U.S. patent number 3,674,800 [Application Number 04/816,013] was granted by the patent office on 1972-07-04 for derivatives pyridinium of polyfluoroisoalkoxyalkanamides.
This patent grant is currently assigned to Allied Chemical Corporation. Invention is credited to Edward Stephen Jones, Aziz Urrehman Khan, Julian A. Otto, Alson K. Price, Richard F. Sweeney.
United States Patent |
3,674,800 |
Sweeney , et al. |
July 4, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
DERIVATIVES PYRIDINIUM OF POLYFLUOROISOALKOXYALKANAMIDES
Abstract
N-methylol and N-halomethyl derivatives of
polyfluoroisoalkoxyalkanamides, and their substituted ammonium
salts characterized in that an ether oxygen links a fluorinated
carbon atom attached to two fluoroalkyl groups and at least one
--CF.sub.2 -- group. These compounds are useful as water and oil
repellency agents.
Inventors: |
Sweeney; Richard F. (Randolph
Township, Morris County, NJ), Khan; Aziz Urrehman
(Elizabeth, NJ), Price; Alson K. (Morristown, NJ), Jones;
Edward Stephen (Whippany, NJ), Otto; Julian A.
(Stockholm, NJ) |
Assignee: |
Allied Chemical Corporation
(New York, NY)
|
Family
ID: |
25219445 |
Appl.
No.: |
04/816,013 |
Filed: |
April 14, 1969 |
Current U.S.
Class: |
546/336; 8/188;
546/102; 546/175; 560/184; 562/586; 564/159; 564/201; 564/202;
8/142; 8/194; 546/146; 546/337 |
Current CPC
Class: |
C07C
59/135 (20130101); C07C 59/135 (20130101); C07C
59/135 (20130101); C07D 215/10 (20130101); D06M
13/402 (20130101); C07C 51/60 (20130101); C07C
51/58 (20130101); C07D 213/20 (20130101); C07C
51/58 (20130101); C07C 51/09 (20130101); C07C
51/09 (20130101); D06M 13/432 (20130101); D06M
13/322 (20130101); C07C 59/135 (20130101); D06M
13/35 (20130101); C07C 335/32 (20130101); C07C
51/60 (20130101) |
Current International
Class: |
C07C
335/00 (20060101); C07C 335/32 (20060101); C07C
51/09 (20060101); C07D 213/20 (20060101); C07C
59/135 (20060101); C07C 59/00 (20060101); C07C
51/60 (20060101); C07C 51/58 (20060101); C07D
213/00 (20060101); C07D 215/00 (20060101); C07D
215/10 (20060101); D06M 13/322 (20060101); D06M
13/402 (20060101); D06M 13/35 (20060101); D06M
13/00 (20060101); D06M 13/432 (20060101); C07d
031/44 () |
Field of
Search: |
;260/295AM ;8/116.2 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rotman; Alan L.
Claims
We claim:
1. A compound of the formula ##SPC10##
wherein
i. R.sub.1 and R.sub.2 independently at each occurrence can be
fluorine, chlorine, perfluoroalkyl of from one to two carbon atoms
or together can form a cyclic perfluoroalkylene group of six carbon
atoms with the proviso that both R.sub.1 and R.sub.2 cannot be
chlorine;
ii. Z is fluorine or chlorine;
iii. r is an integer 1 to 2;
iv. m and n are integers from 0-10, the sum of m and n being
0-20;
v. p is 0 or 1;
vi. Q represents a positively charged quaternary radical selected
from the group consisting of the pyridinium radical and pyridinium
radicals substituted with from one to three methyl groups;
vii. A represents a negatively charged halogen atom.
2. Compound as claimed in claim 1 wherein R.sub.1 and R.sub.2 are
fluorine.
3. Compound as claimed in claim 1 wherein A is chloride or
bromide.
4. A compound as claimed in claim 1 wherein Q is the pyridinium
radical.
5. A compound according to claim 4 wherein Q is pyridinium A is
chloride.
6. A compound according to claim 4 of the formula
7. A compound according to claim 4 of the formula
8. A compound according to claim 4 of the formula
9. A compound according to claim 4 of the formula
10. A compound according to claim 4 of the formula
Description
This invention relates to N-methylol and N-halomethyl derivatives
of fluorocarbon amides and their substituted ammonium salts. More
particularly, this invention relates to N-methylol and N-halomethyl
derivatives of polyfluoroisoalkoxyalkanamides and their substituted
ammonium salts, useful as oil and water repellency agents.
Quaternary ammonium compounds of N-halomethylamides of
fluorocarboxylic acids are known which have oil and water
repellency properties. For example, U.S. Pat. No. 3,147,065 issued
Sept. 1, 1964 discloses quaternary compounds of the formula
R.sub.f --R--CONH--CH.sub.2 Q.sup.+X.sup.-
wherein R.sub.f is a perfluoroalkyl group of four to 12 carbon
atoms, R is an alkylene group of the formula --CH.sub.2
CHCl(CH.sub.2).sub.m -- or --(CH.sub.2).sub.n -- wherein m is an
integer from 1-10 and n is an integer from 3-12, Q is a radical of
a tertiary nitrogenous base and X is chlorine or bromine. These
compounds impart moderate oil repellency to cellulosic materials
such as cotton cloth but inadequate water repellency, at
comparatively high loadings. U.S. Pat. No. 3,147,066, also issued
Sept. 1, 1964 discloses quaternary compounds of the formula
R.sub.f --SO.sub.2 NR(CH.sub.2).sub.m --CONH--CH.sub.2
Q.sup.+X.sup.-
wherein R.sub.f is a perfluoroalkyl group of four to 12 carbons
atoms, m is an integer from 2-12, R is alkyl of four to six carbon
atoms, Q is a radical of a tertiary nitrogenous base and X is
chlorine or bromine. These compounds impart good oil repellency but
inadequate water repellency to cellulosic materials. Quaternary
ammonium compounds substituted with long chain alkyl groups in
place of terminal perfluoroalkyl groups impart water repellency to
fabrics, but no oil repellency. Thus generally formulations or more
than one quaternary ammonium compound have been required to impart
both water and oil resistance to textiles and the like. Known
compounds are also deficient in their durability, that is, their
ability to retain their effectiveness after repeated laundering
and/or dry cleaning cycles. The elaborate formulations required
heretofore add to the cost of imparting durable oil and water
resistance of cellulosic substrates and compounds which impart
durable oil and water repellency have long been sought.
