Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/47—Levelling agents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C59/235—Saturated compounds containing more than one carboxyl group
  • C07C59/305—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups
  • C07C59/315—Saturated compounds containing more than one carboxyl group containing ether groups, groups, groups, or groups containing halogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/45—Anti-settling agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/004—Surface-active compounds containing F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

• the present invention relates to novel compounds having fluorinated end groups, their use as surface-active
• Fluorosurfactants have a superior ability to reduce the
• Surface tension for example, in the hydrophobization of surfaces e.g. of textiles, paper, glass, building materials or adsorbents 0 is used.
• fluorosurfactants contain perfluoroalkyl substituents that in the 5 environment due to biological and / or other oxidation processes too
• 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 to some extent suspected of causing health damage (GL Kennedy, Jr., JL Butenhoff, GW Olsen, JC O 'Connor, AM
• JP-A-2001/133984 discloses surface-active compounds with perfluoroalkoxy
• Wear Trifiuormethoxy group and have a polar end group, surface active and are suitable as surfactants described.
• novel surface-active compounds can be used as individual components or, if advantageous, also in mixtures.
• a first subject of the present invention are compounds of the formula (I)
• R 1 and R 2 independently hydrogen or
• Y 1 , Y 2 and Y 3 independently of one another are O, S or N,
• L, L 2 and L 3 independently of one another are linear or branched alkylene, where one or more nonadjacent C atoms may be replaced by O, S, and / or N,
• a 1 , A 2 and A 3 independently of one another are hydrogen or a group of the structure -Z i (CR 3 R 4 ) mi Rf i ,
• R 3 and R 4 are independently hydrogen or an alkyl group
• Rf is a fluorine-containing radical
• n1, n2 and n3 are independently 1-6,
• Preferred compounds of formula (I) are those in which R 1 and R 2 are not simultaneously -CH 2 -COY 3 -L 3 - (A 3 ) n 3.
• the compounds of the invention may contain one or more Rf groups.
• a 1 , A 2 and A 3 are, independently of each other, preferably a group of the structure -Z '(CR 3 R 4 ) m iRf i .
• n1, n2 and n3 are not the same as 1.
• Particularly preferred are n1, n2 and n3 independently of each other 2-3.
• compounds having at least four Rf groups are preferred.
• a preferred variant are
• fluorine-containing alkyl groups or CF 3 0 groups are used.
• fluorinated groups Rf it is preferred to use branched or unbranched fluorine-containing alkyl radicals, in particular perfluorinated alkyl radicals. Also preferred are fluorine-containing alkyl radicals having 1 to 10, preferably 1 to 6, in particular 1 to 4 carbon atoms. Preference is given to using perfluorinated Rf groups having 1 to 6, in particular 1 to 4, carbon atoms. Preferably, Rf 1 , Rf 2 and Rf 3 have the same meaning. In another variant of the invention, preference may be given to using CF.sub.BO groups, in particular when Y is S or N.
• the invention essential groups Rf are about a group
• Z 'here is preferably O or N, in particular O.
• R 3 and R 4 independently of one another preferably represent hydrogen or an unbranched C 1 -C 3 -alkyl group.
• m1, m2 and m3 are preferably independently of one another 1-3.
• L 1 , L 2 and L 3 may preferably be independently of one another linear or branched alkylene having 1 to 10 carbon atoms.
• L 1 , L 2 and L 3 are independently linear or branched alkylene having 3 to 8 carbon atoms.
• One or more nonadjacent C atoms of the groups L 1 , L 2 and L 3 may preferably be replaced by O or N, preferably by O.
• L 1 and L 2 are identical. 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. In a particularly preferred variant of the invention, all groups L 1 , L 2 and L 3 are the same.
• the compounds of the invention may be present as mixtures in which the individual
• Y 1 and Y 3 are preferably O or N, Y are particularly preferably O. 1, Y 2 and Y 3 are the same
• X is a hydrophilic group, preferably an anionic, cationic, nonionic or amphoteric group.
• a preferred anionic group X may be selected from -COO " , -SO 3 " , -OSO 3 , -PO 3 2 -, -OPO 3 2 -, - (OCH 2 CH 2 ) s -O- (CH 2) r COO-,
• s stands for an integer in the range from 1 to 1000
• t stands for an integer selected from 1, 2, 3 or 4
• w stands for an integer selected from 1, 2 or 3.
