DE102011114651A1 - New diketo compounds containing at least one pentafluorosulfoxy group useful e.g. as surfactants, water or oil repellents, antistatic agents, leather goods, mineral substrates and additives in surface coating formulations and emulsifiers - Google Patents

Abstract

Diketo compounds (I) containing at least one pentafluorosulfoxy group are new. Diketo compounds of formula (R 3>-L 1>-O-C(=O)-C(X)(R 1>)-CH(R 2>)-C(=O)-O-L 2>-R 4>) (I) containing at least one pentafluorosulfoxy group are new. R 1>, R 2>H, OH or CHY 1>-COO-L 3>-OSF 5; R 3>, R 4>H or OSF 5; L 1>-L 3>alkyl, where one or more non-adjacent C atoms are optionally replaced by O, S and/or N and optionally contains one or more double bonds, triple bonds and/or OSF 5groups in its chain and/or side chain; and X, Y 1>an anionic polar group or H. Independent claims are included for: (1) the preparation of (I); and (2) a sulfosuccinate compound of formula (F 5SO-L-O-C(=O)-CH=CH-C(=O)-O-L-OSF 5) (VI) and a sulfotricarballylate compound of formula (F 5SO-L-O-C(=O)-CH=C(C(=O)-O-L-OSF 5)-CH(Y 1>)-C(=O)-O-L-OSF 5) (VII).

Description

Technical area

The present invention relates to novel compounds with OSF _{5 end} groups, their use as surface-active substances and preparation processes for these compounds.

Background of the invention

Fluorosurfactants have an outstanding ability to reduce the surface tension, for example, in the hydrophobization of surfaces z. B. of textiles, paper, glass, building materials or adsorbents is used. In addition, it is possible to use them as an interface or emulsifier or viscosity reducer in paints, varnishes or adhesives.

In general, fluorosurfactants contain perfluoroalkyl substituents which are degraded in the environment by biological and / or other oxidation processes to perfluoroalkylcarboxylic acids (PFCA's) and -sulfonic acids (PFAS's). In recent years, the accumulation of perfluoroalkylcarboxylic acids (PFCA's) and perfluoroalkylsulfonic acids (PFAS's) in nature has been a concern. PFCA's and PFAS's are highly persistent compounds whose long-chain variants (with perfluoroalkyl chains of 8 or more carbon atoms) have bioaccumulative potential. They are partly suspected of causing health damage ( GL Kennedy, Jr., JL Butenhoff, GW Olsen, JC O'Connor, AM Seacat, RG Biegel, SR Murphy, DG Farrar, Critical Review in Toxicology, 2004, 34, 351-384 ).

Sulfosuccinates and / or sulfotricarballylates with different fluorinated side chains are known in US 4,968,599 and US 4,988,610 such as US 6,890,608 described and in AR Pitt et al., Calloids and Surfaces A: Physicochemical and Engineering Aspects, 1996, 114, 321-335 ; AR Pitt, Progr. Colloid Polym. Sci, 1997, 103, 307-317 and Z.-T. Liu et al., Ind. Eng. Chem. Res. 2007, 46, 22-28 ,

The company Omnova markets polymers whose side chains have terminal CF ₃ or C ₂ F ₅ groups. In the International Patent Application WO 03/010128 are described perfluoroalkyl-substituted amines, acids, amino acids and thioethers having a C3-20 perfluoroalkyl group.

Out JP-A-2001/133984 are surface active compounds with perfluoroalkoxy chains known, which are suitable for use in antireflection coatings. Out JP-A-09/111286 the use of perfluoropolyether surfactants in emulsions is known.

In the older German patent application DE 102005000858 Compounds which carry at least one terminal pentafluorosulfuranyl group or at least one terminal pentafluorosulfoxy group and have a polar end group, are surface-active and are suitable as surfactants.

Furthermore, there is a need for alternative surface-active substances, preferably with a, the conventional fluorosurfactants, comparable property profile, as well as a large chemical versatility, which preferably do not degrade during long-chain persistent fluorocarboxylic or fluorosulfonic in oxidative or reductive degradation or are preferably effective in lower dosage as conventional fluorosurfactants.

There have now been found new compounds which are suitable as surface-active substances and preferably one or more of the above-mentioned. Do not have disadvantages.