Thus it is a principal object of the present invention to provide
compounds which impart oil and water repellency when applied to a
substrate.
It is another object to provide compounds which impart improved oil
and water repellency to cellulosic materials.
It is a further object to provide oil and water repellents for
fabrics which retain their effectiveness through successive
laundering and dry cleaning cycles.
It is still another object to provide compounds useful both as
internal and external sizes for paper to impart oil, water and ink
resistance thereto.
Further objects will become apparent from the following detailed
description thereof.
The novel compounds of the invention are N-methylol and
N-halomethyl derivatives of amides of fluorocarbon acids and their
substituted ammonium salts of the formula ##SPC1##
wherein R.sub.1 and R.sub.2 independently at each occurrence can be
fluorine, chlorine or perfluoroalkyl, and together can form a
cyclic perfluoroalkylene group, with the proviso that both R.sub.1
and R.sub.2 cannot be chlorine; Z.sub.1, Z.sub.2, Z.sub.3 and
Z.sub.4 can be fluorine, chlorine or hydrogen with the proviso that
no more than two of Z.sub.1 -Z.sub.4 are chlorine; X.sub.1,
X.sub.2, X.sub.3 and X.sub.4 can be chlorine, fluorine or hydrogen
with the proviso that no more than one of X.sub.1 -X.sub.4 is
chlorine; r is an integer from 1 to 2; m and n are integers from
0-75; the sum of m and n is 0-75; p is an integer from 0-1; Y is
hydrogen or fluorine and W is selected from the group consisting of
hydroxyl, halogen and QA wherein Q is a residue of a
nitrogen-containing quaternizing agent containing at least one
positively charged nitrogen atom and A is at least one negatively
charged halogen atom with the proviso that the number of negatively
charged halogen atoms of A is equal to the number of said
positively charged nitrogen atoms and t is an integer equal to the
number of positively charged nitrogen atoms.
The criticality of the structure of the above-described compounds
is in the polyfluoroisoalkoxyalkyl tail portion of the molecule
wherein an ether oxygen atom links a fluorinated carbon atom
attached to two fluoroalkyl groups and at least one --CF.sub.2 --
group.
The amide starting materials useful in the invention have the
formula ##SPC2##
wherein R.sub.1, R.sub.2, Z.sub.1 -Z.sub.4, X.sub.1 -X.sub.4, Y,
r,m, n and p have the meanings given above.
The amides of formula (2) can be prepared from
polyfluoroisoalkoxytetrafluoroethyl iodides of the formula
##SPC3##
wherein R.sub.1 and R.sub.2 have the meanings given above. These
iodides are prepared by reacting an appropriate ketone with an
ionizable fluoride salt, e. g. CsF or KF to form a fluorinated
organic salt which is reacted with tetrafluoroethylene and iodine.
These reactions are described in copending U.S. applications of
Litt et al. Ser. No. 492,276 filed Oct. 1, 1965 and Ser. No.
513,574 filed Dec. 13, 1965. The pertinent subject matter of these
applications is hereby incorporated by reference.
The iodides of formula (3) can be reacted with unsaturated
compounds having the formulas Z.sub.1 Z.sub.2 C.dbd.CZ.sub.3
Z.sub.4 and/or X.sub.1 X.sub.2 C.dbd.CX.sub.3 X.sub.4 wherein
Z.sub.1 -Z.sub.4 and X.sub.1 -X.sub.4 are as described hereinabove,
to prepare polyfluoroisoalkoxyalkyl iodides of higher molecular
weight. Suitable unsaturated compounds include for example
ethylene, difluoroethylene, difluorochloroethylene,
trifluoroethylene, tetrafluoroethylene and the like. These
reactions can be initiated by heat, e.g. temperatures from about
100.degree. C. to about 350.degree. C., preferably from about
150.degree.-200.degree. C. or by a free radical initiator, e.g.
azobisisobutyronitrile, benzoyl peroxide and the like. These
reactions are described in greater detail in copending U.S.
application of Anello et al., Ser. No. 633,359 filed Apr. 25, 1967.
The pertinent subject matter of that application is hereby
incorporated by reference.
The following series of equations will serve to further illustrate
the preparation of the iodides, wherein R.sub.1, R.sub.2, Z.sub.1
-Z.sub.4, X.sub.1 -X.sub.4, m and n have the meanings given above.
##SPC4##
It will be understood that when m and/or n is 0, the applicable
telomerization equations 3 and/or 4 are omitted.
The amides are derived in conventional manner from their
corresponding carboxylic acids.
The preferred class of carboxylic acid precursors of amides useful
in the invention have the formula ##SPC5##
wherein R.sub.1 and R.sub.2 can be fluorine, chlorine or
perfluoroalkyl of one to two carbon atoms providing both R.sub.1
and R.sub.2 are not chlorine, m and n are integers from 0-10 and Y,
r and p have the meanings given above.
