US3555089A - Perfluoroalkyl ether amido quaternary ammonium salts - Google Patents

Perfluoroalkyl ether amido quaternary ammonium salts Download PDF

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US3555089A
US3555089A US705923A US3555089DA US3555089A US 3555089 A US3555089 A US 3555089A US 705923 A US705923 A US 705923A US 3555089D A US3555089D A US 3555089DA US 3555089 A US3555089 A US 3555089A
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Philip Lee Bartlett
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Definitions

  • a+b is an integer from 0-3, and A is any anion which forms an ammonium salt of the formula NH +A- having a solubility in water of at least about 1%.
  • the starting materials for preparing the products of this invention are the perfluoroalkyl ether acid fluorides of the formula These acid fluorides are available from two sources, polymerization of hexafluoropropylene oxide and polymerization of mixtures of hexafluoropropylene and oxygen.
  • the acid fluorides'prepared by the polymerization of hexafluoropropylene oxide are taught by Moore et al. in US.
  • Patent 3,250,808 and have the structure R O [CF (CF CF 0] CF(CF CFO
  • the products are n-C F- O[CF(CF )CF O],,CF(CF )CFO as described more fully by Moore in Canadian Patent 725,740.
  • COF carbonyl fluoride
  • the product is of the formula n F (CF CF 0 [CF (CF CF 0] CF (CF CFO where m is 0-5.
  • a perfluoroketone of the formula F(CF C(O)(CF F as described by SeIman in US. Patent 3,274,239, the product is of the formula mom), I
  • R may be a branched or straight chain perfiuoroalkyl group of 1-6 carbon atoms.
  • the acid fluorides prepared by polymerization of mixtures of hexafiuoropropylene and oxygen are taught by Pasetti Sianesi and Corti in Die Makromolekulare Chemie, 86, pages 308-311 (1965); Sianesi and Fontanelli in Die Makromolekular Chemie, 102, pages 115124 (1967); and French Patent 1,434,537.
  • the polymerization is carried out at temperatures of about 100 C. to 25 C. in the presence of ultraviolet radiation.
  • these polymers have backbones which are not in a regular head to tail arrangements; they contain both head to head and tail to tail as well as head to tail arrangements.
  • These polymeric acid fluorides are thus best represented by the formula Generically, the polymers from hexafluoropropylene oxide and hexafluoropropylene-oxygen mixtures are best represented by this more general formula.
  • the perfluoroalkyl ether amido quaternary salts of this invention are prepared by first converting the perfluoroalkyl ether acid fluoride to a corresponding alkyl perfiuoroalkyl ether ester, and preferably the methyl ester of the formula R O(C F O) CF(CF )CO CH or to a corresponding perfluoroalkyl ether amide of the formula R;O(C F O),,CF(CF )CONHR' in which R is hydrogen or an alkyl of l-6 carbon atoms.
  • the esters are prepared by esterification of the corresponding acid fluoride using standard methods, for example reaction of the acid fluoride with an alkanol such as methanol as taught by Diesslin et al. in US. Patent 2,567,011.
  • the esterification is carried out by reacting the perfluoroalkyl ether acid fluoride with excess methanol at 20 C., optionally in an inert solvent, in the presence of suflicient pyridine to consume the hydrogen fluoride formed.
  • methanol one can also use ethanol, propanol, butanol or the like equally well.
  • the amides are prepared by reaction of the corresponding acid fluoride with ammonia or an alkylamine of the formula RNH as also taught in the Diesslin et a1. patent.
  • a large number of diamines of the type HN (R) C H2 NR are known. Useful examples include: N'Hg 2N g 2( 2)2 4 9)2 CH NH(CH N(CH 2( 2)a 3 7)2 Suitable compounds of the formula R A are those in which R is an alkyl group of 1-18 carbon atoms and A is any anion which forms an ammonium salt of the formula NHJA- having a solubility in water of at least about 1%.
  • RA Useful examples of RA are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, hexyl, octyl, ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl chlorides, bromides and iodides.
  • the normal alkyl halides i.e., n-propyl, n-butyl, n-octyl or n-hexadecyl, are preferred.
  • methyl or ethyl sulfate (R) the anion A in the product of the present invention will usually be a mixture of RSO; and
  • N-aminoalkyl perfluoroalkyl ether amide product obtained by reacting the perfluoroalkyl ether ester with the primary diamine is then alkylated with at least three moles of alkyl halide, sulfate or sulfonate to form the quaternary salt.
  • the aminoalkyl amide may be alkylated by other procedures such as reductive alkylation with formaldehyde and formic acid, followed by salt formation as before.
  • Another route to the products in which Q is and p is 2-12 is to react the methyl perfluoroalkyl ether ester with an alkanolamine of the formula (R')C Hz OH to form an N-hydroxyalkyl perfluoroalkyl ether amide of the formula R O(C F O) CF(CF )CON(R)C H OH
  • the hydroxyalkyl amide is then treated with a halogenatin'g agent, for example hydrogen chloride, thionyl chloride or the like, to form the -N-haloalkyl perfluoroalkyl ether amide which is treated with a tertiary amine of the formula R2 NR to form the quaternary salt.
  • Suitable alkanolamines include ethanolamine, propanolamine, butanolamine, octanolamine and dodecanolamine.
  • Y is a divalent group of the formula (CH -(CH or R is an alkyl group of 1-16 carbons, and R and Y contain a total of 5-20 carbons
  • the products of this invention are prepared by the samegeneral methods as described above.
