EP2035130A1 - Tensioactifs fluorés - Google Patents

Tensioactifs fluorés

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Publication number
EP2035130A1
EP2035130A1 EP07764996A EP07764996A EP2035130A1 EP 2035130 A1 EP2035130 A1 EP 2035130A1 EP 07764996 A EP07764996 A EP 07764996A EP 07764996 A EP07764996 A EP 07764996A EP 2035130 A1 EP2035130 A1 EP 2035130A1
Authority
EP
European Patent Office
Prior art keywords
compounds according
group
compounds
fatty acid
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07764996A
Other languages
German (de)
English (en)
Inventor
Wolfgang Hierse
Nikolai Ignatyev (Mykola)
Martin Seidel
Elvira Montenegro
Peer Kirsch
Andreas Bathe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2035130A1 publication Critical patent/EP2035130A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/007—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C237/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/12—Dithiocarbonic acids; Derivatives thereof
    • C07C329/14—Esters of dithiocarbonic acids
    • C07C329/16—Esters of dithiocarbonic acids having sulfur atoms of dithiocarbonic groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the present invention relates to fatty acid alkanol or polyolamides having at least one group Y, wherein Y is CF 3 - (CH 2 ) a -O-, SF 5 -, CF 3 - (CH 2 ) B -S-, CF 3 CF 2 S-, [CF 3 - (CH 2 ) a ] 2 N- or [CF 3 - (CH 2 ) a ] NH-, where a is an integer selected from the range of 0 to 5 or
  • Rf is CF 3 - (CH 2 ) r , CF 3 - (CH 2 ) r O-, CF 3 - (CH 2 ) r S-, CF 3 CF 2 -S-, SF 5 - (CH 2 ) r - or [CF 3 - (CH 2 ) J 2 N-, [CF 3 - (CH 2 ) r ] NH- or (CF 3 ) 2 N- (CH 2 ) r,
  • B is a single bond, O, NH, NR, CH 2 , C (O) -O, C (O), S, CH 2 -O,
  • R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r is O. , 1, 2, 3, 4 or 5, preparation methods for these compounds and uses of these surface-active compounds.
  • Fluorosurfactants have a superior ability to lower the surface energy, for example, in the hydrophobization of
  • fluorosurfactants contain perfluoroalkyl substituents, which in the environment through biological and other oxidation processes too
  • Perfluoralkancarbon Acid and sulfonic acids are degraded. These are considered persistent and are z. T. suspected damage to health causing (GL Kennedy, Jr., JL Butenhoff, GW Olsen, JC O'Connor, AM Seacat, RG Perkins, LB Biegel, SR Murphy, DG Farrar, Critical Reviews in Toxicology 2004, 34, 351-384). Longer-chain perfluoroalkanecarboxylic acids and sulfonic acids also accumulate in the food chain.
  • JP-A-2001/133984 discloses surface-active compounds containing perfluoroalkoxy chains which are suitable for use in antireflective
  • JP-A-09/111286 discloses the use of perfluoropolyether surfactants in emulsions.
  • German patent application DE 102005000858 compounds which carry at least one terminal pentafluorosulfurane group or at least one terminal trifluoromethoxy group and have a polar end group, are surface-active and are excellently suitable as surfactants.
  • Fatty acid alkanol or polyolamides which have no F atoms are known as surfactants. These nonionic alkanolamides or polyolamides, in
  • glucosamine referred to as fatty acid glucamides
  • fatty acid glucamides for example, in detergents according to the British Patent 809 060, published 1959 or after Hildreth et al, Biochem. J. 1982, Vol. 207, pages 363-366 or used for cleaning hard surfaces, according to US 2,708,798.
  • Alkanolamides are foam boosters that enhance or stabilize the foam. Ethoxylated alkanolamides are used as thickeners, foam stabilizers or dispersants.