Summary of the invention

wobei:
R¹, R² = unabhängig voneinander Wasserstoff, Hydroxy oder -CHY-COO-L³-OSF₅ sind,
R³, R⁴ = unabhängig voneinander Wasserstoff oder OSF₅ sind, bevorzugt beide gleich OSF₅ sind,
L¹, L², L³ = unabhängig voneinander lineares oder verzweigtes Alkyl sind, wobei ein oder mehrere nicht benachbarte C-Atome durch O, S, und/oder N ersetzt sein können, und/oder ein oder mehrere Doppel- und/oder Dreifachbindungen und/oder eine oder mehrere OSF₅-Gruppen in der Kette und/oder der Seitenkette enthalten sein können, bevorzugt L¹, L² und L³ gleich sind,
X, Y = unabhängig voneinander eine anionische polare Gruppe oder Wasserstoff sind,
und die Verbindungen mindestens eine OSF₅-Gruppe enthalten.A first subject of the present invention are compounds of the formula (I)

in which:
R ¹ , R ² = independently of one another are hydrogen, hydroxy or -CHY-COO-L ³ -OSF ₅ ,
R ³ , R ⁴ = independently of one another are hydrogen or OSF ₅ , preferably both are equal to OSF ₅ ,
L ¹ , L ² , L ³ = are independently linear or branched alkyl, wherein one or more non-adjacent carbon atoms may be replaced by O, S, and / or N, and / or one or more double and / or Triple bonds and / or one or more OSF ₅ groups in the chain and / or the side chain can be contained, preferably L ¹ , L ² and L ^{3 are the} same,
X, Y = independently of one another are an anionic polar group or hydrogen,
and the compounds contain at least one OSF ₅ group.

The compounds according to the invention may contain one or more pentafluorosulfoxy groups, it being possible for the OSF ₅ groups to be bonded to the carboxylate groups as R ³ and / or R ⁴ and / or as substituents of L ¹ , L ² and / or L ³ . Compounds having one to six pentafluorosulfoxy groups, especially those having two or three pentafluorosulfoxy groups, are preferred. In a preferred variant of the invention R ³ and / or R ^{4 are the} same as OSF ₅ groups and bound to the carboxyl groups via linear alkyl chains which contain no further OSF ₅ groups. In another preferred variant of the invention R ³ and / or R ^{4 are the} same as OSF ₅ groups and are bound to the carboxyl groups via branched alkyl chains which contain no further OSF ₅ groups.

L ¹ , L ² and L ³ are preferably, independently of one another, linear or branched alkyl having 1 to 20 C atoms, preferably 1 to 10 C atoms. In particular, L ¹ , L ² and L ³ are each independently linear alkyl having 3 to 10 carbon atoms, more preferably having 3 to 8 carbon atoms. In a preferred variant of the invention, L ¹ and L ^{2 are the} same. If L ^{3 is also} present, preferably L ¹ and L ² or L ¹ and L ³ or L ² and L ^{3 may be the} same. Particularly preferred compounds are those in which L ¹ = L ² = L ³ .

Preferred compounds are in particular those compounds in which all variables have the preferred meanings.

The compounds according to the invention are preferably based on esters of succinic acid and tricarballylic acid, the compounds containing at least one OSF ₅ group.

In a preferred group of compounds of the formula I, R ¹ and R ^{2 are} hydrogen and R ³ and R ^{4 are} an OSF ₅ group. These compounds are represented by formula (Ia):

In another preferred group of compounds of formula I R ^{1 is} H, R ^{2 is} -CHY-COO-L ³ -OCF ₃ and R ³ and R ^{4 are} an OSF ₅ group. These compounds are represented by formula (Ib):

In a further preferred group of compounds of the formula I, R ^{1 is} -CHY-COO-L ³ -OCF ₃ , R _{2 is} hydrogen and R ³ and R ^{4 are} an OSF ₅ group. These compounds are represented by formula (Ic):

Preferably, the anionic or anionic salinizable compounds of formula (I) comprise as counterion an alkali metal ion, preferably Li ⁺ , Na ⁺ or K ⁺ , an alkaline earth metal ion or NR ₄ ⁺ , where R = H ⁺ or C 1 -C 6 -alkyl and all R may be the same or different, preferably NH ₄ ⁺ or triethylammonium.