  • One procedure is by reaction of a diwith the methyl perfluoroalkyl ether ester and the resulting product with an alkyl halide, sulfate or arylsulfonate of the formula R A where R is an alkyl group of 1-16 carbon atoms to form the quaternary salt.
  • N-haloalkyl perfluoroalkyl ether amides described above, including the N-chloromethyl amides, with a cyclic tertiary amine of 5-20 carbons of the formula R N Y to form the quaternary salt.
  • the products of this invention can be prepared by reaction of the N-haloalkyl perfluoroalkyl ether amides described above, including the N-chloromethylamides, with a pyridine of the formula or a quinoline of the formula These pyridines and quinolines are well known.
  • pyridines are pyridine, picoline, lutidine, chloropyridines, bromopyridines, dichloropyridines, dibromopyridines, chloropicolines, bromopicolines, chlorolutidines, bromolutidines and the like.
  • Useful examples of quinolines are quinoline, chloroquinolines, bromoquinolines, quinaldine, chloroquinaldines, bromoquinaldines and the like.
  • the products of this invention can be prepared by reaction of the methyl perfluoroalkyl ether esters described above with an aminoalkylpyridine of the formula The resulting perfluoroalkyl ether amide is then reacted with an alkyl halide, sulfate or sulfonate of the formula R A where R is an alkyl group of 1-4 carbon atoms.
  • aminoalkyl pyridines include 2- aminomethylpyridine, 2-(2'-aminoethyl)pyridine, 3-(2'- aminoethyDpy'ridine, 3 aminomethylpyridine, 2,6-dichloro 3 aminomethylpyridine, 2-methyl-3-(2'-aminoethyl)pyridine, 3 (4' aminobutyl)pyridine, 4-aminomethylpyridine and 4-(2'-aminoethyl)pyridine.
  • Suitable aminoalkylquinolines include 2-, 3-, 4-, 5-, 6-, 7- and 8- aminomethylquinolines, 2-, 3-, 4-, 5-, 6-, 7- and 8-(2- aminoethyl)quinolines, -2-, 3-, 4-, 5-, 6-, 7- and 8-(4'- aminobutyl)qninolines, and 2-, 3-, 4-, 5-, 6-, 7- and 8-(3'- methylaminopropyl) quinolines.
  • alkyl halides include methyl, ethyl, propyl and butyl chlorides, bromides and iodides. Although the alkyl halides are vpreferred with these amides, methyl sulfate or methyl toluenesulfonate could be used with some success, if desired.
  • the products of this invention can be prepared by reaction of the methyl perfluoroalkyl ether ester described above with an aminopyridine of the formula or an aminoquinoline of the formula
  • the resulting perfluoroalkyl ether amide is then reacted with the above defined alkyl halide sulfate or sulfonate of the formula R A.
  • Suitable aminopyridines include 2-aminopyridine, the 3, 4, 5 or 6-methyl-2-aminopyridine, the 3, 4, 5 or 6- ehloro 2 aminopyridines, 3 aminopyridine, 2-chloro-6- methyl-3-aminopyridine, 4-aminopyridine, the dichloro-4- aminopyridines, and the like.
  • Suitable aminoquinolines includes 2, 3, 4, 5, 6, 7 or S-aminoquinolines, the chloroaminoquinolines, the methylaminoquinolines and the like.
  • a convenient inert solvent such as ethers, hydrocarbons, halogenated aromatic hydrocarbons or alcohols may be used at temperatures between 0 C. and the reflux temperature of the system.
  • the methyl perfluoroalkyl ether ester may be heated alone with the amine, allowing the methyl alcohol formed to distill from the system.
  • the solvent is chosen conveniently to dissolve the reactants but not the solid product which is then readily recovered by filtration.
  • n is 0-1
  • the products of the formula of this invention are useful as surface active agents in aqueous systems, for example, as emulsifying agents, dispersants, wetting agents, and the like. These products are particularly useful as dispersing agents for aqueous emulsion polymerizations.
  • Compounds in which n is 2 or greater are insufficiently soluble in water to be useful as surface active agents in aqueous systems.
  • n 0 8
  • the products wherein n is 0-1 are particularly useful as surface active agents in applications where they come in contact with steel such as in steel treating processes, for example in pickling baths.
  • Those products wherein n is 2-8 are useful for other purposes. For example, they are useful as antiwetting agents in applications requiring mold release agents, release agents for glass, and flotation agents.
  • the preferred products of this invention are those obtained from the polymerization of hexafluoropropylene oxide and hence of the formula [R O (CF CF CF 0 CF (CP CON (R' Q] A-
  • n-C F O [CF(CF CF 0] CF(CF 3 CO CH and n-C3F7O 3C1: CO2CH3 can be prepared from the corresponding acid fluorides by the same procedure.
  • n-C F OCF(CF 3 CF OCF (CF CO CH can be reacted with NH (CH N(CH to form n-C F OCF(CF )CF OCF (CF 3 CONH (CH N(CH 2 CHgCHg 9.. to form I g Y a omen. n-omoor FQOFZOCF cmcoNnomonzN H.
  • n-C F OCF(CF )CO CH can be reacted with Z-aminopyridine to give n-cmo omen.
  • n-C3F7O 3 1 1 was reacted with methyl iodide to give [n-C F O 2GP (C1 )CONH(CH N(CH )3] Analysis.Calcd for C H F O N I (percent): F, 49.2; N, 3.2; I, 14.3. Found (percent): F, 48.9; N, 3.1; I, 14.1.