  • the fatty acid alkanol or polyolamides according to the invention have at least one Y group, Y being CF 3 - (CH 2 ) a -O-, SF 5 -, CF 3 - (CH 2 ) a -S-, CF 3 CF 2 S-, [CF 3 - (CH 2 ) a ] 2 N- or [CF 3 - (CH 2 ) a ] NH-, where a is an integer selected from the range of 0 to 5 or
  • Rf is CF 3 - (CH 2 ) r -, CF 3 - (CH 2 ) r -O-, CF 3 - (CH 2 ) r S-, CF 3 CF 2 -S-, SF 5 - (CH 2 ) r or [CF 3 - (CH 2 ) J 2 N-, [CF 3 - (CH 2 ) r ] NH- or (CF 3 ) 2 N- (CH 2 ) r , B is a single bond, O, NH, NR, CH 2 , C (O) -O, C (O), S, CH 2 -O, OC (O), NC (O) 1 C (O) -N , 0-C (O) -N, NC (O) -N, O-SO 2 or SO 2 -O, R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and
  • a first object of the invention are therefore fatty acid alkanol or polyolamides having at least one group Y, wherein Y is CF 3 - (CH 2 ) a -O-, SF 5 -, CF 3 - (CH 2 ) a -S-, CF 3 CF 2 S-, [CF 3 - (CH 2) a] 2 N- or [CF 3 - (CH 2) a] NH-, where a is an integer selected from the range of O to 5, or
  • Rf is CF 3 - (CH 2 ) r -, CF 3 - (CH 2 ) r -O-, CF 3 - (CH 2 ) r -S-, CF 3 CF 2 -S-, SF 5 -
  • B is a single bond, O, NH, NR, CH 2 , C (O) -O, C (O), S, CH 2 -O,
  • R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r is O. , 1, 2, 3, 4 or 5.
  • the compounds according to the invention preferably contain no further fluorinated groups in addition to the stated fluorinated groups Y.
  • the fatty acid amides according to the invention are derived from fatty acids which may be saturated or unsaturated and contain 4 to 25 C atoms, preferably 8 to 22 C atoms, particularly preferably 12 to 20 C atoms.
  • the fatty acids may also carry, for example, OH groups in the side chain.
  • fatty acids examples include lauric acid (C 11 H 23 COOH), myristic acid (C 3 H 27 COOH), palmitic acid (C 15 H 3 iCOOH), stearic acid (C 17 H 35 COOH), oleic acid (C 17 H 33 COOH), linoleic acid (C 17 H 3 I COOH), ricinoleic acid (C 17 H 32 (OH) COOH), linolenic acid
  • straight-chain fatty acids are preferred, i. preferably with 8, 10, 12, 14, 16, 18, 20 or 22 C atoms, particularly preferably with 12, 14, 16, 18 or 20 C atoms.
  • synthetic fatty acids with an odd number of carbon atoms.
  • the group Y is preferably terminal to the amide function.
  • Rf is CF 3 - (CH 2 V-, CF 3 - (CH 2 ) rO-, CF 3 - (CH 2 ) r S-, CF 3 CF 2 -S-, SF 5 - (CH 2 ) r or [CF 3 - (CH 2 ) r ] 2 N-, [CF 3 - (CH 2 ) r ] NH- or (CF 3 ) 2 N- (CH 2 ) r, B represents a single bond, O, NH, NR, CH 2, C (O) -O 1 C (O), S, CH 2 -O 1 0-C (O) 1 NC (O), C (O) -N, O-C (O) -N, NC (O) -N, O-SO 2 or SO 2 -O, R is alkyl of 1 to 4 C atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r
  • the compounds according to the invention are preferably compounds of the formula I. ) in which
  • R 1 is H, alkyl having 1 to 4 carbon atoms or hydroxyalkyl having 2 to 4 carbon atoms
  • N-R may be, for example, NH, N-methyl, N-ethyl, N-propyl,
  • reducing sugars or synonymous carbohydrates
  • reducing sugars are ribose, arabinose xylose, lyxose, allose, altrose, glucose, mannose,
  • Sorbose or agarose In this list both isomers, i. each contain the D or L forms.
  • glucose or galactose especially glucose are preferably used.
  • disaccharides such as sucrose (also called sucrose), lactose, trehalose, maltose, cellobiose, gentiobiose or
  • Melibiose be used. This list includes both the ⁇ and ⁇ forms. From the group of disaccharides are preferably sucrose or
  • Starch sugar syrup for example made from corn, may be used as starting materials for reducing sugars, and this syrup may contain mixtures of reducing carbohydrates.
  • Fatty acid polyolamides based on this starting material are therefore mixtures which, however, can also be used as mixtures in the uses according to the invention.