wobei M für H oder ein Alkalimetall-Ion steht, vorzugsweise Li⁺, Na⁺ oder K⁺, oder NH₄ ⁺, insbesondere Na⁺, s steht für eine ganze Zahl aus dem Bereich von 1 bis 1000, t steht für eine ganze Zahl ausgewählt aus 1, 2, 3 oder 4 und w steht für eine ganze Zahl ausgewählt aus 1, 2 oder 3.In a preferred group of compounds or compounds of the invention to be used, X, Y independently of one another are an anionic polar group selected from -COOM, -SO ₃ M, -OSO ₃ M, -PO ₃ M ₂ , -OPO ₃ M ₂ , - (OCH ₂ CH ₂ ) _s -O- (CH ₂ ) _t -COOM, - (OCH ₂ CH ₂ ) _s O- (CH ₂ ) _t -SO ₃ M, - (OCH ₂ CH ₂ ) _s -O- (CH ₂ ) _t -OSO ₃ M, - (OCH ₂ CH ₂ ) _s -O- (CH ₂ ) _t -PO ₃ M ₂ , - (OCH ₂ CH ₂ ) O- (CH ₂ ) _t -OPO ₃ M ₂ or for the formulas A to C,

where M is H or an alkali metal ion, preferably Li ⁺ , Na ⁺ or K ⁺ , or NH ₄ ⁺ , in particular Na ⁺ , s is an integer from the range of 1 to 1000, t is an integer is selected from 1, 2, 3 or 4 and w is an integer selected from 1, 2 or 3.

The preferred anionic groups include in particular -COOM, -SO ₃ M, -OSO ₃ M, -PO ₃ M ₂ , -OPO ₃ M ₂ , the partial formula A, and - (OCH ₂ CH ₂ ) ₅ -O- ( CH ₂ ) _t -COOM, - (OCH ₂ CH ₂ ) _s -O- (CH ₂ ) _t -SO ₃ M and - (OCH ₂ CH ₂ ) _s -O- (CH ₂ ) _t -OSO ₃ M, where each one of these groups can be preferred on its own.

The most preferred anionic groups include -SO ₃ M, -OSO ₃ M, -PO ₃ M ₂ , or OPO ₃ M ₂ .

A preferred variant of the invention are sulfosuccinates which contain one or two pentafluorosulfoxyalkyl groups and sulfotricarballylates which contain one, two or three pentafluorosulfoxyalkyl groups. In the present invention, sulfosuccinates or sulfotricarballylates are esters, preferably diesters or triesters, of maleic acid or aconitic acid, to the double bond of which a sulfonate group has been added. In particular, sulfosuccinates having two and sulfotricarballylates having three pentafluorosulfoxy groups are preferred.

M und L¹, L² und L³ haben die für die Formel (I) genannten allgemeinen und bevorzugten Bedeutungen. Bevorzugt sind L¹, L² und L³ unabhängig voneinander lineares Alkyl mit 2 bis 10 C-Atomen, insbesondere mit 2 bis 6 C-Atomen, und M ist ein einwertiges Kation. Insbesondere sind Verbindungen der Formeln (II), (III) und (IV) bevorzugt, in denen alle L gleich sind.Particularly preferred compounds according to the invention are compounds of the formulas (II), (III) and (IV):

M and L ¹ , L ² and L ³ have the general and preferred meanings given for the formula (I). L ¹ , L ² and L ³ are preferably, independently of one another, linear alkyl having 2 to 10 C atoms, in particular having 2 to 6 C atoms, and M is a monovalent cation. In particular, compounds of formulas (II), (III) and (IV) are preferred in which all L are the same.

Preferably, M = H ⁺ , an alkali metal cation or NR ₄ ⁺ , where R = H ⁺ or C 1 -C ₆ -alkyl and all Rs may be the same or different. Particularly preferred is X = Na ⁺ , K ⁺ or NH ₄ ⁺ , more preferably Na ⁺ .

Preferably, L ¹ , L ² and L ³ are each independently linear C ² -C 10 -alkyl, in particular linear C ² -C 6 -alkyl. More preferably, L ¹ and L ² are each independently linear C ² -C 6 -alkyl for compounds of formula (II). For compounds of the formula (III) and (IV), L ¹ , L ² and L ^{3 are} preferably, independently of one another, equal to linear C ² -C 6 -alkyl. Particular preference is given to compounds in which L ¹ , L ² and L ³ contain no further OSF ₅ groups.