  • n-C F OCF(CFQ)CONH can be reactedwith methyliodine to form p n I
  • T BLE .Surface activities of aqueous solutions of products -.pre- .pared above were measured using a Du' Nooy Te'nsiometer
  • the coupons were thenimmersed to one-half their length in 10% ⁇ aqueous hydrochloric acid and allowed to stand for five l jtiays at ambient temperature. None of the four Surface tension, dynes/cm. at C.
  • Two Type 1020 mild steel test coupons were each treated with a different 1.0% solution of one of the following products in trichlorotrifluoroethane for five minutesand then air dried.
  • the products used were:
  • Two glass slides were each treated with a different one of the two 1.0% trichlorotrifluoroetliane solutions de- 15 scribed in Example 8 for minutes and air dried.
  • the treated slides were then coated with poly(methyl Z-cyanoacrylate) which is known to be a good adhesive for glass. After setting, the adhesion of the resin coating to the glass was tested. In both cases, the coatings were easily removed with a knife.
  • a salt of claim 1 in which the formula of the salt is [R O[CF(CF )CF O],,CF(CF )CON(R')Q] A wherein R,, n, R, Q and A are as defined in claim 1.

Abstract

PREFLUOROALKYL ETHER AMIDO QUATERNARY AMMONIUM SALTS OF THE FORMULA

(R1O(C3F6O)2CF(CF2)CON(R'')Q)+A-

IS WHICH Q IS SELECTED FROM CERTAIN RADICALS CONTAINING A QUARTERNARY AMMONIUM NITROGEN ATOM AND 4-25 CARBON ATOMS ARE USEFUL AS SURFACE ACTIVE AGENTS OR ANTIVETTING AGENTS AND ARE NONCORRESIVE TO STEEL.

Description

3,555,089 PERFLUOROALKYL ETHER AMIDO QUATERNARY AMMONIUM SALTS Philip Lee Bartlett, Wilmington, Del., assignor to E. I. du
Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No.
621,128, Mar. 7, 1967. This application Feb. 16, 1968,
' Ser. No. 705,923 9 Int. Cl. C07c 103/34 US. Cl. 260561 5 Claims ABSTRACT OF THE DISCLOSURE Perfluoroalkyl ether amido quaternary ammonium salts of the formula in which Q is selected from certain radicals containing a quarternary ammonium nitrogen atom and 4-25 carbon atoms are useful as surface active agents or antiwetting agents and are noncorrosive to steel.
CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part ofapplication Serial No. 621,128, filed Mar. 7, 1967, now abandoned.
BACKGROUND OF THE INVENTION In US. Patent 2,764,602, Ahlbrecht discloses surface active quaternary salts of the structure [C F- CONH (CH NQ] +A- where n is 3-11, m is 2-6, N is a quaternary nitrogen atom, Q is an organic terminal structure which satisfies three of the covalences of the quaternary nitrogen atom and A is an anion.
DESCRIPTION OF THE INVENTION Quite surprisingly, it has now been discovered that certain perfluoroalkyl ether amido quaternary ammonium salts are useful as surface active agents or antiwetting agents and have corrosion inhibiting properties toward steel. These salts have the formula i 3 6 )n (C 3) CON(R')Q] A- wherein R is a perfluoroalkyl group of 1-6 carbon atoms, n is an integer from -8, R is hydrogen or an alkyl of 1-6 carbon atoms, Q is a radical containing a quaternary ammonium nitrogen atom and 4-25 carbon atoms and is selected from the group consisting of -O,,H2,NR \Iv v wherein p. is an integer from 1-12, -R R and R are alkyl' groups of 1-18,carbon atoms, and R R and R contain a total of 3-20 carbon atoms,
total of 5-20 carbon atoms,
United States Patent 0 wherein Z'is halogen or methyl and a is an integer from 0-3,
Zb wherein b and a+b are integers from 0-3,
as N/ z. I
wherein a+b is an integer from 0-3, and A is any anion which forms an ammonium salt of the formula NH +A- having a solubility in water of at least about 1%.
The starting materials for preparing the products of this invention are the perfluoroalkyl ether acid fluorides of the formula These acid fluorides are available from two sources, polymerization of hexafluoropropylene oxide and polymerization of mixtures of hexafluoropropylene and oxygen. The acid fluorides'prepared by the polymerization of hexafluoropropylene oxide are taught by Moore et al. in US. Patent 3,250,808 and have the structure R O [CF (CF CF 0] CF(CF CFO If hexafluoropropylene oxide alone is polymerized, the products are n-C F- O[CF(CF )CF O],,CF(CF )CFO as described more fully by Moore in Canadian Patent 725,740. If the polymerization is carried out in the presence of carbonyl fluoride (COF or a perfluoroacid fluorideof the formula F(CH CFO, as described more fully in French Patent 1,362,548, the product is of the formula n F (CF CF 0 [CF (CF CF 0] CF (CF CFO where m is 0-5. When the'polymerization is carried out in the presence of a perfluoroketone of the formula F(CF C(O)(CF F, as described by SeIman in US. Patent 3,274,239, the product is of the formula mom), I
' CFO[CF(CF3)CF2O]nCF(CFs)CFO 3 where x and y are 1-4 and the total of x+y is 2-5. Thus, R; may be a branched or straight chain perfiuoroalkyl group of 1-6 carbon atoms.