  • p 1 to 9, wherein the ethyleneoxy, propyleneoxy and butyleneoxy units can also be mixed in the chain , p is preferably 2, 3, 4, 5, 6 or 7, most preferably 2, 3 or 4.
  • a is preferably 0, 1 or 2, particularly preferably 0 or 2, very particularly preferably 0 and r is preferably 0 to 3, in particular 0 to 1.
  • Y q is 0 and at least one c and / or b each represents 1.
  • all c and b are 1, i. the aromatics are substituted in the o- and / or p-position with fluorine groups, in particular in o, p, o-position.
  • all q and b are each 0 and at least one c is 1.
  • both c are 1, i. the aromatics are substituted in the o-position with fluorine groups, in particular in o, o-position.
  • all c and q are each 0 and b is 1, i. the aromatics are substituted in the p position with fluorine groups.
  • the group Y as defined above, which determines the modification of the fatty acid, in a preferred variant of the invention consists of CF 3 -O-, CF 3 -CF 2 -S-, CF 3 -S-, (CF 3 ) 2 N-, or
  • Rf is CF 3 - (CH 2 V-, CF 3 - (CH 2 ) r -O-, CF 3 - (CH 2 ) r -S-, CF 3 CF 2 -S-, SF 5 -
  • B represents a single bond, O, NH, NR, CH 2 , C (O) -O, C (O), S, CH 2 -O,
  • R is alkyl of 1 to 4 carbon atoms, b is O or 1 and c is O or 1, q is O or 1, wherein at least one of b and q is 1, and r is O. ,
  • R f is preferably CF 3 - (CH 2 ) r -, CF 3 - (CH 2 ) r -O-, CF 3 - (CH 2 ) r -S or [CF 3 - (CH 2 Jr] 2 N-.
  • a preferred variant of the invention comprises fluorine groups, also referred to below as Rf for short, in which r stands for 0, 1, 2 or 3, in particular for 0, 1 or 2, where r is preferably O.
  • Rf is CF 3 -, CF 3 -O-, CF 3 -CH 2 -CH 2 -O-, CF 3 -S-, CF 3 CF 2 -S-, SF 5 - , CF 3 -CH 2 -CH 2 -S-, (CF 3 J 2 -N- and (CF 3 -CH 2 -CH 2 J 2 -N-, especially for CF 3 -, CF 3 -O-, CF 3 -S- and (CF 3 J 2 -N-.
  • a further preferred variant of the invention comprises the groups Rf is CF 3 -, CF 3 -S-, CF 3 CF 2 -S-, SF 5 - or (CFa) 2 N-.
  • B are O, S, CH 2 O, CH 2 , C (O) and OC (O).
  • B is O and OC (O) are preferred.
  • a particularly preferred variant of the invention comprises the groups Y being CF 3 -Ar-O, CF 3 -O-Ar-O 1 CF 3 -CH 2 -CH 2 -O-Ar-O, CF 3 -S-Ar-O, CF 3 CF 2 -S-Ar-O, SF 5 -Ar-O, CF 3 -CH 2 -CH 2 -S-Ar-O, (CF 3 ) 2 -N-Ar-O, (CF 3 -CH 2 -CH 2 ) 2 -N-Ar-O, CF 3 -Ar-OC (O), CF 3 -O-Ar-OC (O), CF 3 -CH 2 -CH 2 -O-Ar-OC ( O), CF 3 -S-Ar-OC (O), CF 3 CF 2 -S-Ar-OC (O), SF 5 -Ar-OC (O), CF 3 -CH 2 -CH 2 -
  • a particularly preferred variant of the invention comprises Y equal to CF 3 -Ar-O and CF 3 -Ar-OC (O).
  • q is O and at least one c and / or b are each 1.
  • all c and b are 1, i. the aromatics are substituted in the o, p, o position by fluorine groups.
  • all q and b are each O and at least one c is 1.
  • both c are 1, i. the aromatics are substituted in the o, o position with fluorine groups.
  • the particularly preferred compounds of the fatty acid alkanol or polyolamides include the following compounds:
  • the fatty acid amides according to the invention can be prepared by methods known to the skilled person from the literature.