In another variant of the invention, L ¹ , L ² and L ^{3 may} independently be branched alkyl groups and / or contain further OSF ₅ groups.

Particularly preferred are compounds in which both X, Y and L ¹ , L ² and L ^{3 have} the preferred meanings.

Examples of particularly preferred compounds according to the invention are:

The compounds of the invention according to the formulas (I) to (IV) can also be present as isomer mixtures (constitution and / or configuration isomer mixtures). In particular, diastereomeric and / or enantiomeric mixtures are possible.

• – eine Oberflächenaktivität, die der konventioneller Kohlenwasserstoff-Tenside hinsichtlich Effizienz und/oder Effektivität gleich oder überlegen ist,
• – biologische und/oder abiotische Abbaubarkeit der Substanzen ohne Bildung persistenter perfluorierter Abbauprodukte wie PFOA (Perfluoroctansäure) oder PFOS (Perfluoroctansulfonat),
• – schwache Schaumbildung,
• – gute Verarbeitbarkeit in Formulierungen und/oder
• – Lagerstabilität.

Advantages of the compounds according to the invention can be in particular:

• A surface activity equal or superior to conventional hydrocarbon surfactants in terms of efficiency and / or effectiveness,
• - biological and / or abiotic degradability of the substances without formation of persistent perfluorinated degradation products such as PFOA (perfluorooctanoic acid) or PFOS (perfluorooctanesulfonate),
• - weak foaming,
• Good processability in formulations and / or
• - storage stability.

The compounds according to the invention preferably have a particular surface activity.

A second object of the present invention is the use of compounds of the formulas (I), (II), (III) and / or (IV) as surface-active agents, for example for improving the flow behavior and the wetting power of coating formulations.

Preference is given to using compounds of the formulas (I), (II), (III) and / or (IV). In this case, the preferred embodiments of the compounds according to the invention described above can be used particularly advantageously. Sulfosuccinates which contain one or two, in particular two, pentafluorosulfoxyalkyl groups, and sulfotricarballylates which contain one, two or three, in particular three, pentafluorosulfoxyalkyl groups, are preferably used. The compounds of the invention according to the formulas (I) to (IV) can also be used as isomer mixtures (constitution and / or configuration isomer mixtures). In particular, diastereomeric and / or enantiomeric mixtures are possible.

Areas of use are, for example, the use of the compounds according to the invention as additives in surface coating preparations, such as paints, lacquers, protective coatings, special coatings in electronic or semiconductor applications (for example, photoresists, top anti-reflective coatings, bottom anti-reflective coatings) or in optical applications (eg B. photographic coatings, coatings of optical elements) or in additive formulations for the addition of appropriate preparations.

The compounds according to the invention for the application are usually incorporated in 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 respective intended use, as well as optionally further active ingredients and / or optionally adjuvants. Preferred agents are color and lacquer preparations and printing inks.

• – Polykondensationsharze wie Alkydharze, gesättigt/ungesättigte Polyester,
• – Polyamide/imide, Silikonharze; Phenolharze; Harnstoffharze und Melaminharze,
• – Polyadditionsharze wie Polyurethane und Epoxidharze,
• – Polymerisationsharze wie Polyolefine, Polyvinylverbindungen und Polyacrylate.

In addition, water-based coating formulations containing at least one of the compounds according to the invention alone or in a mixture with other surfactants are also the subject of the present invention. Coating formulations based on the following synthetic film formers are preferably used:

• Polycondensation resins such as alkyd resins, saturated / unsaturated polyesters,
• - polyamides / imides, silicone resins; Phenol resins; Urea resins and melamine resins,
• Polyaddition resins such as polyurethanes and epoxy resins,
• - Polymerization resins such as polyolefins, polyvinyl compounds and polyacrylates.

In addition, the compounds of the invention are also suitable for use in paints based on natural substances and modified natural products. Preference is given to lacquers based on oils, polysaccharides such as starch and cellulose and also based on natural resins such as cyclic oligoterpenes, polyterpenes and / or shellac. The compounds according to the invention can be used both in physically curing (thermoplastics) and in crosslinking (elastomers and duromers) aqueous coating systems. The compounds according to the invention preferably improve the flow and wetting properties of the coating systems.