• Preferred anionic groups include, in particular case - COO "-S0 3 ', -OS0 3", -PO3 2 ", -OPO 3 2", the partial formula A, and - (OCH 2 CH 2) s - 0- ( CH2) t-COO-, - (OCH 2 CH 2) s-0- (CH2) t-S03 ", and - (OCH 2 CH 2) s -0- (CH 2) t-OS0 3", wherein each one of these groups can be preferred on its own.
• the most preferred anionic groups include -SO 3 " , -OSO 3 " , -PO 3 2 ' , or OPO 3 2 " , especially -SO 3 " .
• a sulfonate group -SO 3 " is preferred.
• Preferred counterion for anionic groups X is a monovalent cation, in particular H + , an alkali metal cation or NR 4 + , where R is H + or C 1 -C 6 -alkyl and all Rs may be the same or different.
• Na + , K + and NH 4 + are particularly preferred.
• a preferred cationic group X can be selected from -NR 1 R 2 R 3 + Z " , -PR R 2 R 3 + Z "
• R is H or Ci. 4- alkyl in any position, Z "is CI”, Br, I, "CH 3 SO 3", CF 3 S0 3 ", CH 3 PhSO 3 -, PhSO-f
• R 1, R 2 and R 3 are each independently alkyl -30 H, Ci,
• Ar is an unsubstituted or mono- or polysubstituted
• substituted aromatic ring or fused ring systems having 6 to 18 carbon atoms, wherein also one or two CH groups may be replaced by N.
• the preferred cationic groups include in particular -NR 1 R 2 R 3 + Z and
• each of these groups may be preferred per se.
• n is an integer from the range of 1 to 6, preferably 1 to 4
• o is an integer in the range of 1 to 10,
• p 1 or 2
• R 1 , R 2 and R 3 are each independently of one another Ci-3o-alkyl, Ar or -CH 2 Ar, preferably C 1-2 o-alkyl,
• R 4 is C 1-4 -alkyl-OH
• R is H or methyl
• X alkyl
• R- (BA) m - with R H or Ci-4-alkyl, in particular H or CH 3
• A linear or branched alkylene, preferably with 1 to 10 carbon atoms, in particular with 1 to 4
• Particularly preferred as a nonionic group X is the group
• a preferred amphoteric group can be selected from the functional groups of the acetyldiamines, the N-alkylamino acids, the betaines, the amine oxides or corresponding derivatives, in particular selected from:
• Alkyl radical preferably methyl or ethyl
• Particularly preferred compounds according to the invention are those which contain an anionic group X. Particularly preferred
• the group R preferably represents linear or branched alkylene, preferably with 1 to 12 carbon atoms, in particular with 1 to 4
• Carbon atoms Preferably, one or more non-adjacent C atoms may be replaced by O or S, preferably O.
• r may preferably be 0.
• B is a single bond, O, NH, NR ', CH 2 , C (O) -O, S, CH 2 -O, OC (O), O-C (O) -O, NC ( O), C (O) -N, O-C (O) -N, NC (O) -N, SiR ' 2 -, SiR' 2 -0, 0-S0 2 or S0 2 -0, where R ' is linear or branched alkyl.
• B is preferably a single bond, O, S, C (O) -O or OC (O), in particular a single bond.
• 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 the hydroxysuccinic acid and the citric acid, the compounds containing at least one R group.
• R 1 and R 2 are hydrogen and A 1 and A 2 are a -Z '(CR 3 R 4 ) mi Rf i group.
• These compounds are represented by formula (II).
• Particularly preferred compounds of the formula (II) with Y 1 , Y 2 , Z 1 and Z 2 are light O.
• R 1 is H
• R 2 2 -COY 3 -L 3 is -CH - (A 3) n3
• a 1 represents a -Z '(CR 3 R 4 ) miRf i group.
• These compounds are represented by formula (III). Particular preference is given to compounds of the formula (III) where Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 are O.
• R 1 is -CH 2 -COY 3 -L 3 - (A 3 ) n 3
• R 2 is hydrogen and A 1 , A 2 and A 3 is a -Z '( CR 3 R 4) mi i Rf group.
• formula (IV) Particular preference is given to compounds of the formula (IV) where Y 1 , Y 2 , Y 3 , Z 1 , Z 2 and Z 3 are O.
• a preferred variant of the invention are functionalized with X.
• 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 each independently of the same linear or branched C 1 -C 10 -alkylene, in particular linear or branched C 3 -C 8 -alkylene. More preferably, L 1 and L 2 are independently linear or branched C 5 -C 20 -alkylene for compounds of the formula (II).