Depending upon the values of m, n, p and r, the preferred methods
of preparing the acid precursors of the amides from the
polyfluoroisoalkoxyalkyl iodides will vary.
Carboxylic acids of formula (5) wherein r is 2, m is as described
above, p is 0 and n is at least one, can be prepared by reacting a
suitable iodied of formula (4) having a terminal --CH.sub.2 I group
with a water-soluble metal cyanide to form the corresponding
nitrile. The nitrile can be hydrolyzed to the corresponding free
acid in conventional manner.
Carboxylic acids of formula (5) wherein r is 2, m and n are as
described above and p is 0 can be prepared by reacting an iodide of
formula (4) having at least one terminal --CH.sub.2 CH.sub.2 I
group by elimination of HI from the terminal group with a strong
base to form the corresponding terminal olefin and oxidizing the
olefin with a conventional oxidizing agent such as permanganate or
dichromate to the carboxylic acid.
Carboxylic acids of formula (5) wherein r is 2, m is as described
above, n is at least 1, p is 0 or 1 and Y is H, can be prepared by
reacting a suitable iodide of formula (4) with a terminally
unsaturated hydrocarbon carboxylic acid or its corresponding ester
in the presence of a free radical initiator to form the
corresponding iodocarboxylic acid or ester. The iodocarboxylic acid
can be reduced to the free acid in conventional manner, as with
zinc in alcohol. The ester can by hydrolyzed to the free acid in
known manner. Alternatively, the iodo ester can be
dehydrohalogenated in known manner, as with alkali to the
corresponding alkenoic acid, and hydrogenated, as with hydrogen in
the presence of a catalyst such as platinum oxide, to the
corresponding carboxylic acid.
Carboxylic acids of formula (5) wherein n and p are 0, r is 2, and
m is as described above can be prepared by reacting a suitable
iodide of formula (4) with (CN).sub.2 under pressure of 20-200
atmospheres at temperatures of 300.degree. C. or more, to form the
corresponding nitrile. The nitrile can be hydrolyzed to the free
acid in a conventional manner.
Carboxylic acids of formula (5) wherein (a) r is 1, m, n and p are
0, or wherein (b) r is 2, n is at least 1 p is 1, Y is H, and m is
as described above can be prepared by reacting a suitable iodide
with SO.sub.3 to form the pyrosulfate, or with oleum to form the
hydrosulfate and hydrolyzing the pyrosulfate or hydrosulfate to the
corresponding alcohol. The alcohol can be oxidized to the free
carboxylic acid with conventional oxidizing agents. The preparation
of the alcohols is described in greater detail in copending U.S.
application of Anello, et al., Ser. No. 721,089 filed Apr. 12,
1968, now abandoned. The pertinent subject matter of this
application is hereby incorporated by reference.
Carboxylic acids of formula (5) wherein r is 2, n is 0, p is 1, Y
is H or F and m is as described above can be prepared from the
corresponding alcohol wherein n is 1, and X.sub.3 and X.sub.4 are
hydrogen by oxidation as hereinbefore described.
Carboxylic acids of formula (5) wherein r is 2, n is 0, p is 1, Y
is H and the carbon atom in the .beta.-position with respect to the
carboxyl group is substituted with two fluorine atoms, can be
prepared by oxidation of the fluoroolefin containing a terminal
ethylene group having the formula ##SPC6##
wherein R.sub.1, R.sub.2 and m have the meanings given above. These
fluoroolefins can be prepared by reacting a suitable iodide with
allyl alcohol at a temperature between about 10.degree. to
450.degree. C., preferably from 150.degree.-300.degree. C., under
superatmospheric pressure. The terminal ethylene group can be
oxidized to the carboxylic acid in conventional manner.
Carboxylic acids of formula (5) wherein r is 2, n is 0, m is as
described above, p is 1 and Y is F, can be prepared reacting a
suitable iodide with sulfur trioxide to form the corresponding acid
fluoride and fluoropyrosulfate at a temperature of from 50.degree.
to 175.degree. C., preferably from 100.degree.-150.degree. C. and
hydrolyzing the fluoropyrosulfate and/or acid fluoride to the
desired acid by refluxing with water or to the corresponding ester
by refluxing with an alcohol. Alternatively, the corresponding acid
salts can be made by reaction of the acid fluoride and/or
fluoropyrosulfate with alkali metal hydroxide and acidifying the
aqueous mineral acid.
Carboxylic acids of formula (5) wherein r is 2, and m, n and p are
0, can be prepared from the polyfluoroisoalkoxytetrafluoroethyl
iodide of formula (3) by reaction with a Grignard reagent to form a
magnesium halide adduct, reacting this adduct with CO.sub.2 to form
the magnesium halide salt and acidifying the salt with a mineral
acid. The reactions involving the Grignard reagent are preferably
carried out below about 0.degree. C.
The preparation of these acids and their precursors are described
in greater detail in corresponding U.S. applications of Anello et
al. Ser. Nos. 721,113, 721,115 and 721,117 filed Apr. 12, 1968. The
pertinent subject matter of these applications is hereby
incorporated by reference. The carboxylic acids as described can
also be prepared in other ways as will be known to one skilled in
the art.
The amides can be prepared from the carboxylic acids as described
in conventional manner by reacting their lower alkyl ester or acid
chlorides with ammonia.
The N-methylol derivatives of the invention can be prepared by
reacting an amide of formula (2) with formaldehyde. At least 1 mol
of formaldehyde will be required for complete reaction but in
general an excess of the formaldehyde of up to about 5 mols, is
employed. The reaction can be carried out in the presence or
absence of an inert solvent such as benzene, xylene,
trifluorotrichloroethylene and the like. A basic catalyst such as
sodium bicarbonate or sodium carbonate can also be employed if
desired, but is not required. Good results are obtained without the
use of either solvent or catalyst.