The acid fluorides prepared by polymerization of mixtures of hexafiuoropropylene and oxygen are taught by Pasetti Sianesi and Corti in Die Makromolekulare Chemie, 86, pages 308-311 (1965); Sianesi and Fontanelli in Die Makromolekular Chemie, 102, pages 115124 (1967); and French Patent 1,434,537. The polymerization is carried out at temperatures of about 100 C. to 25 C. in the presence of ultraviolet radiation. Unlike the products obtained from the polymerization of hexafluoropropylene oxide, these polymers have backbones which are not in a regular head to tail arrangements; they contain both head to head and tail to tail as well as head to tail arrangements. These polymeric acid fluorides are thus best represented by the formula Generically, the polymers from hexafluoropropylene oxide and hexafluoropropylene-oxygen mixtures are best represented by this more general formula.
The perfluoroalkyl ether amido quaternary salts of this invention are prepared by first converting the perfluoroalkyl ether acid fluoride to a corresponding alkyl perfiuoroalkyl ether ester, and preferably the methyl ester of the formula R O(C F O) CF(CF )CO CH or to a corresponding perfluoroalkyl ether amide of the formula R;O(C F O),,CF(CF )CONHR' in which R is hydrogen or an alkyl of l-6 carbon atoms. The esters are prepared by esterification of the corresponding acid fluoride using standard methods, for example reaction of the acid fluoride with an alkanol such as methanol as taught by Diesslin et al. in US. Patent 2,567,011. Preferably, the esterification is carried out by reacting the perfluoroalkyl ether acid fluoride with excess methanol at 20 C., optionally in an inert solvent, in the presence of suflicient pyridine to consume the hydrogen fluoride formed. In place of methanol one can also use ethanol, propanol, butanol or the like equally well. The amides are prepared by reaction of the corresponding acid fluoride with ammonia or an alkylamine of the formula RNH as also taught in the Diesslin et a1. patent.
When Q is wherein p is an integer from 2-12, R R and R are alkyl groups of 1-18 carbons, and R R and R contain a total of 3-20 carbons, the products are readily prepared by reaction of the alkyl prefluoroalkyl ether ester with a diamine of the formula R2 HN(R')C Hz NR to form a dialkyl-N-tert.-aminoalkyl perfluoroalkyl ether amide of the formula R2 R O(CaFeO)nCF(CFQ)CON(R)C HZ N R;;
by well known techniques such as those described in US. Patent 2,764,603. The amide is then reacted with an alkyl halide, sulfate or arylsulfonate of the formula WA to form the quaternary salt as described in the above cited patent to Ahlbrecht.
A large number of diamines of the type HN (R) C H2 NR are known. Useful examples include: N'Hg 2N g 2( 2)2 4 9)2 CH NH(CH N(CH 2( 2)a 3 7)2 Suitable compounds of the formula R A are those in which R is an alkyl group of 1-18 carbon atoms and A is any anion which forms an ammonium salt of the formula NHJA- having a solubility in water of at least about 1%. Useful examples of RA are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, hexyl, octyl, ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl chlorides, bromides and iodides. The normal alkyl halides, i.e., n-propyl, n-butyl, n-octyl or n-hexadecyl, are preferred. Also useful are the toluene, benzene and chlorobenzene sulfonate esters of methyl, ethyl, propyl, butyl and like alcohols, and methyl and ethyl sulfate. When methyl or ethyl sulfate (R is used, the anion A in the product of the present invention will usually be a mixture of RSO; and
S0 '-[R;O(C F O),,CF(CF CON(R)Q] If the desired diamines of the formula R2 HN(R')C;,Hz NR containing a teritary amino group are not available, primary diamines of the formula NH C H NH may be used. The N-aminoalkyl perfluoroalkyl ether amide product obtained by reacting the perfluoroalkyl ether ester with the primary diamine is then alkylated with at least three moles of alkyl halide, sulfate or sulfonate to form the quaternary salt. Alternatively, the aminoalkyl amide may be alkylated by other procedures such as reductive alkylation with formaldehyde and formic acid, followed by salt formation as before.
Another route to the products in which Q is and p is 2-12 is to react the methyl perfluoroalkyl ether ester with an alkanolamine of the formula (R')C Hz OH to form an N-hydroxyalkyl perfluoroalkyl ether amide of the formula R O(C F O) CF(CF )CON(R)C H OH The hydroxyalkyl amide is then treated with a halogenatin'g agent, for example hydrogen chloride, thionyl chloride or the like, to form the -N-haloalkyl perfluoroalkyl ether amide which is treated with a tertiary amine of the formula R2 NR to form the quaternary salt. Suitable alkanolamines include ethanolamine, propanolamine, butanolamine, octanolamine and dodecanolamine.
'amine of the formula A special procedure is required to obtain the products inwhichQis' ----o,.H2,,1 I- -R= a v and p is 1. .They are readily prepared by reaction of the perfluoroalkyl ether amide of the formula.
-CPH2DNK\Y IKJ s wherein p is an integer from 1-12, Y is a divalent group of the formula (CH -(CH or R is an alkyl group of 1-16 carbons, and R and Y contain a total of 5-20 carbons, the products of this invention are prepared by the samegeneral methods as described above. One procedure is by reaction of a diwith the methyl perfluoroalkyl ether ester and the resulting product with an alkyl halide, sulfate or arylsulfonate of the formula R A where R is an alkyl group of 1-16 carbon atoms to form the quaternary salt. They can also be prepared by reaction of the N-haloalkyl perfluoroalkyl ether amides described above, including the N-chloromethyl amides, with a cyclic tertiary amine of 5-20 carbons of the formula R N Y to form the quaternary salt.
