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Publication numberUS3674800 A
Publication typeGrant
Publication dateJul 4, 1972
Filing dateApr 14, 1969
Priority dateApr 14, 1969
Also published asDE2017399A1
Publication numberUS 3674800 A, US 3674800A, US-A-3674800, US3674800 A, US3674800A
InventorsEdward Stephen Jones, Aziz Urrehman Khan, Julian A Otto, Alson K Price, Richard F Sweeney
Original AssigneeAllied Chem
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Derivatives pyridinium of polyfluoroisoalkoxyalkanamides
US 3674800 A
Abstract  available in
Images(13)
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Claims  available in
Description  (OCR text may contain errors)

nit e States Patent Sweeney et al.

[451 July 4,1972

[54] DERIVATIVES PYRIDINIUM OF POLYFLUOROISOALKOXYAL- KANAMIDES [72] Inventors: Richard F. Sweeney, Randolph Township, Morris County; Aziz Urrehman Khan, Elizabeth; Alson K. Price, Morristown; Edward Stephen Jones, Whippany; Julian A. Otto, Stockholm, all of NJ.

[73] Assignee: Allied Chemical Corporation, New York,

[22] Filed: April 14, 1969 21 Appl. No.: 816,013

[52] US. Cl. ..260/295 AM, 260/287 R, 260/514 R,

260/561 R, 260/561 S, 260/562 R, 260/484 R, 8/116.2, 8/142, 252/152 [51 Int. Cl. ..C07d 31/44 [58] HeldolSearch ..260/295 AM; 8/1 16.2

[56] References Cited UNITED STATES PATENTS 3,510,494 5/1970 Gagliardi et al. ..260/295 AM Primary Examiner-Alan l... Rotman Attorney-Jay P. Friedenson ABSTRACT 10 Claims, No Drawings DERIVATIVES PYRIDINIUM OF POLYFLUOROISOALKOXYALKANAMIDES 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, US. Pat. No. 3,l47,065 issued Sept. l, 1964 discloses quaternary compounds of the formula R,--RCONHCH Q X' wherein R, is a perfluoroalkyl group of four to 12 carbon atoms, R is an alkylene group of the formula CH CHCl(CH or --(Cl-l ),,,wherein m is an integer from l-lO 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. US. Pat. No. 3,147,066, also issued Sept. l, 1964 discloses quaternary compounds of the formula R,SO NR(Cl-l bCONHCH Q*X wherein R, 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 and R cannot be chlorine; 2,, 2,, Z and 2, can be fluorine, chlorine or hydrogen with the proviso that no more than two of Z,-Z,, are chlorine; X,, X X and X, can be chlorine, fluorine or hydrogen with the proviso that no more than one of X,-X, is chlorine; r is an integer from l 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-l; 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 l 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 andat least one CF group.

The amide starting materials useful in the invention have the formula wherein R,, R Z,-Z X,-X 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 wherein R, and R 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 US. applications of Litt et a]. Ser. No. 492,276 filed Oct. 1, 1965 and Ser. No. 5 l3,574 filed Dec. 13, I965. 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,Z C C2 2 and/or X,X C CX X wherein Z,-Z., and X, 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 C. to about 350 C., preferably from about l50-200 C. or by a free radical initiator, e.g. azobisisobutyronitrile, benzoyl peroxide and the like. These reactions are described in greater detail in copending US. 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 illuswherein R and R can be fluorine, chlorine or perfluoroalkyl of one to two carbon atoms providing both R and R 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 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 CH l 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 O or I 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 offormula (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) under pressure of 20-200 atmospheres at temperatures of 300 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 l, m, n and pare O, or wherein (b) ris 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 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 US. 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 fonnula (5) wherein r is 2, n is 0, p is I, Y is H or F and m is as described above can be prepared from the corresponding alcohol wherein n is l, and X and X are hydrogen by oxidation as hereinbefore described.

Carboxylic acids of formula (5) wherein r is 2, n is 0, p is I, Y is H and the carbon atom in the B-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 wherein R R, and m have the meanings given above. These fluorooleflns can be prepared by reacting a suitable iodide with ally] alcohol at a temperature between about 10 to 450 C., preferably from l50-300 C., under superatmospheric pressure. The tenninal 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 l 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 to 175 C., preferably from ll50 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 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, 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 C.