  • the invention therefore further provides a process for the preparation of the fatty acid alkanol- or polyolamides according to the invention, characterized in that a fatty acid containing the group Y, as defined above, or a derivative of this fatty acid, preferably an acid chloride, an active ester or an anhydride, with a Alkanolamine or polyolamine is reacted.
  • Derivatives of the modified fatty acid whose synthesis is described in detail below are, for example, their fatty acid chlorides or lower esters of these fatty acids, in particular the methyl esters, active esters or anhydrides.
  • modified fatty acid esters in particular preferably methyl esters
  • an organic solvent in the presence of a base catalyst with the corresponding amines.
  • acid chlorides in an organic Solvent reacted in the presence of a base catalyst with the corresponding amines.
  • Suitable basic catalysts are alkoxides, hydroxides or carbonates or amines. Preference is given to alkoxides, such as sodium methoxide,
  • Potassium ethoxide used is triethylamine.
  • Suitable solvents for the conversion to N-polyolamides are organic solvents such as methanol, ethanol, propanol, isopropanol,
  • the reaction is preferably carried out below 100 0 C.
  • a suitable solvent is also tetrahydrofuran.
  • Alkylpolyhydroxyamines are described in detail in EP 0 558 515 or in US 2,703,798.
  • the corresponding disclosure relating to the method mentioned in EP 0 558 515 or US Pat. No. 2,703,798 thus expressly also belongs to the disclosure content of the present application.
  • the preparation of the / VR 1 polyhydroxyamine can be accomplished, for example, by reacting a reducing carbohydrate or reducing carbohydrate derivative with a primary amine at molar ratios of amine: carbohydrate of not more than about 7: 1 in a suitable solvent.
  • the suitable reaction temperature is between 0 ° C. and 80 ° C.
  • the resulting adduct is reacted under inert gas conditions with hydrogen under mild conditions in the presence of a catalyst, for example Raney nickel or nickel adhering to silica or alumina, and the catalyst and the resulting water away.
  • a catalyst for example Raney nickel or nickel adhering to silica or alumina
  • ⁇ / -R 1 polyhydroxyamines are also commercially available, such as N-methylglucamine.
  • Suitable bases have previously been described.
  • Suitable Lewis acids are, for example, boron trifluoride, tin tetrachloride or antimony pentachloride, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry 2002, 2000ullmann-Surfactants, Section 7.2, pages 59 to 114.
  • modified fatty acid can be prepared according to variant B:
  • 2-bromoethanol is converted to the fluoroformate and then the carbonyl group is transformed with SF 4 to OCF 3 -Ether.
  • the fatty acid is now obtained by: 1. Williamson ether synthesis, 2. the subsequent hydrogenolytic debenzylation, and 3. the subsequent oxidation with stoichiometric amounts of sodium periodate and catalytic amounts of ruthenium chloride. hypd / C
  • DIAD diisopropyl azodicarboxylate
  • the modified fatty acid may also be double etherified
  • the aliphatic SFs group may, for. B. at terminal double bonds via the radical addition of SF 5 CI or SF 5 Br are inserted.
  • a dehydrohaiogenation or a hydrogenation can be carried out. The first two of these reaction steps are described in the literature (R. Winter, PG Nixon,
  • SFs-modified fatty acid is the addition of SF 5 Cl to a terminal double bond of a fatty acid ester, for example a methyl ester, the elimination of HCl and subsequent ester cleavage.
  • CF 3 -CF 2 -S group is carried out, for example, according to the following scheme and according to Anselmi, E. et al. J. Fluorine Chem. 2000, 105, 1, 41-44 or optionally preparable by: Se (trifluoromethyl) dibenzoselenophenium triflate (Umemotos reagent): T. Umemoto et al. J. Am. Chem. Soc. 1993, 115, 2156-2164.
  • the introduction of the aliphatic (CF 3 ) 2 N- to the fatty acids succeeds first by reacting corresponding tetramethylammonium salts with halides, which have a corresponding number of C atoms for the desired fatty acid and a terminal double bond according to the scheme given.
  • the respective tetramethylammonium salts can be obtained analogously to the description of EP 1081129.
  • the corresponding disclosure to the method mentioned in the cited References thus expressly also belong to the disclosure content of the present application.
