The preparation of poly(polyfluoroalkylene-glycol) mono (hydroxy polyfluoroalkylene) ethers from fluoroalkylene oxides is described

Trischler, F. D.

English

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(NflSi-Case-HFS-10507) FLOOBOHYD80XY
ETHEBS Patent (Whittaker Corp.) 2 p
CSCL 07C
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United States Patent Office 3,452,103Patented June 24, 1969
3,452,103
FLUOROHYDROXY ETHERS
Floyd 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. 605,994
Int. Cl. C07c 41/04, 43/28,41/10
U.S. Cl. 260—615 10 Claims
fluoroalkylene oxides with the alkali salt of a polyfluoro-
alkylene diol: .
ABSTRACT OF THE DISCLOSURE
This patent describes the preparation of poly(poly-
fluoralkylene-glycol) mono (hydroxy polyfluoralkylene)
ethers from fluoroalkylene oxides. 15
30
35
This invention is concerned with the preparation of
the new novel fluorohydroxy ethers.
The polymerization of trifluoropropylene oxide by cat-
ionic initiators has been reported previously. Among the ^0
initiators used were aluminum chloride, boron trifluoride
and ferric chloride. No effort was expended to determine
end groups. The polyether failed to react with maleic
anhydride; when it was reacted with hexamethylene diiso-
cyanate, the viscosity increased somewhat, but the prod- ,25
uct was not determined. The efforts of these investigators
was summarized as follows: "Previous attempts by other
investigators have not been very successful. Such a reac-
tion would be possible only if the polymer molecules were
terminated by reactive functional groups. No attempts
were made to determine the type of. end groups present
in the liquid polyethers prepared in this program."
Trifluoropropylene oxide has been polymerized using
boron trifluoride as the cationic catalyst. The product
contained unsaturated end groups believed to be
CFjF=CH—O—
Trifluoropropylene oxide was also polymerized with
aluminum chloride. The resultant polymer failed to yield 40
a solid elastomer when reacted with a diisocyanate, in-
dicating the polyether was not difunctional. In addition,
trifluoropropylene oxide was previously polymerized with
potassium hydroxide to obtain 10% polymer. This was
recently repeated to yield a 61% of polymer having a
molecular weight of 4300. The polymer, however, con-
tained terminal unsaturation believed to be
CFjj—CH=CH—
The polyether prepared by previous.investigators using 50
cationic initiators contain end groups which cannot be
utilized for chain extension by reaction with acids, acid
chlorides, acid anhydrides, esters, isocyanates, etc. The
polyether prepared by previous investigators using potas-
sium hydroxide initiation contain end groups in which 55
only one of the end groups will react with acids, acid
chlorides, acid anhydrides, esters, isocyanates, etc.
Accordingly, it is a principal object of this invention
to provide a novel class of polyethers.
More particularly, it is an object of this invention to 60
provide a novel method for the synthesis of polyethers.
It is also a part of an object of the instant invention
to prepare new fluorine-containing polyethers having a
plurality of functional terminal groups.
These and other objects and advantages of the pres- 65
ent invention will be apparent from the more detailed
description which follows.
Briefly, this invention is concerned with the prepara-
tion of poly (polyfluoralkylene - glycol)mono(hydroxy
polyfluoroalkylene) ethers, unique compositions of mat- 70
ter.
They are prepared by initiating the polymerization of
45
B( o
/ N r? i4_C Fr4-A O-I-CH—CHt-O-J-H\ J» L J»
wherein A is alkylene, normally containing from 1 to 5
carbons, Bf is a fluoroalkyl group having from 1 to
about 8 carbon atoms, M is an alkali .metal such as so-
dium, potassium and the like, « is an integer from 1 to
about 10, and m is an integer from 1 to about 1000.
Typically, Bf is monofluoromethyl, perfluoromethyl, per-
fluorethyl, perfluoroisopropyl, perfluorobutyl, and the
like.
The polymer obtained contains two primary alcohol
end groups which can be reacted with acids, acid chlo-
rides, acid anhydrides, esters, isocyanates, etc., for chain
extension and crosslinking..
The following example is presented solely to illustrate
the invention and should not be regarded as limiting in