The preparation of these acids and their precursors are described in greater detail in corresponding U.S. applications ofAnello 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-l50 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 fonnula (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 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 fonnaldehyde, 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 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 quatemizing 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 to about 70 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 to 100 C., but preferably at about 60 to 80 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'-

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.

1n 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 CFO(CF CF l, 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 iceacetone trap. The vessel was flushed with nitrogen, sealed and heated at about 140 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 CFO(CF CF CF COF and 7.5 parts of the pyrosulfuryl fluoride (CF CFO(CF CF OSO OSO F.

A mixture of 12.2 parts of (CF CFO(CF .,COF and 10.8 parts of (CF CFO(CF CF OSO OSO F prepared as above was charged to a vessel fitted with a reflux condenser and dropping funnel. The mixture was cooled to 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 driedover anhydrous sodium sulfate and distilled under reduced pressure.

The corresponding methyl ester, (CF CFO(CF COOCH 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 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 C. were distilled off and the product mixture was then further evaporated at room temperature under reduced pressure of 20 mm.

6-Heptafluoroisopropoxyperfluorohexanamide, (CF CF O(CF CONH (18 parts) was obtained having a melting point of 65-67 C.

The amide prepared as above (2.39 parts) and 0.30 parts of paraformaldehyde were heated at about 90 C. for 20 minutes, cooled and dissolved in 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 tlrictl under vacuum.

A solution of 10.55 parts of -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 l-( 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, .,F, H,,ClN O 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,NN-tetramethyl-1,3-propane diamine as quaternizing agent.

A 100% yield (1 1.7 parts) of N,N,N',N'-tetramethyl-N,N- bis( 6-heptafluoroisopropoxyperfluorohexanam idomethyl)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 75-90 microns and ether absorption at 10.1 microns. The compound was soluble in water.

Elemental analysis calculated fro C F H Cl N O C, 27.3; F, 54.2; H, 2.0; C1, 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 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 CFO(CF CONHCH 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 7.59.0 microns and ether absorption at 10.1 microns.

Elemental analysis for C ,F H ,NO C, 23.6; F, 63.4; H, 0.8. Found: C, 23.6; F, 63.3; H, 0.7.

EXAMPLE An ester of the formula (CF:,) CFO(CF COOCH 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 l2-heptafluoroisopropoxyperfluorododecanamide and 0.15 part of paraformaldehyde was heated at 100 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 CFO(CF CONHCl-l OH was obtained as a white solid having a melting point of 4245 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 CFO(CF CONHCH 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 l2-heptafluoroisopropoxyperfluorododecanamidomethyl chloride of the formula (CF;,) CF O(CF CONHCH CI 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 65-70 C. for 18 hours. The solid product was triturated with ether and dried.

1 l 2-heptafluoroisopropoxyperfluorododecan amidomethyl)pyridinium chloride having the formula was obtained as a water soluble solid having a melting point of 5964 C. The structure was confirmed by infrared analysis.

EXAMPLE 8 (CF CFO(CF CF l, (618 parts), 184 parts ofmethyl undecenoate and 4.1 parts of azobisisobutyronitrile were charged to a vessel fitted with a stirrer, thermometer and condenser and warmed to 7080 C. An exothermic reaction occurred. The mixture was maintained at 70-80 C. for one hour and at 90-95 C. for four hours longer. The unreacted ether iodide was distilled off.

An ester having the formula (CF ),CFO(CF cf C1-l Cl-lI(Cl-l CH COOCH 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 l 10-l C. and 65 parts of zinc dust. An additional 65 parts of zinc dust was added after about half of the ester was charged. 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 CFO(CF CF (CH CH COOCH was recovered having a boiling point of 148-154 C./l.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 CFO(CF CF (CH CH COOH was obtained having a melting point of 6 l-65 C.