The reaction is generally carried out at temperatures of about
70.degree.-150.degree. C. but this is not critical and higher or
lower temperatures can be employed if desired. When the reaction is
carried out in the absence of a solvent, the temperature is usually
maintained above the melting point of the amide reactant.
The N-halomethyl amides of the invention can be prepared by
reacting an amide of formula (2) with a hydrogen halide or thionyl
halide and formaldehyde. The reaction can be carried out
conveniently by adding the hydrogen halide into a solution of the
amide and formaldehyde in an inert solvent at a temperature from
about room temperature up to about 100.degree. C. Suitable solvents
include aromatic hydrocarbons such as benzene, toluene, xylene and
the like.
Any source of formaldehyde can be employed in preparing the
N-methylol or N-halomethyl compounds such as formaldehyde,
paraformaldehyde and trioxane. The anhydrous form of these reagents
is preferred.
Known condensing agents can be employed to increase the rate of
reaction, such as metallic halides including zinc chloride, lithium
chloride and the like. They are generally employed in amounts of
from 0.1 to 1 mol per mol of amide.
Suitable halogenation agents include hydrogen chloride, hydrogen
fluoride, hydrogen bromide, hydrogen iodide, thionyl chloride,
thionyl bromide and the like.
At least 1 mol of formaldehyde and 1 mol of halide is required for
complete reaction with 1 mol of the amide, but in general an excess
of formaldehyde, on the order of 1.5 to 2.0 mols per mol of amide,
is employed. Higher amounts can be employed if desired. When a
gaseous halogenating agent is used, it can conveniently be bubbled
into the reaction mixture until reaction is complete.
The reaction will proceed readily at room temperature, but higher
or lower temperatures can be employed if desired, as from 0.degree.
C. to reflux temperatures and the like.
Alternatively, the N-halomethyl amides can be prepared from the
N-methylol amides by reacting the N-methylol amide with a
halogenating agent in solution as described above.
The N-halomethyl and N-methylol compounds of the invention can be
employed as is, or can be further purified if desired in
conventional manner as by distillation, recrystallization or
trituration with a suitable solvent as will be known to one skilled
in the art.
The substituted ammonium derivatives of the invention can be
prepared by reacting the N-halomethyl compounds of the invention
with a quaternizing agent, either thiourea or a tertiary
nitrogenous base. This reaction can be carried out conveniently at
room temperature, but higher or lower temperatures, on the order of
from 0.degree. to about 70.degree. C. can be employed if desired.
The reaction is generally complete in a short time, i.e. in from 5
minutes to 1 hour.
Alternatively, the substituted ammonium salts can be prepared
directly from the amides by reacting the amide, formaldehyde and a
hydrohalide salt of a tertiary nitrogenous base in a suitable
solvent. This may avoid the use of the corrosive hydrogen halide
gases. An excess of the nitrogenous base employed can act as the
solvent for the reaction. Generally an excess of the formaldehyde
and amine salt is used, on the order from 2 to 4 mols per mol of
the amide. The reaction can be carried out at temperatures from
about 25.degree. to 100.degree. C., but preferably at about
60.degree. to 80.degree. C. Preferably the reactants are heated for
several hours, conveniently 18-20 hours to ensure complete
reaction.
Any known tertiary nitrogenous base capable of forming a salt or
quaternary ammonium derivative can be employed to prepare the
quaternary ammonium compounds of the invention. Suitable bases
include trialkyl-substituted amines such as trimethylamine,
triethylamine, triisobutylamine, tridodecylamine,
methyldiethylamine, dimethylhexylamine, methylethylhexylamine and
the like; cycloalkyl amines such as tricyclohexylamine,
propyldicyclohexylamine and the like; aromatic amines such as
dimethylaniline, benzyldimethylamine, diethylaniline and the like,
hydroxyalkyl-substituted amines such as triethanolamine,
dimethylethanolamine and the like; heterocyclic amines such as
pyridine, the lutidines, quinoline, isoquinoline, acridine, 2,4,6-
collidine and the like. Polyfunctional amines can also be employed,
and in such case more than one mol of an N-halomethyl compound as
described hereinabove can react with one mol of the amine to
prepare quaternary ammonium compounds having more than one
positively charged nitrogen atom. Suitable polyfunctional amines
include N,N,N+, N'-tetramethyl-1,3-propane diamine, aziridine
polymers and the like. Thiourea is also a satisfactory quaternizing
agent. Pyridine is preferred for the preparation of textile
treating agents due to its low cost and ready availability.
Quaternization can be effected using an excess of the amine as
solvent, or a different solvent can be added, such as benzene,
toluene, or trichlorotrifluoroethane. The substituted ammonium
compounds can be isolated by evaporation of the solvent, addition
of a nonsolvent, such as ether, and the like as will be known to
one skilled in the art. The product can be further purified if
desired by recrystallization from a suitable solvent such as
acetonitrile or chloroform, or by trituration with an inert solvent
such as ether.
The compounds of the invention are useful oil repellency agents and
can be applied to a variety of substrates, including paper,
cellulosic films, wood, leather, textile fibers, yarns and fabrics,
metals, glass and the like. The resultant articles or treated
substrates are oil repellent and have a measure of soil, water and
grease resistance.
The substituted ammonium slats of the invention are water soluble
and thus are particularly useful as sizes for papers and textile
treating agents. In addition, these compounds are highly durable
and treated fabrics retain their oil and water resistance after
numerous laundering and/or dry cleaning cycles. This durability may
be enhanced in some cases by curing, as by heating to promote
reaction between the compounds of the invention and the fabric
substrate, or by use of a catalyst to facilitate attachment of the
compounds of the invention to the fabric substrate.