Another area of use of the compounds according to the invention lies in production processes of polymers, in particular of fluoropolymers. Important technical methods for the preparation of fluoropolymers such. B. polytetrafluoroethylene (PTFE) are z. B. emulsion and suspension polymerization. Suspension and emulsion polymerization processes are common polymerization processes well known to those skilled in the art. In the case of suspension and emulsion polymerization processes, the system always contains at least four constituents: (predominantly) water-insoluble monomer, water, dispersant or emulsifier and initiator. The execution of the stated polymerization processes is familiar to the person skilled in the art. In this process, the polymer is prepared in an autoclave containing water or the corresponding, usually gaseous, monomers, initiators, surfactants and other auxiliaries, with stirring and constant temperature and pressure control. The compounds according to the invention are suitable as surfactants to keep the very hydrophobic fluoropolymer droplets or particles dispersed in the aqueous solution.

In addition, the compounds of the present invention may be useful in water repellents, oleophobicizing agents, wetting / flow control agents, stain and soil protectants, stain releases, antifoggants, lubricants, defoamers, deaerators, drying accelerators, abrasion resistance and mechanical durability improvers, and antistatics, especially in the art Treatment of textiles (in particular clothing, carpets and rugs, upholstery coverings in furniture and automobiles) and hard surfaces (in particular kitchen surfaces, sanitary facilities, tiles, glass), non-woven textile materials, leather goods, paper and cardboard, wood and wood-based materials, mineral Substrates such as stone, cement, concrete, gypsum, ceramics (glazed and unglazed bricks, earthenware, porcelain) and glasses, as well as for plastics and metallic substrates are used. For metallic substrates, the use in anticorrosion agents is additionally the subject matter of the claims. For plastics and molds for plastics processing, the use in mold release agents is additionally subject matter of the claims. In the case of detergents and stain removers, the use as detergents or soil emulsifying and dispersing agents is additionally the subject matter of the claims.

Furthermore, the compounds of the invention can be used as antimicrobial agent, in particular as a reagent for the antimicrobial surface modification.

Another area of use of the compounds according to the invention is additives or additive formulations in printing inks, having one or more of the following functions: defoamer, deaerator, friction control agent, wetting agent, leveling agent, pigment compatibility improver, printing resolution improver, drying accelerator.

The compounds according to the invention can also be used as foam stabilizers and / or to support film formation, in particular in aqueous film-forming fire-extinguishing foams, both synthetic and protein-based, also for alcohol-resistant formulations (AFFF and AFFF-AR, FP, FFFP and FFFP-AR).

Furthermore, the compounds according to the invention can be used as additives in polymeric materials (plastics) with one or more of the following functions: lubricants, internal friction reducers, UV stabilizers, water repellents, oil repellents, stain and soil protectants, fillers, flame retardants , Migration inhibitor (especially against migration of plasticizers), anti-fogging agents.

In addition, the compounds according to the invention are also suitable for use as additives in liquid media for cleaning, etching, reactive modification and / or substance deposition on metal surfaces (in particular electroplating and anodization) or semiconductor surfaces (in particular for semiconductor photolithography: developer, stripper, edge Bead Remover, etching and cleaning agents), suitable as a wetting agent and / or improvers of the quality of deposited films.

In addition, the compounds useful according to the invention as surfactant for washing and cleaning applications, as well as for use as additives / surfactants in cosmetic products such. Hair and body care products (e.g., shampoos, hair conditioners and hair conditioners), foam baths, creams or lotions having one or more of the following functions: emulsifiers, wetting agents, foaming agents, lubricants, antistatic agents, enhancers of skin fat resistance.

The compounds of the invention further comprise the use as additives in herbicides, pesticides and fungicides having one or more of the following functions: substrate wetting agent, adjuvant, foam inhibitor, dispersing agent, emulsion stabilizer.

In addition, the compounds according to the invention can also be used as additives in deicing or anti-icing agents.

In addition, the compounds of the invention are useful as additives in ore processing formulations, particularly flotation and leaching solutions, having one or more of the following functions: wetting agents, foaming agents, foam inhibitors, and as additives in petroleum source stimulation agents, with one or more of the following Functions: Wetting agent, foaming agent, emulsifier.