The acid prepared as above (36.5 parts) was dissolved in 25 parts by volume of methylene chloride and warmed to 35 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 parts by volume of methylene'chloride cooled to 0 C. 5 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 CFO(CF CF (CH CH ),,CONH was obtained having a melting point of 93-95 C. Elemental analysis calculated for 20H gFmN()gI( 36.2; H, 3.3; F. 54.0; N. 2.1. Found: 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 C. for 6 hours and stirred overnight at room temperature. An equal volume of acetone was added, and the mixture cooled to -30 C. The quaternized product was filtered, washed with cold acetone, and recrystallized from acetone.

1 7-Heptafluoroisopropoxyl2,l2,l3,13,14,14,15,15,l6,16,17,17-dodecafluoroheptadecanamidomethyl pyridinium chloride (25.4 parts) having the formula was obtained having a melting point of 122 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 ,,F H ClN O 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 %0 (C Fa)zC F O (G F20 Fz) (CH CHz)sC\ NHz 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.

1 9-l-leptafluoroisopropoxy- 12,12,l3,13,l4,14,15,15,16,16,17,17,18,18,19,19-hexadecafluorononadecanamidomethyl pyridinium chloride (47 parts) was obtained having the formula and a melting point of l28130 C. The structure was confirmed by infrared analysis.

Elemental analysis calculated for CzgFzaHggClNgOzl 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 substitutin g 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.

lS-Heptafluoroisopropoxy-l2,12,13,13,14,14,15,l5-octafluoropentadecanamidomethyl pyridinium chloride (22 parts) was obtained having the formula and a melting point of 1 18l20 C. The structure was confirmed by infrared analysis.

Elemental analysis calculated for C F H CIN O C, 41.4; C1, 5.1; N, 4.0. Found: C, 42.0; CI, 4.9; N, 4. 1.

EXAMPLE 1 1 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 T41 1-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 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 re sistance.

19-Heptafluoroisopropoxy- 12,12,13,13,14,14,l5,15,16,16,17,17,18,18,19,19-hexadecafluorononadecanmidomethyl 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 1 10 C. The results obtained are summarized below.

Concentration Kit no. lnk flotation, sec. Cobb size 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 1 15 C. and tested for oil, water and ink resistance. The results are given below.

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 or higher is considered excellent.

0.1% in water containim. 4.8% starch and 0.1% 01 Nolan water repellent" llll A product of E. l. duPont tle Nomours and C0.

EXAMPLE 14 EXAMPLE l 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 l l5 C. for 8 minutes. The treated cloth had a water repellency rating of 70 and an oil repellency rating of I20.

EXAMPLE l6 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 C. for 2 minutes. The treated cloth was then rinsed in warm water, dried at 80C. 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:

was applied to cotton cloth from an aqueous emulsion prepared by dissolving 3 parts of the compound in parts by volume of hot isopropanol and adding 130 parts by volume of hot C.) 2% aqueous starch solution. The total dry pick-up on the cloth was adjusted to 0.35%. The results are given below.

Oil Rcpellency Water Rcpellency Rating Rating lnitial test I30 I00 After 5 launderings l3() I00 After 15 launderings I30 EXAMPLES 1 8-28 10 Additional illustrative examples are listed below. These products are prepared as described hereinabove substituting the appropriate fluorinated amide and quaternizing agents.

Example 26 NH: (01%)20 FOCFzCFzCFzCONHCHzS-C Cl- Example 27 E ahCFOCFzCHzCONHCH Ii 1"- Example 28 /CH1CH2OH -CHzCHzN CII NHCO (CH2)4(C F2) C F (C Fa):

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.

We claim:

1. A compound of the formula wherein 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, and R are 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 ofthe formula 9. A compound according to claim 4 of the formula UNITED STATES PATENT OFFICE Page 1. CERTIFICATE-OF CORRECTION Patent No. 3 ,6? ,800 t d July U 1972 Inventor,(s) I Richard F; Sweeney et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Abstract Page and Col. 1 in the title "DERIVATIVES PYRIDINIUM" should read PYRIDINIUM DERIVATIVES Col. 1, line 27 "four to six" should read one to six cdI. 3, line 3 "X -X should read X -x coil 4 line :22" "iodied" should read iodide Col. 14, line 56 5- "at least 1 p is should read;

