unsupported films, for coating fabrics or
solid surfaces, and for forming adhesive bonds between
a wide variety of plastics, elastomers, fabrics, metals,
wood, leather, ceramics and the like.
The hydroxy-termmated polyethers of this invention
are obtained in accordance with the teaching of my con-
currently .'filed .United States patent application Ser. No.
605,994, the disclosure of which is expressly incorpo-
rated herein by reference.
Having fully described the invention, it is intended that
it be limited only by the lawful scope of the appended
claims.
762
4
I claim:
1. A polyurethane polymer prepared by reacting (i) a
polyether having the formula:
HO—A- -A—O—1-CH-CHz-O-GA 2—j—.n.  vy r~v^ AA—\s AAI—'-'"/—
X n \ /n
wherein A is an alkylene group, B is a fluorine-contain-
ing alkyl group, n is an integer from 1 to about 10 and
in is an integer from 1 to about 200, with (ii) a diiso-
10 cyanate having the formula:
OCN—A'—NCO
wherein A' is a divalent organic group.
2. The polyurethane of claim 1 wherein A contains
15 from 1 to about 5 carbon atoms.
3. The polyurethane of claim 1 wherein A' contains
from 2 to about 20 carbon atoms.
4. The polyurethane of claim 1 wherein B contains
from 1 to about 10 carbon atoms.
20 5. The polyurethane of claim 1 wherein A' is selected
from the group consisting of aromatic hydrocarbon,
aliphatic hydrocarbon, halo hydrocarbon, and hetero-in-
terrupted aromatic groups.
6. The polyurethane of claim 1 wherein an excess of
25 diisocyanate is used to prepare the prepolymer.
7. The polyurethane of claim 1 wherein an excess of
polyether is used to prepare the polymer.
8. The polyurethane of claim 1 wherein the polymer
is isocyanate-terminated.
30 9. The polyurethane of claim 1 wherein the polymer
is hydroxy-terminated.
10. The polymers of claim 8 which are advanced by
reaction with an active hydrogen-containing compound.
11. The polymers of claim 9 which are advanced by
35 reaction with an isocyanate compound.
40
45
50
References Cited
UNITED STATES PATENTS
2,911,390 11/1959 Smith 260—77.5
2,929,800 3/1960 Hill 260—77.5
3,196,132 7/1965 Rosen 260—75
3,304,334 2/1967 Jones 260—618
3,305,497 2/1967 Stallings et al. 260—2.5
3,330,872 7/1967 Weesner 260—615
FOREIGN PATENTS
965,220 7/1964 Great Britain.
OTHER REFERENCES
Smith: "Industrial and Engineering Chemistry," vol-
ume 49, number 8, August 1957, pp. 1241-1246 relied
upon.
DONALD E. CZAJA, Primary Examiner
M. J. WELSH, Assistant Examiner
U.S. Cl. X.R.
117—161; 156—331; 260—37, 47


Polyurethanes from fluoroalkyl propyleneglycol polyethers

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