• Examples of particularly preferred compounds according to the invention are compounds of the formulas (V) and (VI) in which the variables have the general and preferred meanings given for the formula (I) and yi and zi independently of one another are 1 to 10:
• Rf are fluorine-containing alkyl radicals having 1 to 6, in particular 1 to 4, C atoms. Preference is given to using perfluorinated Rf groups having 1 to 4 C atoms.
• yi and zi independently of one another may be equal to 1-10, preferably equal to 1-6, in particular 1-3.
• Advantages of the compounds according to the invention may be in particular: a surface activity that is equal or superior to the conventional hydrocarbon surfactants in terms of efficiency and / or effectiveness, biological and / or abiotic degradability of the substances without
• PFOS perfluorooctanesulfonic acid, 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 at least one compound of the formula (I) as surfactants, for example for improving the flow behavior and the wetting power of coating formulations.
• Succinates containing at least four, especially four, Rf groups, and tricarballylates containing at least six, especially six, Rf groups are preferably used.
• 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 (eg photoresists, top anti-reflective coatings, bottom anti-reflective coatings) or in optical applications (eg Coatings, coatings of optical elements) or in additive formulations for the addition of appropriate preparations.
• surface coating preparations such as paints, lacquers, protective coatings, special coatings in electronic or semiconductor applications (eg photoresists, top anti-reflective coatings, bottom anti-reflective coatings) or in optical applications (eg 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 dyestuff and lacquer preparations and printing inks.
• 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.
• polycondensation resins such as
• Alkyd resins saturated / unsaturated polyesters, polyamides / imides,
• Polyaddition resins such as polyurethanes and epoxy resins
• Polymerization resins such as polyolefins, polyvinyl compounds and
• 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. 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 purposes mentioned is known to the person skilled in the art, so that the use of the invention to be used
• a third object of the present invention is a process for the preparation of compounds of formula (I).
• the preparation of the compounds according to the invention can be carried out according to methods known to the skilled person from the literature.
• the compounds of the invention may preferably by
• L and A in the formula (VII) and in the following formulas (VIII) to (XI) have the meaning described for L 1 , L 2 and L 3 or A, A 2 and A 3 in formula (I), in particular also the preferred meanings.
• the Alcohols of the formula (VII) may contain two or more Rf groups, preferably two Rf groups.
• the alcohols used are commercially available and / or their
• the synthesis of succinates or tricarballylates according to the invention is preferably carried out in a two-stage synthesis via the corresponding maleates or hydroxysuccinates or the corresponding aconite or
• Citric acid esters which in the presence of a conventional catalyst, such as. B. toluene-4-sulfonic acid monohydrate are prepared:
• the introduction of the group X- (R) r B then takes place by addition to the double bond or derivatization of the OH group according to methods familiar to the person skilled in the art.
• the formula (X) 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.
• PEG polyethylene glycol
• a mixture of 1, 3-dichloro-2-propanol, 3 eq 1H, 1 H-pentafluoropropanol and 3 eq potassium hydroxide is heated to 100 ° C for 24 h. It is then cooled to room temperature and treated with demineralized water and MTB ether and the phases were separated. The aqueous phase is extracted with MTB ether and the combined organic phases are washed with water, dried over sodium sulfate and filtered. The solvent is dissolved on
• Measurement method used Measurement of surface tension using the Wilhelmy plate method.
• the surface area or interfacial tension of the surfactant solution is calculated from the force acting on the wetted length of a plate according to the following formula.
• ⁇ limit or surface tension
• F force acting on the balance
• L wetted length (19.9 mm)
• ⁇ contact angle
• the plate consists of roughened platinum and is therefore optimally wetted, so that the contact angle ⁇ is close to 0 °.
• the term cos ⁇ therefore reaches approximately the value 1, so that only the measured force and the length of the plate must be taken into account.
• Example 4 Determination of the dynamic surface tension The dynamic surface tension ⁇ becomes a 0.1%
• Pmax maximum pressure
• p density of the fluid
• h immersion depth
• r radius of the capillary

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• Engineering & Computer Science (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Paints Or Removers (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2011
  • 2011-11-26 JP JP2013545078A patent/JP2014510021A/ja active Pending
  • 2011-11-26 US US13/995,233 patent/US20130269568A1/en not_active Abandoned
  • 2011-11-26 CN CN2011800620189A patent/CN103270021A/zh active Pending
  • 2011-11-26 EP EP11788382.7A patent/EP2655324A1/de not_active Withdrawn
  • 2011-11-26 WO PCT/EP2011/005952 patent/WO2012084118A1/de active Application Filing

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