at least 1, p is C01. 5, 1Ine ,1 2 "'1o" should read 100 Col. 6, li nel63 "N,N,N+,N' should read VN,N,N'N'-Q ----5 Col. 7, line 6 "sdats" should read salcs Col. 8, line 3 9- "N,N,N',N'" should rea N,N,N'N',-;. Col. 8, line 57 "fro" should read for Col. 9, line 46 "59-6uc." should read 59-6uc. Col. 9 line 57 (CF CFO(CF cf C H should r ad I Col. 11, line 10 "produce" should read product FQRM FO-IOSO (10-69) I USCOMM-DC 603764 69 t 0.5. oovtmmlmv nmmm orncz: was o-asa-su UNITED STATES PATENT OFFICE Page 2 -CERTIFICATE OF CORRECTION Patent No. 3,67%800 D d July 4 1972 Inventofls) Richard F. Sweeney et a1 It is certified that error appears in the above-identified patent .andthat; said Letters Patent are hereby corrected as shown below:

Col. 11, in the Table "Parts by Kit No. Volume of Castor 011- I should read Kit No. Parts by Volume of Castor 011 1 200 2 180 3 l 1H0 5 120 6 100 7 80 8 6O 9 40 10 20 11 0 '12 O FORM PO-105O (10-69) USCOMM-DC GONG-P80 a 0.5. qovrmuum PRIN'HNG OFIICI: I9" 0-366d3 Patent No. 3,67 4,8OO d July 4 1972 Inventor) Richard F. Sweeney et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

001, 12, first table "Concentration Kit should read Concentration, Kit

Col. 12, second table "Concentration Kit 4 no.

should read Concentration, Kit

Col. 13, third formula, that part which reads A v v "(CF CF' should read (CF CF Col. 1 second formula, that hart which reads 7 "(CH CH OH)Cl"" should read d (CH CH 'OH) Cl Col. 1, fifth formula, that part which reads "coN1 I c1"? should read comm? 01 FORM PO-1050 (10-69) USCOMM-DC 60376-P69 r u.s. GOVERNMENT PRINTING OFFICE: I969 o-sss-aaa a I I UNITED STATES PATENT OFFICE Page l 7 CERTIFICATE OF CORRECTION Patent No. 3, 7 l 0Q Dated July s 1972 lnventofls) Richard F. Sweeney et a1 It is certified that error appears is the above-identified patent and that said Letters Patent are hereby corrected as shown below:

' Col. 15, thirdi formula, that part which reads "(CF )OCF(CF should read 2 )6 F Col. 16, lineiI-i; "wherein Q is' should read wherein QA is 001. 16, line. 15 "um A is chloride? should read I I I um chloride h Col. 16, last formula, that part which reads "(CF CF should read (CF CF )u Signed and sealed-this 16th day of July 197 (SEAL) Attest: McCOY M. GIBSON, JR. v c.' MARSHALL DANN Attesting Officer Commissioner of Patents FORM P0405) USCOMM-DC 60376-P69 .5. GOVERNMENT PRINTING OFFICE: I955 0-356-33

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US4032566 *Sep 4, 1975Jun 28, 1977The United States Of America As Represented By The Secretary Of The Air ForceOmega-carbomethoxyperfluoroalkylene oxide iodides
US5424438 *Jan 6, 1994Jun 13, 1995Ausimont S.P.A.Polishes for metal surfaces containing cationic emulsifiers, and cationic emulsifiers contained therein
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Classifications
U.S. Classification546/336, 546/337, 546/146, 564/201, 564/159, 8/188, 546/175, 8/142, 564/202, 546/102, 560/184, 562/586, 8/194
International ClassificationD06M13/322, C07C51/09, C07C59/135, D06M13/402, D06M13/35, C07C51/60, C07C51/58, C07D213/20, C07D215/10, C07C335/32, D06M13/432
Cooperative ClassificationC07C51/09, D06M13/322, D06M13/402, C07D215/10, C07C59/135, C07C335/32, C07D213/20, D06M13/432, C07C51/60, C07C51/58, D06M13/35
European ClassificationC07C51/09, C07C51/58, C07C51/60, C07D215/10, C07C59/135, C07C335/32, D06M13/402, D06M13/35, D06M13/322, D06M13/432, C07D213/20