  • the terminal double bond can be converted into the carboxy function by methods known to those skilled in the art. Examples can be taken from the following scheme, wherein Rf in the following scheme can be N (CF 3 ) 2 but also SCF 3 or SC 2 F 5 :
  • CF 3 S or CF 3 CF 2 S or CF 3 (CH) a end groups can also be introduced instead of (CF 3 ) 2 N end groups.
  • sulfur-containing compounds instead of Pd
  • the end group CF 3 NH- in compounds CF 3 NH-R can by means of literature methods by reacting corresponding
  • the corresponding starting materials are in each case obtainable by methods known from the literature and the radicals R of the products can be chemically modified by means of established methods.
  • R f CF 3 - (CH 2 ) r, CF 3 - (CH 2 VO-, CF 3 - (CH 2 VS-, CF 3 CF 2 -S-, SF 5 - (CH 2 Jr or [CF 3 - ( CH 2 ) r ] 2 N-, [CF 3 - (CH 2 ) r ] NH- or (CF 3 ) 2 N- (CH 2 ) r
  • B is a single bond, O, NH, NR, CH 2 , C (O) -O, C (O), S, CH 2 -O, OC (O), NC (O), C (O) -N, O-C (O) -N, NC (O) -N, O-SO 2 or SO 2 -O
  • R is alkyl of 1 to 4 carbon atoms
  • b is O or 1 and c is O or 1
  • q is O or 1 at least one radical from b and q is 1
  • r is O
  • Rf is CF 3 - (CH 2 ) r -, CF 3 - (CH 2 ) r -O-, CF 3 - (CH 2 JrS-, CF 3 CF 2 -S-, SF5- (CH 2 ) r, [CF 3 - (CH 2 ) J 2 N-, [CF 3 - (CH 2 ) JNH- or (CF 3 ) 2 N- (CH 2 ) r -, with indices as described above, can be obtained by means of substitution reactions If Rf is used in the following schemes, unless otherwise stated, the definition given here applies.
  • W O, NH, NR
  • the Arylsulfonklarechlorid is obtained by reaction with CISO 3 H from the corresponding aromatic.
  • W O, NH, NR 1
  • the CF 3 groups can be obtained by reacting aromatic carboxylic acids with HF and SF 4 under elevated pressure and elevated temperature, as indicated in the following scheme
  • DBH 1,3-dibromo-5,5-dimethylhydantoin 0
  • TPAP tetra-n-propylammonium perruthenate
  • G ' -OH, -Br, -NH 2 , -NO 2 , -CHO, -CO 2 H
  • Aromatic trifluoromethylthioethers and pentafluoroethylthioethers are obtainable by substitution of iodoaromatics or etherification of thiophenols, as indicated in the following scheme:
  • G " -OH, -I, -Br, -Cl, -NH 2 , -SH, -B (OH) 2 , -CHO, -CO 2 H, -CO 2 Me , -CONH 2 , -CN, -CH 2 OH, -CH 2 Br 1 -CH 2 CN.
  • Trifluoromethoxyaromaten can be obtained by reacting phenols with carbon tetrachloride and hydrogen fluoride.
  • nitroresorcinol can be prepared according to the following literature: ref. 1 spark; Krucker; BSCFAS; Soc. Soc. Chim. fr .; 1953; 744, 746. Ref. 1 Grosheintz; Fischer; JACSAT; J. Am. Chem. Soc. 70; 1948; 1476, 1478.
  • G " -OH, -I, -Br, -Cl, -NH 2 , -NHAc, -CHO, -CO 2 H, -CO 2 Me, -CONH 2 , -CN , -CH 2 OH, -CH 2 Br, -CH 2 CN.
  • a surface activity that may be the same or superior to conventional hydrocarbon surfactants in terms of efficiency and / or effectiveness, and / or
  • the compounds which can be used according to the invention as surfactants are particularly suitable for use as water repellents or oleophobicizing agents.
  • the compounds according to the invention or the compounds to be used according to the invention can advantageously be used with one or more of the following functions: anti-fogging agent, dispersing agent, emulsion stabilizer,
  • the compounds according to the invention or the compounds to be used according to the invention can also be used advantageously and have one or more of the following functions: defoamer, deaerator, friction control agent, wetting agent, leveling agent, pigment compatibility improver, printing resolution improver, drying accelerator.