In the treatment of fabrics, the compounds of the invention can be
used alone or in combination with known fabric finishes such as
mildew preventatives, moth resistant agents, crease resistant
resins, lubricants, softeners, sizes, flame retardants, antistatic
agents, dye fixatives and the like. In the treatment of paper, the
compounds of the invention can be used alone or can be added as an
ingredient in a wax, starch, casein, elastomer or wet strength
resin formulation. The compounds of the invention can be applied in
conventional manner as by dipping, coating, spraying, brushing and
the like from organic or aqueous solution or from aqueous
suspension as will be known to one skilled in the art.
The invention will be illustrated further by the following
examples, but it is to be understood that the invention is not
meant to be limited to the details described herein. In the
examples, all parts and percentages are by weight unless otherwise
noted.
EXAMPLE 1
6-Heptafluoroisopropoxyperfluorohexyl iodide (50.2 parts),
(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.3 I, and 26.2 parts of
liquid sulfur trioxide were charged to a glass lined pressure
vessel fitted with a pressure gauge and stirrer and connected to a
dry ice-acetone trap. The vessel was flushed with nitrogen, sealed
and heated at about 140.degree. C. for 34 hours. The vessel was
cooled to room temperature, vented, and the product mixture
withdrawn. The product was a mixture of 7.6 parts of the acid
fluoride, (CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.2 CF.sub.2
COF and 7.5 parts of the pyrosulfuryl fluoride (CF.sub.3).sub.2
CFO(CF.sub.2 CF.sub.2).sub.3 OSO.sub.2 OSO.sub.2 F.
A mixture of 12.2 parts of (CF.sub.3).sub.2 CFO(CF.sub.2).sub.5 COF
and 10.8 parts of (CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.3
OSO.sub.2 OSO.sub.2 F prepared as above was charged to a vessel
fitted with a reflux condenser and dropping funnel. The mixture was
cooled to 0.degree. C. and 26 parts of methanol were added over a
20 minute period. The mixture was refluxed for 19 hours, cooled to
room temperature and washed with ice water. The organic layer was
dried over anhydrous sodium sulfate and distilled under reduced
pressure.
The corresponding methyl ester, (CF.sub.3).sub.2
CFO(CF.sub.2).sub.5 COOCH.sub.3 was obtained.
A solution of 18.5 parts of the methyl ester prepared as above in
50 parts by volume of ethyl ether was cooled to 0.degree. C.
Gaseous ammonia was bubbled slowly into the solution until
saturation was complete (about 4 hours) and the mixture warmed to
room temperature. Volatiles boiling up to 69.degree. C. were
distilled off and the product mixture was then further evaporated
at room temperature under reduced pressure of 20 mm.
6-Heptafluoroisopropoxyperfluorohexanamide, (CF.sub.3).sub.2
CFO(CF.sub.2).sub.5 CONH.sub.2 (18 parts) was obtained having a
melting point of 65.degree.-67.degree. C.
The amide prepared as above (2.39 parts) and 0.30 parts of
paraformaldehyde were heated at about 90.degree. C. for 20 minutes,
cooled and dissolved in 10 parts by volume of
trifluorotrichloroethane. Zinc chloride (0.68 part) was added and
the mixture stirred for 5 minutes. Anhydrous hydrogen chloride was
bubbled into the mixture for 2.5 hours and the mixture filtered.
The solvent was evaporated to yield a yellow, viscous liquid which
was triturated with ether. The product was dried under vacuum.
A 76% yield (2.0 parts) of
6-heptafluoroisopropoxyperfluorohexanamido methyl chloride of the
formula (CF.sub.3).sub.2 CFO--(CF.sub.2).sub.5 CONHCH.sub.2 Cl was
obtained. The structure was confirmed by infrared analysis which
showed amide absorption at 3.0, 5.85 and 6.5-6.55 microns; C-F
absorption at 7.5-9.0 microns; and ether absorption at 10.1
microns.
Elemental analysis calculated for C.sub.10 F.sub.17 H.sub.3
ClNO.sub.2 : C, 22.8; F, 61.2; H, 0.6; Cl, 6.7; N, 2.7. Found: C,
21.9; F, 59.7; H, 0.8; Cl, 6.8; N, 2.6.
EXAMPLE 2
A solution of 10.55 parts of
6-heptafluoroisopropoxyperfluorohexanamido methyl chloride as
prepared in Example 1 in 50 parts by volume of
trifluorotrichloroethane was treated with 1.58 parts of pyridine.
After evaporating the solvent the product was triturated with
petroleum ether.
A 60% yield (7.4 parts) of
1-(6-heptafluoroisopropoxyperfluorohexanamidomethyl)pyridinium
chloride of the formula
was obtained. This compound was soluble in water. The structure was
confirmed by infrared analysis which showed pyridinium absorption
at 6.15 and 6.75 microns; amide absorption at 3.3, 5.8 and 6.5
microns; C-F absorption at 7.5-9.0 microns and ether absorption at
10.1 microns.
Elemental analysis calculated for C.sub.15 F.sub.17 H.sub.8
ClN.sub.2 O.sub.2 : C, 29.4; F, 53.2; H, 1.3; Cl, 5.9; N, 4.6.
Found: C, 29.7; F, 50.9; H, 1.5; Cl, 5.5; N, 4.7.
EXAMPLE 3
A solution of 10.55 parts of
6-heptafluoroisopropoxyperfluorohexanamido methyl chloride as
prepared in Example 1 in 100 parts by volume of
trifluorotrichloroethane was treated with 1.30 parts of
N,N,N'N'-tetramethyl-1,3-propane diamine as quaternizing agent.