Another area of use of the compounds according to the invention is the use as additives in adhesives, with one or more of the following functions: wetting agent, penetrating agent, substrate adhesion promoter, defoamer.

Furthermore, the compounds according to the invention can be used as additives in lubricants and hydraulic fluids, with one or more of the following functions: wetting agent, corrosion inhibitor. In the case of lubricants, the use as a dispersant (in particular for fluoropolymer particles) is additionally the subject of the claims.

Also, the compounds of the invention may be used as additives in putties and fillers, with one or more of the following functions: water repellents, oil repellents, soil protectants, weatherability improvers, UV stabilizers, silicone bleed-off agents.

All uses of compounds according to the invention to be used according to the invention are the subject of the present invention. The particular use of surfactants for the stated purposes is known to the person skilled in the art, so that the use of the compounds to be used according to the invention causes no problems. The compounds of the formula (I) are preferably used in color and lacquer preparations and in the production processes of polymers, in particular of fluoropolymers.

In a further aspect, the object of the invention was surprisingly achieved by providing the use of compounds of the invention as surfactants, as hydrophobing or Oleophobiermittel, in particular in the surface modification of textiles, paper, glass, porous building materials or adsorbents, as an antistatic agent, in particular in the treatment of Textiles such as clothing, carpets and rugs, upholstery coverings in furniture and automobiles, non-woven textile materials, leather goods, papers and cartons, wood and wood-based materials, mineral substrates such as stone, cement, concrete, plaster, ceramics, such as glazed and unglazed bricks , Stoneware, porcelain, and glasses, as well as for plastics and metallic substrates, as additives in surface coating formulations, such as printing inks, paints, paints, coatings, photographic coatings, special coatings for semiconductor photolithography, such as photoresists, top antirefle ctive coatings, bottom antireflective coatings, or in additive formulations for the addition of appropriate preparations, as a foam stabilizer and / or to aid film formation, in particular in fire-extinguishing foams, as an interface mediator or emulsifier, in particular for the production of fluoropolymers, or as an antimicrobial agent, in particular as a reagent for the antimicrobial surface modification.

bevorzugt in Gegenwart eines Katalysators, und anschließende Addition an die Doppelbindung der Aconit-Ester, bevorzugt von Natriumhydrogensulfit, oder durch Funktionalisierung der OH-Gruppe der Zitronensäure-Ester hergestellt werden, wobei L die für L¹, L² und L³ in Formel (I) beschriebene Bedeutung hat, und die Alkohole der Formel (V) eine oder mehrere OSF₅-Gruppen enthalten.The compounds according to the invention can preferably be prepared by esterification of aconitic acid or the anhydride or acid chloride or of citric acid with one or more alcohols of the formula (V)

preferably in the presence of a catalyst, and subsequent addition to the double bond of the aconitic esters, preferably of sodium bisulfite, or by functionalization of the OH group of the citric acid esters, where L is the same as for L ¹ , L ² and L ³ in formula ( I), and the alcohols of the formula (V) contain one or more OSF ₅ groups.

A third object of the present invention is thus a process for the preparation of compounds of formula (I), in particular sulfosuccinates containing one or two pentafluorosulfoxyalkyl groups, and sulfotricarballylates containing one, two or three pentafluorosulfoxyalkyl groups.

The synthesis of the alcohols of the formula (V) is known from the literature and in the WO 2006/072401 described.

The synthesis of the succinates is preferably carried out in the presence of a conventional catalyst, such as. B. Toluene-4-sulfonic acid monohydrate:

In a second step, the introduction of the group X is then carried out by addition to the double bond. The following scheme shows, by way of example, the synthesis of the sulfosuccinates by the addition of sodium hydrogen sulfite, which can be carried out under conditions known to the person skilled in the art:

The synthesis of the Aconitester preferably takes place in the presence of a conventional catalyst, such as. B. Toluene-4-sulfonic acid monohydrate:

The preparation of the corresponding citric acid ester is preferably carried out in the presence of a conventional catalyst, such as. B. Toluene-4-sulfonic acid monohydrate:

In a second step, the introduction of the group X is then carried out by addition to the double bond of the aconite ester or derivatization of the OH group of the citric acid esters according to methods familiar to the person skilled in the art. The following scheme shows, by way of example, the synthesis of the sulfotricarballylates by the addition of sodium hydrogen sulfite, which can be carried out under conditions known to the person skilled in the art:

