A polyurethane polymer prepared by reacting a hydroxy-terminated polyformal with an organic diisocyanate is presented

Trischler, F. D.

English

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POLXOBETHaUE Patent (Whittaker Corp.)
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United States Patent Office 3,475,384Patented Oct. 28, 1969
3,475,384
FLUORINE-CONTAINING POLYURETHANE
Floyd D. Trischler, San Diego, Calif., assignor to
Whittaker Corporation, Los Angeles, Calif., a cor-
poration of California
No Drawing. Filed Dec. 30, 1966, Ser. No. 605,964
Int. Cl. C08g 22/14
S. Cl. 260—77.5 5 Claims
ABSTRACT OF THE DISCLOSURE
A polyurethane polymer prepared by reacting a hy-
droxy-terminated polyformal having the formula
HO— A
wherein A, A' and A"' are alkylene, m and n are integers
from 1 to about 10, and x is an integer from 1 to about
100 with an organic diisocyanate having the formula
OCN— A'"— NCO
wherein A'" is a divalent organic group.
effects of acid, strong oxidizing agents, and elevated tem-
peratures. This the present invention provides to a very
significant degree, and hence involves a substantial ad-
vance in the state of the art.
5 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 in-
vention to provide a novel class of polyurethane poly-
Even more specifically, it is an object of the present
j0 invention to provide a novel class of polyurethane poly-
mers which are acid, alkali and oxidizing agent resistant,
based upon fluorine-containing formals and fluorine-con-
taining diisocyanates.
mers which are fluorine-containing and which are based
15 upon hydroxy-terminated fluorine-containing formals.
In another aspect of the present invention it is an ob-
ject thereof to provide a new method for the preparation
of novel fluorine-containing polyurethanes.
These and other objects and advantages of the present
20 invention will be apparent from the more detailed descrip-
tion which follows.
Briefly, the present invention comprises a novel fluorine-
containing polyurethane having the following repeating
unit:
A_0_/A/_0_A,,
\
o H H o
\
This invention relates to a novel class of fluorine-
containing polyurethane polymers prepared by the reac-
tion of fluorinated diisocyanates with fluorine-containing
hydroxy-terminated formals.
This application is a continuation-in-part of United
States patent application Ser. No. 554,959, now U.S.
Patent No. 3,419,531, the disclosure of which is expressly
incorporated herein by reference.
In the printed literature there has been brief reference
to the synthesis of urethane polymers based on hydroxy-
containing formals. However, these formals and the previ-
ously reported polyurethane polymers based thereon do
not possess any significant 'improvement in chemical and
thermal stability over the ordinary commercially avail-
able polyurethane polymers. In general, the ordinary
polyurethanes do not possess a high degree of stability
in the presence of strong acids and oxidizing agents. In
addition the ordinary elastomeric polyurethanes are sub-
ject 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 exhibit 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
polymer possessing a high degree of resistance to the
prepared by reacting a fluorine-containing hydroxy-ter-
„. minated formal having the formula:
oo
with a fluorine-containing organic diisocyanate having
40
 the formula:
. OCN—A'"—NCO
wherein A, A' and A" are alkylene groups, preferably
containing from 1 to about 5 carbon atoms, such as
45 methylene, ethylene, propylene, butylene and the like,
A'" is a divalent organic group, preferably a fluorine-con-
taining aromatic group such as perfluorophenylene and
the like, x and y are integers from 1 to about 100, and
m and n are integers from 1 to about 10.
50 In the above formulae, A'" may typically be:
~C/~ ~CSf \ 71CHi—
60 wherein x is hydrogen, chlorine, fluorine or lower alkyl,
3,475,384
normally having from 1 to about 5 carbon atoms; A""
is oxygen, sulfur, imino, alkylated imino
(J-)
or alkylene; q is an integer from 1 to 4, and z is an
integer from 1 to about 10. Generally, when A"" is
alkylated imino or alkylene, it contains from 1 to about
10 carbon atoms.
The novel polyurethanes of the present invention are
 1Q
generally prepared by reacting approximately stoichio-