A 100% yield (11.7 parts) of
N,N,N',N'-tetramethyl-N,N'-bis(6-heptafluoroisopropoxyperfluorohexanamidom
ethyl)propane-1,3-diammonium chloride having the formula
was obtained. The structure was confirmed by infrared analysis
which showed C-H absorption at 6.8 and 6.9 microns; amide
absorption at 3.3, 5.8 and 6.5-6.6 microns; C-F absorption at
7.5-9.0 microns and ether absorption at 10.1 microns. The compound
was soluble in water.
Elemental analysis calculated fro C.sub.27 F.sub.34 H.sub.24
Cl.sub.2 N.sub.4 O.sub.4 : C, 27.3; F, 54.2; H, 2.0; Cl, 6.0; N,
4.7. Found: C, 26.8; F, 53.0; H, 2.3; Cl, 5.1; N, 4.5.
EXAMPLE 4
A mixture of 23.95 parts of
6-heptafluoroisopropoxyperfluorohexanamide as prepared in example 1
and 3.0 parts of paraformaldehyde was heated at about 80.degree. C.
for 5 hours. A clear, yellow, viscous liquid was obtained (20.6
parts) which was triturated with petroleum ether.
N-methylol-6-heptafluoroisopropoxyperfluorohexamide having the
structure (CF.sub.3).sub.2 CFO(CF.sub.2).sub.5 CONHCH.sub.2 OH was
obtained. The structure was confirmed by infrared analysis which
showed absorption at 3.0 microns for --NH and --OH; amide
absorption at 5.85 and 6.55-6.6 microns; C-F absorption at 7.5-9.0
microns and ether absorption at 10.1 microns.
Elemental analysis for C.sub.10 F.sub.17 H.sub.4 NO.sub.3 : C,
23.6; F, 63.4; H, 0.8. Found: C, 23.6; F, 63.3; H, 0.7.
EXAMPLE 5
An ester of the formula (CF.sub.3).sub.2 CFO(CF.sub.2).sub.11
COOCH.sub.3 was prepared following the procedure given in Example
1, but substituting the appropriate iodide. The corresponding amide
was prepared by reaction with ammonia.
A mixture of 1.95 parts of the resultant
12-heptafluoroisopropoxyperfluorododecanamide and 0.15 part of
paraformaldehyde was heated at 100.degree. C. for 1 hour. The
product was purified by recrystallization from
trichlorotrifluoroethane.
A 60% yield (1.2 parts) of
N-methylol-12-heptafluoroisopropoxyperfluorododecanamide having the
formual (CF.sub.3).sub.2 CFO(CF.sub.2).sub.11 CONHCH.sub.2 OH was
obtained as a white solid having a melting point of
42.degree.-45.degree. C. The structure was confirmed by infrared
analysis.
EXAMPLE 6
Zinc chloride (0.09 part) was added to a solution of 0.5 part of
the N-methylolamide (CF.sub.3).sub.2 CFO(CF.sub.2).sub.11
CONHCH.sub.2 OH prepared as in Example 5 in 15 parts by volume of
trifluorotrichloroethane. The mixture was stirred for 5 minutes and
anhydrous hydrogen chloride bubbled in for 2 hours. The mixture was
filtered and the solvent evaporated. The soft, white, solid product
was further purified by triturating with ether and drying.
An 80% yield (0.40 part) of
12-heptafluoroisopropoxyperfluorododecanamidomethyl chloride of the
formula (CF.sub.3).sub.2 CFO(CF.sub.2).sub.11 CONHCH.sub.2 Cl was
obtained. The structure was confirmed by infrared analysis.
EXAMPLE 7
A mixture of 5.0 parts of
12-heptafluoroisopropoxyperfluorododecanamide prepared as in
Example 2, 2.94 parts of pyridine hydrochloride, 0.6 part of
paraformaldehyde and 30 parts by volume of pyridine was heated at
65.degree.-70.degree. C. for 18 hours. The solid product was
triturated with ether and dried.
1-(12-heptafluoroisopropoxyperfluorododecanamidomethyl)pyridinium
chloride having the formula
was obtained as a water soluble solid having a melting point of
59.degree.-64.degree. C. The structure was confirmed by infrared
analysis.
EXAMPLE 8
(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.3 I, (618 parts), 184
parts of methyl undecenoate and 4.1 parts of azobisisobutyronitrile
were charged to a vessel fitted with a stirrer, thermometer and
condenser and warmed to 70.degree.-80.degree. C. An exothermic
reaction occurred. The mixture was maintained at
70.degree.-80.degree. C. for one hour and at 90.degree.-95.degree.
C. for four hours longer. The unreacted ether iodide was distilled
off.
An ester having the formula (CF.sub.3).sub.2 CFO(CF.sub.2
cf.sub.2).sub.3 CH.sub.2 CHI(CH.sub.2 CH.sub.2).sub.4 COOCH.sub.3
was obtained.
The ester was added dropwise over about 1.5 hours to a vessel
containing 1,500 parts by volume of acetic acid heated to
110.degree.-115.degree. C. and 65 parts of zinc dust. An additional
65 parts of zinc dust was added after about half of the ester was
charged. 20 Parts more of zinc dust were added and the mixture was
refluxed for five hours. The mixture was poured into 3,000 parts of
water and the layers separated. The aqueous layer was washed with
ether and the washings were combined with the organic layer. The
organic layer was then washed with water, dried over magnesium
sulfate and distilled.