'Useful'exampl'es of diamines of the formula NHtR C H N wherein is an integer from 1-12 and Q is wherein Z is halogen or methyl, and a, 'b and iz+'b are integers from 0-3, the products of this invention can be prepared by reaction of the N-haloalkyl perfluoroalkyl ether amides described above, including the N-chloromethylamides, with a pyridine of the formula or a quinoline of the formula These pyridines and quinolines are well known. Some useful examples of pyridines are pyridine, picoline, lutidine, chloropyridines, bromopyridines, dichloropyridines, dibromopyridines, chloropicolines, bromopicolines, chlorolutidines, bromolutidines and the like. Useful examples of quinolines are quinoline, chloroquinolines, bromoquinolines, quinaldine, chloroquinaldines, bromoquinaldines and the like.
When Q is C H Q' wherein p is an integer from 1-12 and Q is wherein Z is halogen or methyl, a, b and a+b are integers from 0-3, and R is an alkyl of 1-4 carbon atoms, the products of this invention can be prepared by reaction of the methyl perfluoroalkyl ether esters described above with an aminoalkylpyridine of the formula The resulting perfluoroalkyl ether amide is then reacted with an alkyl halide, sulfate or sulfonate of the formula R A where R is an alkyl group of 1-4 carbon atoms. Suitable examples of aminoalkyl pyridines include 2- aminomethylpyridine, 2-(2'-aminoethyl)pyridine, 3-(2'- aminoethyDpy'ridine, 3 aminomethylpyridine, 2,6-dichloro 3 aminomethylpyridine, 2-methyl-3-(2'-aminoethyl)pyridine, 3 (4' aminobutyl)pyridine, 4-aminomethylpyridine and 4-(2'-aminoethyl)pyridine. Suitable aminoalkylquinolines include 2-, 3-, 4-, 5-, 6-, 7- and 8- aminomethylquinolines, 2-, 3-, 4-, 5-, 6-, 7- and 8-(2- aminoethyl)quinolines, -2-, 3-, 4-, 5-, 6-, 7- and 8-(4'- aminobutyl)qninolines, and 2-, 3-, 4-, 5-, 6-, 7- and 8-(3'- methylaminopropyl) quinolines.
Suitable examples of alkyl halides include methyl, ethyl, propyl and butyl chlorides, bromides and iodides. Although the alkyl halides are vpreferred with these amides, methyl sulfate or methyl toluenesulfonate could be used with some success, if desired.
When Q is wherein Z is halogen or methyl, a, b and a+b are integers from 0-3, and R is an alkyl of 1-4 carbons, the products of this invention can be prepared by reaction of the methyl perfluoroalkyl ether ester described above with an aminopyridine of the formula or an aminoquinoline of the formula The resulting perfluoroalkyl ether amide is then reacted with the above defined alkyl halide sulfate or sulfonate of the formula R A.
Suitable aminopyridines include 2-aminopyridine, the 3, 4, 5 or 6-methyl-2-aminopyridine, the 3, 4, 5 or 6- ehloro 2 aminopyridines, 3 aminopyridine, 2-chloro-6- methyl-3-aminopyridine, 4-aminopyridine, the dichloro-4- aminopyridines, and the like. Suitable aminoquinolines includes 2, 3, 4, 5, 6, 7 or S-aminoquinolines, the chloroaminoquinolines, the methylaminoquinolines and the like.
All of the above procedures are generally well known in the art. A convenient inert solvent such as ethers, hydrocarbons, halogenated aromatic hydrocarbons or alcohols may be used at temperatures between 0 C. and the reflux temperature of the system. Alternatively, particularly when the product is a liquid, the methyl perfluoroalkyl ether ester may be heated alone with the amine, allowing the methyl alcohol formed to distill from the system. When a quaternary salt is being formed, the solvent is chosen conveniently to dissolve the reactants but not the solid product which is then readily recovered by filtration.
While specific schemes have been described for preparing the compounds of this invention, it is not intended that this invention be limited to any particular method of synthesis. Other methods may occur to those skilled in the art.
When n is 0-1, the products of the formula of this invention are useful as surface active agents in aqueous systems, for example, as emulsifying agents, dispersants, wetting agents, and the like. These products are particularly useful as dispersing agents for aqueous emulsion polymerizations. Compounds in which n is 2 or greater are insufficiently soluble in water to be useful as surface active agents in aqueous systems.
All of the products of this invention, that is, those in which n is 0 8, are effective as anticorrosion agents for steel. The products wherein n is 0-1 are particularly useful as surface active agents in applications where they come in contact with steel such as in steel treating processes, for example in pickling baths. Those products wherein n is 2-8 are useful for other purposes. For example, they are useful as antiwetting agents in applications requiring mold release agents, release agents for glass, and flotation agents. The preferred products of this invention are those obtained from the polymerization of hexafluoropropylene oxide and hence of the formula [R O (CF CF CF 0 CF (CP CON (R' Q] A- The following examples, illustrating the preparation and utility of the novel compounds of this invention, are
given without any intention that the invention be limited thereto. All parts and percentages are by weight.
