WO2016162215A1 - Dispersions polymères contenant de la n-acylpyrrolidine - Google Patents

Dispersions polymères contenant de la n-acylpyrrolidine Download PDF

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WO2016162215A1
WO2016162215A1 PCT/EP2016/056417 EP2016056417W WO2016162215A1 WO 2016162215 A1 WO2016162215 A1 WO 2016162215A1 EP 2016056417 W EP2016056417 W EP 2016056417W WO 2016162215 A1 WO2016162215 A1 WO 2016162215A1
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polyurethane
general formula
diols
groups
aqueous polymer
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PCT/EP2016/056417
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German (de)
English (en)
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Karl Haeberle
Juan Marina SALGADO
Ulrich Karl
Thomas Reissner
Ulrich Abel
Nicolas Marion
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to aqueous polymer dispersions containing at least one N-acylpyrrolidine according to the following general formula (I).
  • the present invention furthermore relates to a process for preparing aqueous polymer dispersions, in particular polyurethane dispersions, using at least one N-acylpyrrolidine as solvent.
  • the present invention further relates to the use of N-acylpyrrolidines as solvents for the preparation of aqueous polymer dispersions and to the use of such aqueous polymer dispersions for coating, impregnating or bonding, for example, wood or leather.
  • the present invention relates to coating compositions, adhesives or impregnating compositions comprising such an aqueous polymer dispersion according to the invention.
  • Polymer dispersions are used in many fields of technology. Widely used, for example, for coating surfaces. Polyurethane dispersions are frequently produced industrially by the so-called "prepolymer mixing process". In it polyurethanes are first prepared in an organic solvent, often N-methylpyrrolidone, and then dispersed the resulting solution of the polyurethane in water. During and / or after their dispersion in water, the molecular weight of the polyurethane can then be further increased by means of a chain extension.
  • the solvent also remains in a distillative separation to more or less large proportions in the dispersion and influences the properties of the polyurethane dispersion.
  • WO 2005/090430 A1 teaches the use of N- (cyclo) alkylpyrrolidones with (cyclo) alkyl radicals having 2 to 6 C atoms for this purpose.
  • WO 10/142617 describes ring-substituted N- (cyclo) alkylpyrrolidones as suitable solvents.
  • the object of the present invention was to provide novel polymer dispersions, in particular polyurethane dispersions, which are toxicologically harmless and show advantageous performance properties.
  • This object according to the invention is achieved by aqueous polymer dispersions which contain at least one N-acylpyrrolidine according to the general formula (I)
  • R 1 to R 9 are independently H (hydrogen) or C-
  • Aqueous polymer dispersions according to the invention in particular polyurethane dispersions or polyurethane dispersions, which have been prepared by the process according to the invention have at least one of the following advantages over polymer dispersions or polyurethane dispersions known from the prior art:
  • the dispersions are easier to spray or atomise, since less incrustations or impurities are deposited on injection tools;
  • the prepolymer solutions have a lower viscosity
  • N-acylpyrrolidines to polymer dispersions, either before, during or after the preparation and / or dispersion of the polymer or polyurethane, improves the adhesion of the coating produced from such a polymer dispersion to the support material. This applies in particular to support materials which have a polymer surface, in particular a surface of polyurethane.
  • polymer dispersions according to the invention have a low viscosity.
  • - C 18 -alkyl, as defined above for the radical R 1 in formula (I), mean that this substituent (radical) is an alkyl radical having a carbon atom number of 1 to 18.
  • the alkyl radical can be linear or branched and optionally cyclic.Alkyl radicals which have both a cyclic and a linear component are likewise included in this definition and are assigned to the cyclic alkyl radicals in the context of the present invention
  • the term "linear alkyl” means that the corresponding alkyl radical is chain-shaped and has no branching (ie unbranched) and / or cyclic components. The same applies to other alkyl radicals, for example a C 1 -C 3 -alkyl radical or a C 1 -C 6 -alkyl radical.
  • alkyl radicals are methyl, ethyl, N-propyl, sec-propyl, n-butyl, isobutyl, 2-ethylhexyl, tertiary-butyl (tert-Bu / t / t-Bu), pentyl, hexyl, heptyl, cyclohexyl , Octyl, nonyl or decyl.
  • the alkyl radicals may also have one or more substituents such as halogen, amine, etc.
  • the alkyl radicals of the present invention are unsubstituted.
  • Preferred cyclic alkyl radicals are cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl.
  • Preferred linear or branched alkyl radicals are methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl or n-hexyl. More preferred linear alkyl radicals are methyl, ethyl and n-butyl, particularly preferred linear alkyl radicals are methyl or ethyl.
  • Particularly preferred as a cyclic alkyl radical is cyclohexyl.
  • the novel aqueous polymer dispersion containing at least one N-acylpyrrolidine according to the general formula (I) is further specified below.
  • N-acylpyrrolidines according to the general formula (I) as such are known to the person skilled in the art.
  • the N-acylpyrrolidine is preferably used in the context of the aqueous polymer dispersion according to the invention as a solvent of the corresponding polymer, in particular during its production process.
  • the N-acylpyrrolidine is defined according to the invention according to the general formula (I)
  • R 1 to R 9 are independently H or C-
  • the substituent H contained in the radicals R 1 to R 9 is hydrogen.