A 54% yield of an ester of the formula (CF.sub.3).sub.2
CFO(CF.sub.2 CF.sub.2).sub.3 (CH.sub.2 CH.sub.2).sub.5 COOCH.sub.3
was recovered having a boiling point of 148.degree.-154.degree.
C./1.5 mm. This ester was hydrolyzed to the free acid by heating
with 32 parts of sodium hydroxide in 300 parts by volume of alcohol
and 100 parts of water in a steam bath for three hours and
neutralizing. The acid product was recrystallized from petroleum
ether.
(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.3 (CH.sub.2
CH.sub.2).sub.5 COOH was obtained having a melting point of
61.degree.-65.degree. C.
The acid prepared as above (36.5 parts) was dissolved in 25 parts
by volume of methylene chloride and warmed to 35.degree. C. 12
Parts of thionyl chloride were added dropwise and the mixture
refluxed for 3 hours. The solvent and excess thionyl chloride were
stripped off under vacuum. A quantitative yield of the acid
chloride was obtained.
The acid chloride was dissolved in 50 parts by volume of methylene
chloride and the solution added slowly to a mixture containing 8
parts of triethylamine, 4 parts of ammonia and 100 parts by volume
of methylene chloride cooled to 0.degree. C. .+-. 5.degree. C. A
precipitate formed. The slurry was stirred for 2 hours at room
temperature. 50 Parts of water were added while stirring
vigorously. The precipitate was filtered, washed with cold water,
and dried. The crude amide product was recrystallized from hot
ethanol.
An 81% yield (29.5 parts) of an amide having the formula
(CF.sub.3).sub.2 CFO(CF.sub.2 CF.sub.2).sub.3 (CH.sub.2
CH.sub.2).sub.5 CONH.sub.2 was obtained having a melting point of
93.degree.-95.degree. C. Elemental analysis calculated for C.sub.20
H.sub.22 F.sub.19 NO.sub.2 : C, 36.2; H, 3.3; F, 54.0; N, 2.1.
Found: C, 36.2; H, 3.1; F, 54.4; N, 2.0.
The amide prepared as above (26.8 parts) 1.5 parts of
paraformaldehyde and 5 parts of dry pyridinium chloride in 150
parts by volume of pyridine were heated to 80.degree. C. for 6
hours and stirred overnight at room temperature. An equal volume of
acetone was added, and the mixture cooled to -30.degree. C. The
quaternized product was filtered, washed with cold acetone, and
recrystallized from acetone.
17-Heptafluoroisopropoxy-12,12,13,13,14,14,15,15,16,16,17,17-dodecafluorohe
ptadecanamidomethyl pyridinium chloride (25.4 parts) having the
formula
was obtained having a melting point of 120.degree.- 122.degree. C.
The structure was confirmed by infrared analysis which showed bands
at 6.0 and 6.5 microns, characteristic of a secondary amide.
Elemental analysis calculated for C.sub.26 F.sub.19 H.sub.28
ClN.sub.2 O.sub.2 : C, 39.2; H, 3.5; Cl, 4.5; N, 3.5. Found: C,
37.2; H, 4.5; Cl, 3.7; N, 2.6.
EXAMPLE 9
An amide having the formula
was prepared following the procedure of Example 1 but substituting
the appropriate iodide starting material.
A mixture of 61.5 parts of the amide, 3.2 parts of paraformaldehyde
and 10 parts of dry pyridinium chloride in 300 parts by volume of
pyridine was reacted as in Example 1. The crude product was
isolated and recrystallized from acetone.
19-Heptafluoroisopropoxy-12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19-he
xadecafluorononadecanamidomethyl pyridinium chloride (47 parts) was
obtained having the formula
and a melting point of 128.degree.-130.degree. C. The structure was
confirmed by infrared analysis.
Elemental analysis calculated for C.sub.28 F.sub.23 H.sub.28
ClN.sub.2 O.sub.2 : C, 37.5; H, 3.2; N, 3.1. Found: C, 35.6; H,
4.6; N, 4.7.
EXAMPLE 10
An amide having the formula
was prepared following the procedure of Example 1 but substituting
the appropriate iodide starting material.
A mixture of 34.2 parts of the amide, 2.4 parts of paraformaldehyde
and 7.5 parts of dry pyridinium chloride in 225 parts by volume of
pyridine as reacted following the procedure of Example 1. The
produce was isolated and recrystallized from acetone as in Example
1.
15-Heptafluoroisopropoxy-12,12,13,13,14,14,15,15-octafluoropentadecanamidom
ethyl pyridinium chloride (22 parts) was obtained having the
formula
and a melting point of 118.degree.-120.degree. C. The structure was
confirmed by infrared analysis.
Elemental analysis calculated for C.sub.24 F.sub.15 H.sub.28
ClN.sub.2 O.sub.2 : C, 41.4; Cl, 5.1; N, 4.0. Found: C, 42.0; Cl,
4.9; N, 4.1.
EXAMPLE 11
This example demonstrates the use of a typical substituted ammonium
compound of the invention as an internal sizing for paper.
Papers are tested for oil and water resistance according to the
following test:
The water repellency of treated papers is determined according to
standard test T411-os-63 of the Technical Association of the Pulp
and Paper Industry (Cobb Test). This test determines the amount of
water absorbed by the paper after two minutes. A value of 20-25 or
lower indicates excellent water resistance.
The oil resistance of treated papers is determined by the
following: A kit of 12 solutions of varying proportions of castor
oil, toluene and heptane is prepared, as set forth in the following
Table. A value of 12 shows superior oil repellency.