  • Another use according to the invention of compounds according to the invention or the compounds to be used according to the invention is the use as an interface mediator or emulsifier. Especially for the preparation of fluoropolymers by means of emulsion polymerization, these properties can be advantageously exploited.
  • antistatic agents according to the invention or compounds to be used according to the invention.
  • the antistatic effect is particularly in the treatment of textiles, especially clothing, carpets and carpets, upholstery in furniture and automobiles, non-woven textile materials, leather goods, papers and carton, wood and wood-based
  • compounds according to the invention or compounds to be used according to the invention are suitable as protection agents against stains and stains, stain releases, anti-fogging agents, lubricants, and as abrasion resistance and mechanical improvers
  • compounds according to the invention or compounds to be used according to the invention may advantageously have one or more of the following functions: wetting agents, flow control agents, water repellents, oil repellents, stain protectors and soiling, lubricants, defoamers, deaerators, drying accelerators can be used.
  • wetting agents wetting agents, flow control agents, water repellents, oil repellents, stain protectors and soiling, lubricants, defoamers, deaerators, drying accelerators can be used.
  • the use as detergent or soil emulsifying and dispersing agent is additionally an advantageous embodiment of the present invention
  • the compounds according to the invention or compounds to be used according to the invention can be advantageously used with one or more of the following
  • Lubricant Internal friction reducer, UV stabilizer, water repellent, oil repellent, stain repellent and Contaminants, coupling agents for fillers, flame retardants, migration inhibitor (especially against migration of plasticizers), anti-fogging agents are used.
  • the function as a haze inhibitor with or without foaming action is additionally an object of the present invention.
  • the compounds which can be used according to the invention as surfactants are suitable for washing and cleaning applications, in particular of textiles. Cleaning and polishing hard surfaces is also a possible field of application for the compounds which can be used according to the invention as surfactants.
  • the compounds which can be used according to the invention as surfactants can advantageously be used in cosmetic products, such as, for example, foam baths and hair shampoos, or as emulsifiers in creams and lotions.
  • hair and personal care products e.g., hair conditioners and hair lotions
  • Hair conditioners with one or more of the following functions: wetting agents, foaming agents, lubricants, antistatic agent, increase in resistance to skin fats, the compounds of the invention or the compounds used according to the invention can also be used advantageously.
  • compounds according to the invention or compounds to be used according to the invention have one or more of the following functions: substrate wetting agent, adjuvant, foam inhibitor, dispersant, emulsion stabilizer.
  • wetting agents As additives in adhesives, with one or more of the following functions: wetting agents, penetrating agents, substrate adhesion promoters, defoamers, compounds according to the invention or compounds to be used according to the invention can likewise be used to advantage.
  • additives in lubricants and hydraulic fluids with one or more of the following functions: wetting agent, corrosion inhibitor, compounds of the invention or used according to the invention compounds can serve.
  • wetting agent corrosion inhibitor
  • compounds of the invention or used according to the invention compounds can serve.
  • dispersant in particular for fluoropolymer particles
  • compounds of the invention or compounds to be used according to the invention may have one or more of the following functions: water repellents, oil repellents, soil protection agents, weatherability improvers, UV stabilizers, silicone bleed-off agents.
  • a further field of application for the compounds which can be used according to the invention as surfactants is flotation, ie the application and separation of ores and minerals from deaf rock.
  • flotation ie the application and separation of ores and minerals from deaf rock.
  • they are used as additives in preparations for mineral processing, in particular flotation and leaching solutions, with one or more of the following functions: wetting agent, foaming agent, foam inhibitor.
  • the use as additives in stimulants is also related of petroleum sources, with one or more of the following functions: wetting agent, foaming agent, emulsifier.
  • preferred compounds of the invention which can be used as surfactants can also be used as emulsifiers or dispersing agents in foods. Further fields of application lie in the metal treatment, as leather auxiliary, the building chemistry and in the plant protection.
  • surfactants of the invention are also useful as antimicrobial agents, especially as reagents for antimicrobial surface modification.
  • the compounds according to the invention for the application are usually introduced into appropriately designed preparations.
  • Corresponding agents containing at least one compound according to the invention are likewise provided by the present invention.