The formula (VIII) represents the presence of Z / E double bond isomers. The preparation of further compounds according to the invention can be carried out analogously to the exemplary reactions shown above. The preparation of further compounds according to the invention can also be carried out by other methods known per se from the literature to the person skilled in the art. In particular, other esterification catalysts can be used.

wobei L und Y die im Vorangegangenen beschriebene Bedeutung und bevorzugten Ausgestaltungen haben.A fourth subject of the present invention are compounds of the formulas (VI) and (VIII) which occur as intermediates in the above-described syntheses of the compounds of the formula (I) according to the invention, in particular the sulfosuccinates and sulfotricarballylates:

wherein L and Y have the meaning and preferred embodiments described above.

A fifth object of the present invention is the use of the compounds of formulas (VI) and (VIII) as monomers or co-monomers in the synthesis of fluorinated polymers by the methods described above.

In addition to 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.

The disclosures in the cited references are hereby also expressly incorporated into the disclosure of the present application.

The following examples further illustrate the present invention without limiting the scope of protection. In particular, the features, properties and advantages of the compounds and reaction conditions underlying the examples in question are also applicable to other substances and compounds not mentioned in detail but covered by the scope of protection, unless otherwise stated elsewhere. Incidentally, the invention is embodied in the entire claimed area and is not limited to the examples mentioned here.

Examples

Example 1: Synthesis of the sulfotricarballylate of the formula (K)

a) esterification

A mixture of 72.4 mmol of alcohol, 18.1 mmol aconitic acid (90%, Alfa Aesar) and 3.6 mmol of toluene-4-sulfonic acid monohydrate (Merck KGaA) in 50 ml of toluene is stirred for 48 hours under reflux. The water released during the reaction is removed by means of a water separator. It is quenched with water. It is then extracted with toluene and the combined organic phases are washed with water, dried over sodium sulfate and filtered. The solvent is distilled off on a rotary evaporator.
Purification: column chromatography on silica gel;
Eluent: toluene / ethyl acetate
Substance: C ₃₆ H ₆₃ F ₁₅ O ₉ S ₃ ; M = 1021.07 g / mol

b) Addition

To a solution of 13.5 mmol of triester in 50 ml of 1,4-dioxane (Merck KGaA) is added dropwise at 50 ° C 340 mmol sodium bisulfite solution (39% in water, Merck KGaA) and allowed to stir at reflux. After the dropping, the reaction temperature is maintained at 88 ° C for 65 hours. After 24 hours and 48 hours, another 115 mmol of sodium bisulfite solution (39% strength in water, Merck KGaA) are added dropwise. The solvent is removed on a rotary evaporator. The crude product is then taken up in diethyl ether (Merck KGaA), stirred and filtered. The diethyl ether phases are combined and the organic solvent is removed on a rotary evaporator.
Substance: C ₃₆ H ₆₄ F ₁₅ O ₁₂ S ₄ Na; M = 1125.13 g / mol

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 4968599 [0004]
• US 4988610 [0004]
• US 6890608 [0004]
• WO 03/010128 [0005]
• JP 2001/133984 A [0006]
• JP 09/111286 A [0006]
• DE 102005000858 [0007]
• WO 2006/072401 [0056]

Cited non-patent literature

• GL Kennedy, Jr., JL Butenhoff, GW Olsen, JC O'Connor, AM Seacat, RG Biegel, SR Murphy, DG Farrar, Critical Review in Toxicology, 2004, 34, 351-384 [0003]
• AR Pitt et al., Calloids and Surfaces A: Physicochemical and Engineering Aspects, 1996, 114, 321-335 [0004]
• AR Pitt, Progr. Colloid Polym. Sci, 1997, 103, 307-317 [0004]
• Z.-T. Liu et al., Ind. Eng. Chem. Res. 2007, 46, 22-28 [0004]

Claims (15)