any way. In the example, the parts and percentages are
by weight unless otherwise indicated.
EXAMPLE
The sodium salt of hexafluoropentanediol (11.7 g.,
0.05 mole), which can be obtained in the manner de-
scribed in J.A.C.S., Volume 74, page 444 (1952), and
trifluoropropylene oxide (45.0 g., 0.30 mole) were heated
at 88°-90° C. for 88 hours. The mixture was washed
with water, neutralized, dissolved in ether and dried. The
ether was removed to yield 41.0 g. (72.3% of poly-
ether) The molecular weight by vapor pressure osmom-
etry was 1000, and the hydroxyl equivalent weight was
500. A polyether (5.9 g., 0.01 mole) prepared as above
having a molecular weight of 585, tolyene-2,4-diisocya-
nate (2.1 g., 0.012 mole) and stannous octoate (2 drops)
were mixed and cured 1 hour at 105° C. to yield a solid
polymer suitable for use as a coating, adhesive, foam,
or laminating resin.
The infrared data, molecular weight and end group
analysis verified the identity of this compound.
The polyethers of this invention are usable for further
reactions with diacids, diacid chlorides, anhydrides, di-
esters, diisocyanates, etc., which then can be used for
coatings, foams, adhesives, laminates, etc.
The polymers prepared according to this invention
have many varied uses. They may be employed in the
preparation of tires, inner tubes, belts, hose and tubing,
wire and cable jackets, footwear, sponges, coated fabrics,
and a wide variety of coated or molded articles. They are
characterized by a number of advantageous properties
including excellent resistance to heat and cold, direct sun-
light, oxygen and ozone, oil and solvents. They display
unusually outstanding resistance to mechanical abrasion
and to deterioration caused by flexing, stretching and the
like.
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 oxides,
calcium and magnesium carbonate, titanium dioxide, and
plasticizers. Inorganic and organic coloring agents may
be incorporated to give well defined colors. Conven-
tional rubber processing machinery such as rubber mills
or Werner-Pfieiderer or Banbury mixers may be used.
3,452,103
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 un-
cured polymers of this invention may be for -forming 5
supported or unsupported films, for laminates, for coat-
ing fabrics or solid surfaces, and for forming adhesive
bonds between a wide variety of plastics, elastomers,
fabrics, metals, wood, leather, ceramics and the like.
Having fully described the invention, it is intended ,„
that it be limited to the full scope of the claims.
I claim:
1. A novel polyether having the formula:
G II
x /D L
15
J»
wherein A is alkylene containing up to 5 carbon atoms,
n is an integer from 1 to about 10, Bf is a fluoroalkyl
group having from 1 to about 8 carbon atoms, and m
is an 'integer from 1 to about 1000.
. 2. The polyether of claim 1 wherein A is methylene.
3. The polyether of claim 1 wherein n is equal to 3.
4. The polyether of claim 1 wherein B( is trifluoro-
methylene.
5. The method of preparing novel polyether having
the formula:
with an alkali salt of a polyfluoroalkylene diol of the
formula:
wherein A is an alkylene group containing up to 5 carbon
atoms, Bf is a fluoroalkyl group having from 1 to about
8 carbon atoms. M is an alkali metal, n is an integer
from 1 to about 10 and m is an integer from 1 to about
1000, neutralizing, and recovering the polyether product.
6. The method of claim 5 wherein A is methylene.
7. The method of claim 5 wherein Bf is trifluoro-
methylene.
8. The method of claim 5 wherein M is sodium.
9. The method of claim 5 wherein n is equal to 3.
10. The method of preparing a novel polyether which
comprises heat reacting the sodium salt of hexafluoro-
pentanediol with trifluoropropylene oxide, neutralizing,
and recovering the polyether product.
20
25
GilH-C -O-j-H
Jm 30
which comprises heat reacting a fluoroalkylene oxide hav-
ing the formula:
Bt—CI -CHi
2,723,999
3,244,754
3,318,960
528,136
736,991
References Cited
UNITED STATES PATENTS
11/1955 Cowenetal.
4/1966 Bruson et al.
5/1967 Earing.
FOREIGN PATENTS
7/1956
9/1955
Canada.
Great Britain.
LEON ZrrVER, Primary Examiner.
H. T. MARS, Assistant Examiner.
35
U.S. Cl. X.R.
260—2, 2.5, 37, 75, 77.5


Fluorohydroxy ethers

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