metric amounts of the diisocyanate and formal of the
above formulae. However, the invention envisions the use
particularly of a slightly stoichiometric excess of diiso-
cyanate. In this manner the polyurethane product is iso- 35
cyanate-terminated, and hence is readily curable by mate-
rials which are complementary reactive with isocyanate
groups. In general, any active hydrogen-containing ma-
terial may be utilized to cure or chain-extend an isocy-
anate terminated polyurethane. Typical of such active 20
hydrogen-containing compounds are diols, triols, water,
amines, thiols, and the like.
This invention also includes the formation of pre-
polymers for use as coatings or adhesives. Isocyanate-
terminated prepolymers can be prepared by using a 25
greater than stoichiometric amount of diisocyanate. This
prepolymer 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. 30
This prepolymer is subsequently advanced with additional
diisocyanate.
The following example is presented to illustrate the
invention. In the example, the parts and percentages are
by weight unless otherwise indicated. 35
Example
Tetrafluoro-p-phenylene diisocyanate (3.7 g., 0.0160
mole) was added to the hydroxyl-terminated poly(hexa-
fluoropentamethylene formal) of 600 molecular weight -40
(8.0 g., 0.0133 mole) at 100° C. and mixed. The poly-
mer was then post-cured at 165° C. for Vi hour to yield
an extremely tough, flexible elastomer.
The properties of these polymers may be varied by
suitable compounding. The amount and type of com- 45
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 car- 50
bon black, clay, silica, talc, zinc and magnesium oxides,
calcium and magnesium carbonate, titanium dioxide, and
plasticizers. Inorganic and organic coloring agents may
be incorporated to give well denned colors.
Conventional rubber processing machinery such as rub- 55
ber 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 uncured polymers of this invention may be used for 60
HO-A-C Fr
forming supported or unsupported films, for coating fab-
rics or solid surfaces, and for forming adhesive bonds
between a wide variety of plastics, elastomers, fabrics,
metals, wood, leather, ceramics and the like.
Diisocyanates suitable for the practice of this invention,
but not limited thereto, are tetrafluoro-m-phenylene di-
isocyanate, tetrafluoro-p-phenylene diisocyanate, fluoro-
trichloro - p-phenylene diisocyanate, fluorotrichloro-m-
phenylene diisocyanate, difluorodichloro-p-phenylene di-
isocyanate, difluorodichloro-m-phenylene diisocyanate,
chlorotrifluoro-p-phenylene diisocyanate, chlorotrifluoro-
m-phenylene diisocyanate, tetrachloro-m-phenylene diiso-
cyanate, tetrachloro - p-phenylene diisocyanate, difluoro-
trimethylene diisocyanate, tetrafluorotetramethylene di-
isocyanate, hexafluoropentarhethylene diisocyanate, octa-
fluorohexamethylene diisocyanate, octafluorobiphenylene
diisocyanate, oxybis (tetrafluorophenyl isocyanate),
thiobis (teterafluorophenyl isocyanate), and methylene
bis(tetrafluorophenyl isocyanate).
I claim:
1. A polyurethane polymer prepared by reacting a
hydroxy-terminated polyformal having the formula
^ ^-A-0-£-A'-0-A"-(-C F,-^-A"— 0 J-H
V. / n \ V. Xm / x
wherein A, A' and A" are alkylene, in and n are integers
from 1 to about 10 and x is an integer from 1 to about
100 with an organic diisocyanate having the formula
OCN— A'"'— NCO
wherein A'" is a divalent organic group.
2. The polyurethane of claim 1 wherein, A, A' and A"
are methylene and A'" is a divalent .perfluoro aromatic
group.
3. The polyurethane of claim 1 wherein an excess of
diisocyanate is used to prepare the polymer.
4,. The polyurethane of claim 1 wherein an excess of
polyformal is used to prepare the polymer.
5. The polyurethane of claim 1 wherein A, A' and A"
contain from 1 to 5 carbon atoms.
References Cited
UNITED STATES PATENTS
2,511,544 6/1950 Rinke et al. ________ 260—77.5
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
3,234,184 2/1966 McShane et al. ______ 260—75
3,326,855 6/1967 Matzner et al ------ ___ 260 — 47
OTHER REFERENCES
Schonfeld, Journal of Polymer Science, vol. 59, pp.
87-92 (May 1962).
DONALD E. CZAJA, Primary Examiner
M. J. WELSH, Assistant Examiner
U.S. Cl. X.R.
117^-161; 156—331; 260—37, 67


Fluorine containing polyurethane

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