Compounds of the formula (I)

wherein: R ¹ , R ² = independently of one another are hydrogen, hydroxy or -CHY-COO-L ³ -OSF ₅ , R ³ , R ⁴ = independently of one another are hydrogen or OSF ₅ , L ¹ , L ² , L ³ = independently each of which is linear or branched alkyl, wherein one or more nonadjacent C atoms may be replaced by O, S, and / or N, and / or one or more double and / or triple bonds and / or one or more OSF ₅ - X, Y = independently of one another are an anionic polar group or hydrogen, and the compounds contain at least one OSF ₅ group. Compounds according to claim 1, characterized in that in X, Y independently of one another the anionic polar group -SO ₃ M, -OSO ₃ M, -PO ₃ M ₂ , or -OPO ₃ M ₂ , where M is an alkali metal ion, is an alkaline earth metal ion or NR ₄ ⁺ , with R = H or C 1 -C ₆ alkyl, and all Rs may be the same or different. Compounds according to one or more of claims 1 to 2, characterized in that the compounds contain two or three OSF ₅ groups. Compounds according to one or more of claims 1 to 3, characterized in that L ¹ = L ² = L ³ and are linear or branched alkyl having 1 to 20 carbon atoms. Compounds according to one or more of claims 1 to 4, characterized in that R ¹ and R ^{2 are} hydrogen or hydroxy and R ³ and R ^{4 are} an OSF ₅ group. Compounds according to one or more of claims 1 to 4, characterized in that R ^{1 is} H, R ^{2 is} -CHY-COO-L ³ -OSF ₅ and R ³ and R ^{4 is} an OSF ₅ group. Compounds according to one or more of claims 1 to 4, characterized in that R ^{1 is} -CHY-COO-L ³ -OSF ₅ , R _{2 is} hydrogen and R ³ and R ^{4 is} an OSF ₅ group. Compounds according to one or more of claims 1 to 7, characterized in that L ¹ and L ² are each independently equal to linear C ² -C 10 -alkyl. Compounds according to one or more of claims 1 to 8, characterized in that L ¹ , L ² and L ^{3 are} independently linear C2-C6-alkyl. Compounds according to one or more of claims 1 to 9, characterized in that L ¹ , L ² and L ³ contain no further OSF ₅ groups. Compounds according to one or more of claims 1 to 10, characterized in that they satisfy the formulas (II), (III) or (IV)

wherein: M = H or an alkali metal ion, preferably Li ⁺ , Na ⁺ or K ⁺ , or NH ₄ ⁺ and L ¹ , L ² , L ³ = are independently linear or branched alkyl, with one or more non-adjacent C atoms may be replaced by O, S, and / or N, and / or one or more double and / or triple bonds and / or one or more OSF ₅ groups may be contained in the chain and / or the side chain, is. Compounds according to one or more of claims 1 to 11 selected from the group consisting of:

Use of compounds according to one or more of claims 1 to 12 as surfactants, as water repellents or Oleophobiermittel, in particular in the surface modification of textiles, paper, glass, porous building materials or adsorbents, as an antistatic agent, in particular in the treatment of textiles, such as clothing, carpets and carpets, upholstery coverings in furniture and automobiles, non-woven textile materials, leather goods, paper and cardboard, wood and wood-based materials, mineral substrates such as stone, cement, concrete, plaster, ceramics, such as glazed and unglazed bricks, earthenware, porcelain, and Glasses, as well as for plastics and metallic substrates, as additives in surface coating formulations, such as printing inks, paints, paints, varnishes, photographic coatings, special coatings for semiconductor photolithography, such as photoresists, top anti-reflective coatings, bottom anti-reflective coatings, or in additive preparation for the addition of appropriate preparations, as a foam stabilizer and / or to support film formation, in particular in fire-extinguishing foams, as an interface mediator or emulsifier, in particular for the production of fluoropolymers, or as an antimicrobial agent, in particular as a reagent for antimicrobial surface modification. Process for the preparation of compounds according to one or more of Claims 1 to 12 comprising a) the esterification of maleic acid and aconitic acid or their anhydrides or acid chlorides with one or more alcohols of the formula (V)

preferably in the presence of a catalyst, and subsequent addition to the double bond of the aconitic esters, preferably of sodium bisulfite, or by functionalization of the OH group of the citric acid esters, where L is the same as for L ¹ , L ² and L ³ in formula ( I), and the alcohols of the formula (V) contain one or more OSF ₅ groups. Compounds of the formulas (VI) and (VIII)

where L has the meaning described for L ¹ , L ² and L ³ in formula (I) and Y has the meaning described in formula (I).