EXAMPLE 1 Perfiuoroalkyl ether esters were prepared as follows:
oxide and 100 parts of pyridine in 500 parts of anhydrous diethyl ether was cooled to 1015 C. under anhydrous conditions. Then parts of anhydrous methanol was added over a period of one hour with agitation while maintaining the temperature of the reaction mass at 10-15" C. Agitation was continued for four hours at 10-15 C., then the pyridine hydrofluoride was collected by filtration and the filtrate was washed twice with 250 parts of water, twice with 250 parts of 5% aqueous sodium bicarbonate solution and finally five times with water until the final water was neutral. The ether solution was dried over anhydrous sodium sulfate and the ether was evaporated. The residue was distilled under reduced pressure, giving 430 parts (93.3% of theory) of a n-C F OCF(CF )CF OCF(CF )CO CH boiling point 43 C./9 mm. Hg.
(b) Using essentially thesame procedure, the ester, n-C F OCF(CF )CO CH boiling point 109-1 10 C./ 760 mm. Hg, was prepared in 75.1% yield from 200.0 parts of the acid fluoride and 50.0 parts of methanol. Likewise, the methyl esters,
n-C F O [CF(CF CF 0] CF(CF 3 CO CH and n-C3F7O 3C1: CO2CH3 can be prepared from the corresponding acid fluorides by the same procedure.
EXAMPLE 2 N-tert.-aminoperfluoroalkyl ether amides were prepared as follows:
(a) A solution of 100 parts of in 250 parts of anhydrous diethyl ether was cooled to 10-15 C. under anhydrous conditions and a solution of 22.5 parts of 3-dimethylaminopropylamine in 50 parts of anhydrous diethyl ether was added over a one hour period with agitation. Agitation was continued for four hours at 10-15 C. The ether and excess amine were evaporated at reduced pressure (50 C./5 mm. Hg) and the residue filtered, giving 112.4 parts (98.6% of theory) of n-C F OCF(CF )CF OCF(CF )CONH(CH N(CH as a light yellow liquid.
Analysis.-Calcd for C14H13F17N203 (percent): F, 55.4; N, 4.83. Found (percent): F, 55.3; N, 5.05.
(b) Using the same procedure, the amide,
n-C F OCl=(CF )CONH(CH N(CH3) was prepared.
Using the same procedure n-C F OCF(CF 3 CF OCF (CF CO CH can be reacted with NH (CH N(CH to form n-C F OCF(CF )CF OCF (CF 3 CONH (CH N(CH 2 CHgCHg 9.. to form I g Y a omen. n-omoor FQOFZOCF cmcoNnomonzN H.
5 with omen.
NH; (CH2)4N CH2 C1320 2 to' form omcm n-"omocmomcmoomcmoortmomp CH2 I i CHzC z or with unionismto form n-omoo F 0 F3 0 moon 0 F3) CONHCHZCH \N CF OCF(CF oo crr can be reacted with H3)2N(cH.').NH2 to form CF OCF (CF )CONH(CH N(CH C F OCF(CF CF OCF (CF CO CH can be reacted with NH (CH N (CH 2 to form I C F OCF(CF CF 0 CF (CF CONH (CH N(CH 2 and l (CF CFOCF(CF CF OCF(CF 3 CO CH can be reacted with NH (CH N (CH 2 to form (CF CFOCF(CF )CF OCF(CF CONH (CH N (CH 2 (0) Using the same procedure, 51.0 parts of n-C F OCF(CF CF OCF(CF )CO CH in 250' parts of diet-hyl ether were reacted with 18.8
parts of 2-am'inopyridine to'give 57.0: parts (99.8% of theory) of In the sam'manner, n-C F OCF(CF )CO CH can be reacted with Z-aminopyridine to give n-cmo omen. o ONHO 11051 70 CF (013 under cm 0 ONH (e) Using the procedure of part (a),
' g l'l-CgFqO [CF(CF 3 CF 0] el (CF CO2CH3 Perfluoroalkyl ether amino quaternary ammonium salts were prepared as follows:
(a) A solution of parts of n-C F OCF(CF )CF OCF(CF )CONH(CH N(CH 25.7 parts of methyl iodide and 200 parts of anhydrous methanol was heated under reflux for one hour. The solvent and excess methyl iodide were evaporated under reduced pressure (50 C./5 mm. Hg), to give 123.2 parts (99.1% of theory) of [H-C3F7O CF (CF CF OCF CF CONH (CH N(CH 1- Analysis.Calcd for C H F N O I (percent): F, 44.7; N, 3.88; I, 17.6. Found (percent): F, 44.5; N, 4.05; I, 17.4.
(b) Repeating the above procedure using 15.0 parts of I1-C3F7OCF (CF )CONH(CH N(CH 6.0 parts of methyl iodide and 50.0 parts of methanol gave 20.1 parts (99.6% of theory) of (c) Repeating procedure (a) except that the methyl iodide was replaced with 66.7 parts of methyl chloride and the reaction was carried out under autogeneous pressure gave 106.9 parts (98.5% of theory) of [n-C F OCF (C1 )CFzOCF (CF (d) Repeating procedure (a) except that the methyl iodide was replaced with 60.7 parts of hexadecyl iodide, gave 146.0 parts (99.4% of theory) of (e) Repeating procedure (a) except that the methyl iodide was replaced with 32.0 parts of methyl p-toluenesulfonate gave 132.0 parts (100% of theory) of (f) Using procedure (a) 10.0 parts of H'C3F7OCF 3N 2 8.5 parts of hexadecyl iodide and 25.0 parts of methanol gave 18.2 parts (98.4% of theory) of (g) Using the procedure of part (a),
n-C3F7O 3 1 1 was reacted with methyl iodide to give [n-C F O 2GP (C1 )CONH(CH N(CH )3] Analysis.Calcd for C H F O N I (percent): F, 49.2; N, 3.2; I, 14.3. Found (percent): F, 48.9; N, 3.1; I, 14.1.