  • Such agents preferably contain a carrier suitable for the particular intended use and optionally further specific active substances and / or, if appropriate, auxiliaries.
  • these are color and lacquer preparations, fire-extinguishing agents, lubricants, detergents and Detergents, deicers or water repellents for textile finishing or glass treatment.
  • the agents are water repellents for finishing textiles and carpets.
  • the hydrophobic finishing of textiles, especially weatherproof clothing, serves to render it either water-repellent or water-impermeable.
  • the hydrophobizing agent is applied to the fibers of the textiles and arranges there so that the hydrophobic parts of the molecule perpendicular to
  • the water takes on the spherical shape due to the cohesive forces and rolls off the textile surface.
  • agents according to the invention are dyestuff and lacquer preparations, fire-extinguishing agents (powders and foams), lubricants, detergents and de-icers.
  • the preparation of the agent can be carried out according to known methods; for example, by mixing the compounds according to the invention with a carrier suitable for the particular intended use and, if appropriate, further specific active substances and, if appropriate, auxiliaries.
  • the preparation of the compounds to be used according to the invention can be carried out by methods known to the skilled person from the literature.
  • the preferred compounds mentioned in the description their use, compositions and methods, further preferred combinations of the subject matters of the invention are disclosed in the claims.
  • PE Petroleum ether
  • acylation 13 g of methylaminohexanol are dissolved in 150 g of THF, and 32 g of the acid chloride and 10 g of triethylamine are added. After completion of the reaction, the product is isolated and purified by standard laboratory methods.
  • acylation 20 g of N-methylglucosamine are dissolved in 150 g of THF, and 32 g of (EJ-IO-pentafluorosulfanyl-dec-O-ene-carboxylic acid chloride prepared analogously to Example 1 and 10 g of triethylamine are added usual laboratory methods isolated and cleaned.
  • the solvent is removed on a rotary evaporator. Subsequently, 90 ml of cold MTB ether are added, whereby triphenylphosphine oxide precipitates. The solid is sucked off and the solution stored over the weekend in the refrigerator, so that the rest still falls. The residual solid is filtered off with suction and the residue is washed with MTB. The product solution is concentrated by rotary evaporation and purified by column chromatography.
  • Example 2 Analogously to Example 1, initially 24 g of 7- (3,3,3-trifluoropropoxy) heptanoic acid in 100 g of toluene are introduced and reacted with 24 g of SOCl 2 and the resulting acid chloride with 13 g of methylaminohexanol in 80 ml of THF and in the presence of triethylamine acylated.
  • acylation 20 g of N-methylglucosamine are dissolved in 150 g of THF, and 26 g of 7- (3,3,3-trifluoropropoxy) -heptanoic acid chloride, prepared analogously to Example 2 and 10 g of triethylamine, are added. After completion of the Reaction, the product is isolated and purified using standard laboratory methods.
  • reaction mixture is quenched with 1200 ml of ice water, the organ. Phase separated, the aqueous phase extracted twice with MTB ether and the combined organic extracts washed with saturated NaCl solution. After drying the organ. Phase and
  • the batch is then quenched with about 10% NHUCI solution (200 ml).
  • the phases are separated.
  • the water phase is washed twice with 100 ml of MTB ether.
  • the organic phases are combined and then washed once with 10% strength 100 ml of saturated NaCl solution, separated and dried with Na 2 SO 4 , filtered and concentrated on a rotary evaporator to residue.
  • the reaction mixture is 1 h at
  • the RG is heated to 19 ° C and then about 1 hour at this
  • the dark red reaction solution becomes a yellowish suspension.
  • KOH in 400 ml deionised water are added to this suspension until a pH of 7 is reached.
  • the suspension is getting thinner and thinner.
  • the phases are separated, the aqueous extracted with MTB ether 2 times.
  • the collected organic phases are washed once with brine, dried over sodium sulfate and then concentrated.
  • the crude product is stirred with activated charcoal and purified by column chromatography in petroleum ether.