Parts by Parts by Parts by Kit No. Volume of Volume of Volume of
Castor Oil Toluene Heptane
__________________________________________________________________________
1 200 0 0 2 180 10 10 3 160 20 20 4 140 30 30 5 120 40 40 6 100 50
50 7 80 60 60 8 60 70 70 9 40 80 80 10 20 90 90 11 0 100 100 12 0
90 110
__________________________________________________________________________
The Kit value is the highest numbered solution that will stand on
the surface to be tested in the form of a drop for 15 seconds, with
no penetration of the solution, noted by any darkening of the area
under the drop.
The ink resistance is measured according to the following
procedure: a 1.5 inch square of treated paper is folded to turn up
all the edges. The square is floated on standard writing ink. The
time in seconds required for the ink to penetrate evenly to the
upper surface of the paper is noted as the ink penetration. A time
of 900 seconds or longer denotes excellent ink resistance.
19-Heptafluoroisopropoxy-12,12,13,13,14,14,15,15,16,16,17,17,18,18,19,19-he
xadecafluorononadecanmidomethyl pyridinium chloride prepared as in
Example 9 was dispersed in various amounts in a 3% cationic starch
solution (Cato-15, a product of National Starch and Chemical Co.).
A 50:50 mixture of softwood and hardwood bleached kraft paper pulps
was stirred in water for 3-5 minutes and the starch solution added.
Stirring was continued 3-5 minutes longer and hand sheets were
formed and dried. The treated sheets were tested for oil, water and
ink resistance immediately after curing the sheets for 48 hours at
110.degree. C. The results obtained are summarized below.
Concentration % Kit no. Ink flotation, sec. Cobb size
__________________________________________________________________________
1.0 12 > 900 22.8 0.5 12 > 900 27.6 0.25 10 > 900 40.4
__________________________________________________________________________
It is apparent that the compounds of the invention impart excellent
oil, water and ink resistance when applied as an internal size for
paper.
EXAMPLE 12
This example demonstrates the use of a typical substituted ammonium
compound of the invention as an external size for paper.
Various amounts of
prepared as in Example 9 were dissolved in a 7:1 mixture by volume
of isopropanol: trichlorotrifluoroethane. Performed paper
handsheets were dipped into the solutions, dried for 10 minutes at
115.degree. C. and tested for oil, water and ink resistance. The
results are given below.
Concentration % Kit no. Ink flotation, sec. Cobb size
__________________________________________________________________________
0.5 12 >900 21.6 0.25 7 150 24.0
__________________________________________________________________________
EXAMPLE 13
This example demonstrates the use of typical N-halomethyl and
N-methylol derivatives of the invention as treating agents for
textiles. Pieces of cotton print cloth were soaked in a solution or
emulsion of the test compound and dried in air. The treated textile
was then tested for oil repellency according to the method
described on pages 323-4 of the April, 1962 edition of the Textile
Research Journal. According to this procedure, drops of mixtures of
mineral oil and n-heptane in varying proportions are gently placed
on the treated fabric and are allowed to stand for 3 minutes. At
this time the wetting and penetration by the drops on the fabric is
observed. The number corresponding to the mixture containing the
highest proportion of heptane which does not penetrate or wet the
fabric is taken as the oil repellency of the treated fabric. A
rating of 90 or higher is considered excellent. ##SPC7##
EXAMPLE 14
This example demonstrates the use of typical substituted ammonium
compounds of the invention as treating agents for textiles. The
compounds were dissolved in water (2% solution) and cotton cloth
dipped into the solution, squeezed to remove excess liquid and air
dried. The treated cloths were tested for oil repellency according
to the procedure of Example 13 and for water repellency according
to AATCC test method 22-1952. The data is given below. ##SPC8##
EXAMPLE 15
as prepared in Example 6 was dissolved in water (3.3% solution).
Samples of cotton cloth were soaked in the solution for 8 minutes,
blotted on paper towels, air dried for one hour and cured at
115.degree. C. for 8 minutes. The treated cloth had a water
repellency rating of 70 and an oil repellency rating of 120.
EXAMPLE 16
This example illustrates the excellent durability of compounds of
the invention to repeated dry cleaning and laundering.
as prepared in Example 8 was dissolved in hot acetone (0.75%
solution) and padded onto dry cotton cloth to a total pickup of
0.4% based on the dry weight of the fabric. The cloth was air dried
and cured at 160.degree. C. for 2 minutes. The treated cloth was
then rinsed in warm water, dried at 80.degree.C. for 10 minutes,
ironed, cooled to room temperature and tested for water and oil
repellency. The cloth was then subjected to standard home
laundering cycles using a heavy duty detergent, followed by drying
in an automatic dryer. The cloth was also subjected to 5 commercial
dry cleanings. The data is summarized below:
Oil Repellency Water Repellency Rating Rating
__________________________________________________________________________
Initial test 130 100 After 5 launderings 130 100 After 15
launderings 130 80+ After 5 dry cleanings 130 100-
__________________________________________________________________________
EXAMPLE 17
was applied to cotton cloth from an aqueous emulsion prepared by
dissolving 3 parts of the compound in 20 parts by volume of hot
isopropanol and adding 130 parts by volume of hot (50.degree. C.)
2% aqueous starch solution. The total dry pick-up on the cloth was
adjusted to 0.35%. The results are given below.
Oil Repellency Water Repellency Rating Rating
__________________________________________________________________________
Initial test 130 100 After 5 launderings 130 100 After 15
launderings 130 80+
__________________________________________________________________________
EXAMPLES 18-28
Additional illustrative examples are listed below. These products
are prepared as described hereinabove substituting the appropriate
fluorinated amide and quaternizing agents. ##SPC9##
It will be apparent that numerous modifications and variations may
be effected without departing from the novel concepts of the
present invention and the illustrative details disclosed are not to
be construed as imposing undue limitations on the invention.
* * * * *