(h) Using the procedure of part (a), n-(C F O[CF(CF )CF O] CF (CF )CONH(CH N(CH was reacted with methyl iodide to give [H-C3F7O[CF(CF3)CF2O] CF 3) 2)3 a)a] 1" Analysis.Calcd for C H F N I (percent): F, 52.3; N, 2.; I, 12.0. Found (percent): F, 52.1; N, 2.6; I, 12.7.
(i) Using the procedure of part (a) 1'1'C3F70 CONH(CH N (CH was reacted with hexadecyl iodide to give [n-C F O [CF CF CF CF(CF CONH(CH N(CH 16 33] Analysis.Calcd for C H F O N (percent): F, 59.7; N, 1.5; I, 6.7. Found (percent): F, 59.5; N, 1.4; I, 6.5.
(j) Using the procedure of part (a) I1-C3Fq0 [CF (CF CF 0] CF (CF )CONH(CH N(CH was reacted with methyl iodide to give [II-C3F1O [CF (CF CF 0] CF (CF )CONH(CH N(CH ]""I Using the same procedure methyl iodide can be reacted with 11-C3F7OCF (CF, CF OCF (CF CONH CH N (CH 2 to give CONH(CH N(CH +I- CHzCHz n-CaF OCF(CFa)CF OCF(CF )CONHCH:CH2N CH CHzCHg to form CHzCHa n-O3F OCF(CFa)CFzOCF (CFa)GONHOH CH N CH 1- C zCHz with CHzCHn n-CaF OCF(CF51)CFzOCF(CF3)CONH(CHz)4N CH2 CHzCH2 to form CH2C 2 Il-CaFzOCF (CF3)CF2OCF (CFa)OONH(C z)4N OH; I-
or with to form n-CaF- o C F (C Fa) CF 0 CF (C F3) C ONHCHzCH; N
I CH
CF OCF(CF CF OCF(CF CONH(CH N(CH 3 can be reacted with CH CI to form [CF OCF(CF CF 0CF(CF CONH 2) a 3 a] C Perfiuoroalkyl ether amido quaternary ammonium salts were prepared as follows:
(a) A solution of 10. 0 parts of 3.8 parts of methyl iodide and 50.0 parts of anhydrous methanol was heated under reflux for two hours. The solvent and excess methyl iodide were evaporated under reduced pressure (50 C./5 mm. Hg) to give 11.5 parts (943% of theory) of n-HCaF7OCF(CF3) oraocr on) CONH \N CH3 Analysis.Calcd for C H F N O I (percent): F, 46.2; N, 3.70; I, 18.1. Found (percent): F, 46.1; N, 3.71;
(b) In the same manner, 10.0 parts of 3.5 parts of methyl iodide and 50 parts of anhydrous methanol were reacted to give 12.0 parts (98.4% of theory) of I I CH3'N\/ I Analysis.-Calcd for C H F N O I (percent): F, 42.3; N, 3.63; I, 16.6. Found (percent): F, 42.2; N, 3.61;
In the same manner,
n-C F OCF(CFQ)CONH can be reactedwith methyliodine to form p n I,
. 1 EXAMPLE 5' 1 Utility as surface active .agents was determined as'follows: 1
in the usual manner. The results a re shownin the following table. Water containing no additive had a surface tension of 72 dynes per centimeter at 25 -C.
T BLE .Surface activities of aqueous solutions of products -.pre- .pared above were measured using a Du' Nooy Te'nsiometer The coupons were thenimmersed to one-half their length in 10% {aqueous hydrochloric acid and allowed to stand for five l jtiays at ambient temperature. None of the four Surface tension, dynes/cm. at C.
Concentration, percent Surface active agent; 0.005 0.01 0.05 0.1 0.5 1.0 lii-carvoomom oonmonmmonaflu- I 50.3 53.0 43.0 39.2 27.0 20.2 ln-omoomorz)onioomcmooNn onamwmnrr- 22.1 17.0 10.9 14.7 14.4 14.3 [ri-G3F OCF(CF )CFzOOF(OF3)COHN(GHz) N(CH )'3] Ol 22.0 18.1 17.1 14.8 14.3 14.2 n-ozmoomcra)orzoomoln)ooNnronmN(onmlfi -cnr-otnisoal- 23.1 19.1 13.4 15.1 14.5 14.3
l I I- 49.5 35.0 20.0 nC F OCF(CF )CF20.CF(CH )CONH (Ba.
n-csmooF(CF CFmOFw-F CQ-TNH. 1 1- 51.0 36.2 28.5
EXAMPLE .6
Utility of water-soluble -salt productsas anti-corrosion agents was determined as follows;
Five Type 1020 mildsteel test coupons were each con- 'tacted for 56 wfifiksw th a diiferent 10% hydrochloric acid solution containing about 0.01% of [C F CONH(CI 7I N( 3)a] which is not within the scope of the present invention but is illustrated in Example 1 of the Ahlbrecht patent described above. Severe corrosion occurred.