  • Example 1 22.6 mmol of the alcohol are dissolved in a mixed solvent of carbon tetrachloride (80 ml), acetonitrile (80 ml) and water (100 ml), then the sodium metaperiodate (10.88 g, 50.8 mmol, 2.25 eq) and the ruthenium (III) chloride (468 mg, 2.26 mmol, 0.1 eq) was added and the reaction mixture stirred for 3 hours at 22 ° C - 26 ° C (RT). Thereafter, 100 ml of dichloromethane are added to the reaction mixture, the phases are separated and the aqueous phase is back-extracted twice with 100 ml of dichloromethane. The combined dichloromethane solutions are dried with sodium sulfate, filtered and the solvent is distilled off. The carboxylic acid is obtained as an oily residue.
  • Example 2 Analogously to Example 1, initially 21 g of 7-trifluoromethoxyheptanoic acid are initially charged in 100 g of toluene and reacted with 24 g of SOCl 2 and the resulting acid chloride is acylated with 13 g of methylaminohexanol in THF and in the presence of 10 g of triethylamine.
  • acylation 20 g of N-methylglucosamine are dissolved in 150 g of THF, and 23 g of trifluoromethoxyheptanoic acid chloride, prepared analogously to Example 5, and 10 g of triethylamine are added. After completion of the reaction, the product is isolated and purified by standard laboratory methods.
  • the methyl ester (27 mmol) is taken up in 250 ml of THF and treated with 5% palladium on activated carbon (10 mol%). After creating the
  • the reaction mixture is stirred for 3 h and worked up after completion of the reaction.
  • the catalyst is filtered off under a protective gas atmosphere and the solution is evaporated on a rotary evaporator.
  • the product can be used directly in the next stage.
  • Example 2 Analogously to Example 1, 0.1 mol of the carboxylic acid from stage 1 are initially charged in 100 g of toluene and reacted with 24 g of SOCb and the resulting acid chloride is acylated with 13 g of methylaminohexanol in THF and in the presence of 10 g of triethylamine.
  • the biochemical degradability of the compounds is determined by the dental
  • test substances approx. 100 to 200 mg / l as DOC ventilation: with purified air
  • Used measuring module ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Lubricants (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des amides d'alkanol ou de polyol d'acide gras comportant au moins un groupe Y qui désigne CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>a</SUB>-O-, SF<SUB>5</SUB>-, CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>a</SUB>-S-, CF<SUB>3</SUB>CF<SUB>2</SUB>S-, [CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>a</SUB>]<SUB>2</SUB>N- ou [CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>a</SUB>]NH-, a étant un nombre entier choisi entre 0 et 5, ou bien (formule I), dans laquelle Rf désigne CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>r</SUB>, CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>r</SUB>-O-, CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>r</SUB>-S-, CF<SUB>3</SUB>CF<SUB>2</SUB>-S-, SF<SUB>5</SUB>- (CH<SUB>2</SUB>)<SUB>r</SUB>- ou [CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>r</SUB>]<SUB>2</SUB>N-, [CF<SUB>3</SUB>-(CH<SUB>2</SUB>)<SUB>r</SUB>]NH- ou (CF<SUB>3</SUB>)<SUB>2</SUB>N-(CH<SUB>2</SUB>)<SUB>r</SUB>, B signifie une liaison simple, O, NH, NR, CH<SUB>2</SUB>, C(O)-O, C(O) S, CH<SUB>2</SUB>-O, O-C(O), N-C(O), C(O)-N, 0-C(O)-N, N-C(O)-N, O-SO<SUB>2</SUB> ou SO<SUB>2</SUB>-O, R représente alkyle doté de 1 à 4 atomes C, b désigne 0 ou 1 et C désigne 0 ou 1, q désigne 0 ou 1, au moins un groupe de b et q signifiant 1, et r représente O, 1, 2, 3, 4 ou 5. L'invention porte également sur des procédés de production de ces composés et sur des utilisations de ces composés tensioactifs.
EP07764996A 2006-07-04 2007-07-02 Tensioactifs fluorés Withdrawn EP2035130A1 (fr)

Applications Claiming Priority (2)

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DE102006031151A DE102006031151A1 (de) 2006-07-04 2006-07-04 Fluortenside
PCT/EP2007/005840 WO2008003445A1 (fr) 2006-07-04 2007-07-02 Tensioactifs fluorés

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WO (1) WO2008003445A1 (fr)

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US20090312432A1 (en) 2009-12-17
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US8049022B2 (en) 2011-11-01

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