EXAMPLE 7 Utility of water-insoluble salt products as anti-corrosion agents was determined as follows:
Four Type 1020 mild steel test coupons were each treated with a different 1.0% solution of one of the followcoupons had any evidence of corrosion on their surfaces which remained bright.
For comparison, another Type 1020 mild steel test coupon which had not been surface treated was immersed in 10% hydrochloric acid and allowed to stand'for 5 days at ambient temperature. The coupon turned black and was badly corroded.
EXAMPLE 8 Utility as release agents for metal surfaces was determined as follows:
Two Type 1020 mild steel test coupons were each treated with a different 1.0% solution of one of the following products in trichlorotrifluoroethane for five minutesand then air dried. The products used were:
in-ca ot n ra) Fz iz n m CONH(CH2) 3 3 31 and ll-0 1 0 [OF(CF3) C 20] 8 3) CONH (CH2) 3N (CH3 3] +1- To test the antiwetting or release properties of the treated surfaces, each treated coupon was bonded to an untreated coupon with a typical epoxy resin metal bonding agent (Epon 828 cured with diethylene triamine). In each case the bond could be broken by hand.
For comparison, two untreated Type 1020 mild steel test coupons were bonded together with the same bonding agent. The bond was very strong and could not be broken by hand.
EXAMPLE 9 Utility as release agents for glass surfaces was determined as follows:
Two glass slides were each treated with a different one of the two 1.0% trichlorotrifluoroetliane solutions de- 15 scribed in Example 8 for minutes and air dried. The treated slides were then coated with poly(methyl Z-cyanoacrylate) which is known to be a good adhesive for glass. After setting, the adhesion of the resin coating to the glass was tested. In both cases, the coatings were easily removed with a knife.
For comparison, a similar coating was placed on an untreated glass slide. The film was strongly bonded to the glass as evidenced by the fact that it was not easily removed with a knife.
EXAMPLE Usefulness as flotation agents was determined as follows:
One drop of one of the 1.0% trichlorotrifiuoroethane solutions of Example 8 was added to each of three beakers, each containing 100 ml. of water. One drop of the other of the 1.0% trichlorotrifluoroethane solutions of Example 8 was also added to three different beakers, each containing 100 ml. of water. For each solution, to one beaker was added powdered Cr O to the second was added powdered Cu O, and to the third was added powdered =Fe O For comparison, similar samples of powdered Cr O Cu O and Fe O were also to beakers containing 100 ml. of water, but no added solution. In all cases when the trichlorotrifinoroethane solution was added, the powdered oxide floated. In those cases where the trichlorotrifiuoroethane solution was not added, the oxide sank.
In each of the preceding examples, one may substitute the corresponding compounds containing the group R O(C F O) CF(CF derived from the polymerization of mixtures of hexafluoropropylene and oxygen with essentially equivalent results.
Although the invention has been described and exemplified by way of specific embodiments, it is intended that it not be limited thereto. As will be apparent to those skilled in the art, numerous modifications and variations of these embodiments may be made without departing from the spirit of the invention or the scope of the following claims.
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
16 v t 1. A perfiuoroalkyl ether amido quaternary ammonium salt of the formula wherein R is perfluoroalkyl of 1-6 carbon atoms; n is an integer of from 0-8; R is hydrogen or alkyl of 1-6 carbon atoms; Q is a'radical of 4 -25 carbon atoms and is represented by the formula R2 --C,,H NR R wherein p is an integer of from 1-12, R R and R are alkyl groups of 1-18 carbon atoms and the combined number of carbon atoms in the R R and R groups is between 3 and 20; and A is an anion selected from sulfonate, 804 H3C-SO4 OI H3CCHZSO4 2. A salt of claim 1 in which the formula of the salt is [R O[CF(CF )CF O],,CF(CF )CON(R')Q] A wherein R,, n, R, Q and A are as defined in claim 1.
3. A salt of claim 1 in which the formula is n-C F OCF(CF )CF OCF(CF CONH(CH N(CH +A in which A is defined as in claim 1.
4. The salt of claim 3 in which A is chloride. 5. The salt of claim 3 in which A is iodide.
References Cited UNITED STATES PATENTS ALEX MAZEL, Primary Examiner J. TOVAR, Assistant Examiner US. Cl. X.R.
US705923A 1967-03-07 1968-02-16 Perfluoroalkyl ether amido quaternary ammonium salts Expired - Lifetime US3555089A (en)

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US20040077237A1 (en) * 2002-05-24 2004-04-22 Audenaert Frans A. Fluorochemical composition comprising perfluoropolyether and an extender for the treatment of fibrous substrates
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US4098811A (en) * 1976-12-02 1978-07-04 Ciba-Geigy Corporation Perfluoroalkylthioamido amine and ammonium compounds
US4104452A (en) * 1977-10-06 1978-08-01 The United States Of America As Represented By The Secretary Of The Navy Vinyl polymer-fluoroalkylether oligomer composition
US7094829B2 (en) 2002-05-24 2006-08-22 3M Innovative Properties Company Fluorochemical composition comprising a fluorinated polymer and treatment of a fibrous substrate therewith
US20040077237A1 (en) * 2002-05-24 2004-04-22 Audenaert Frans A. Fluorochemical composition comprising perfluoropolyether and an extender for the treatment of fibrous substrates
US20040077775A1 (en) * 2002-05-24 2004-04-22 Audenaert Frans A. Fluorochemical composition comprising a fluorinated polymer and treatment of a fibrous substrate therewith
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