  • N-acylpyrrolidines contained in the aqueous polymer dispersion are defined by the general formula (I)
  • R 1 is H or linear or branched C 1 -C 6 -alkyl
  • R 2 to R 5 are independently H or C-
  • R 6 to R 9 are H.
  • R 1 is H or linear C 1 -C 3 -alkyl
  • R 2 to R 5 independently of one another are H, methyl, ethyl, isopropyl or cyclohexyl, and R 6 to R 9 are H.
  • R 1 is H, methyl or ethyl
  • R 2 to R 9 is H, wherein at most one of the radicals R 2 to R 5 may also be methyl, ethyl, iso-propyl or cyclohexyl.
  • Preferred compounds according to the general formula (I) are N-formylpyrrolidine, N-acetylpyrrolidine or N-propionylpyrrolidine, particular preference is given to N-formylpyrrolidine or N-acetylpyrrolidine.
  • the N-acylpyrrolidine is (I) formylpyrrolidine. In a further preferred embodiment, the N-acylpyrrolidine (I) is N-acetylpyrrolidine.
  • mixtures are mixtures of up to four different substituted N-acylpyrrolidines, preferably up to three and more preferably two.
  • the two N-acylpyrrolidines are generally in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3 and most preferably 2: 1 to 1 : 2 ago.
  • polymer dispersions according to the invention in particular polyurethane dispersions, contain N-formylpyrrolidine and N-acetylpyrrolidine in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3 and very particularly preferably 2: 1 to 1: 2.
  • the amount of N-acylpyrrolidines based on the polymer, in particular the polyurethane, is generally 0.01 to 100 wt .-%, preferably 1 to 100 wt .-%.
  • N-acylpyrrolidines used according to the invention can be used alone, mixed with one another or else mixed with one or more other suitable solvents.
  • solvents are, for example, open-chain or preferably cyclic carbonates, lactones, di (cyclo) alkyl dipropylene glycol ethers and N- (cyclo) alkylcaprolactams.
  • Carbonates are described, for example, in EP 697424 A1, there in particular from page 4, lines 4 to 29, to which reference is expressly made.
  • Preferred are 1,2-ethylene carbonate, 1,2-propylene carbonate and 1,3-propylene carbonate, more preferably 1,2-ethylene carbonate and 1,2-propylene carbonate.
  • Preferred lactones are beta-propiolactone, gamma-butyrolactone, epsilon-caprolactone and epsilon-methylcaprolactone.
  • Di (cyclo) alkyl dipropylene glycol ethers are, for example, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di-n-propyl ether and dipropylene glycol di-n-butyl ether, preference being given to dipropylene glycol dimethyl ether.
  • the di (cyclo) alkyl dipropylene glycol ether and especially dipropylene glycol dimethyl ether are generally mixtures of the position isomers and diastereomers.
  • the exact composition of the isomer mixtures does not play a role according to the invention. In general, that is major isomer
  • Dipropylene glycol dimethyl ether is commercially available as such a mixture of isomers and is usually by the CAS no. 1 1 1 109-77-4.
  • Dipropylene glycol dimethyl ether is commercially available in high purity of mostly more than 99% by weight, for example under the trade name Proglyde® DMM from The Dow Chemical Company, Midland, Michigan 48674, USA or from Clariant GmbH, 65840 Sulzbach am Taunus, Germany.
  • N- (Cyclo) alkylcaprolactams are those having an aliphatic (open-chain) or cycloaliphatic (alicyclic, ring-shaped), preferably open-chain, branched or unbranched, hydrocarbon radical having 1 to 6 carbon atoms, preferably 1 to 5, particularly preferably 1 to 4, in particular 1 to 3 and specifically 1 or 2 carbon atoms.
  • N- (cyclo) alkylcaprolactams are, for example, N-methylcaprolactam, N-ethylcaprolactam, Nn-propylcaprolactam, N-isopropylpropylcaprolactam, Nn-butylcaprolactam, N-isobutylcaprolactam, N-sec-butylcaprolactam, N-tert-butyl caprolactam, N-cyclopentylcaprolactam or N-cyclohexylcaprolactam, preferably N-methylcaprolactam or N-ethylcaprolactam.
  • Aqueous polymer dispersions according to the invention also contain at least one polymer.
  • aqueous polymer dispersions according to the invention contain from 10 to 75% by weight of polymer, based on the dispersion. Suitable polymer dispersions are known per se to the person skilled in the art.
  • aqueous polymer dispersions according to the invention contain from 90 to 25% by weight of water, based on the dispersion, the proportions of polymer, N-acylpyrrolidine, other additives and water supplementing to 100% by weight.
  • the aqueous polymer dispersion according to the invention contains 0.01 to 30 wt .-% of at least one N-acylpyrrolidine according to the general formula (I).
  • the weights are based on the total weight of the aqueous polymer dispersion according to the invention.
  • the aqueous polymer dispersions according to the invention are preferably aqueous polyurethane dispersions.
  • Aqueous polyurethane dispersions according to the invention furthermore contain at least one polyurethane.
  • aqueous polyurethane dispersions according to the invention contain from 10 to 75% by weight of polyurethane, based on the dispersion. Suitable polyurethane dispersions are known per se to the person skilled in the art.
  • polyurethane dispersions according to the invention comprise polyurethanes which have been prepared by the prepolymer mixing process, in particular those which are described by the process according to the invention for preparing polyurethane dispersions described below.
  • aqueous polyurethane dispersions according to the invention contain from 90 to 25% by weight of water, based on the dispersion.
  • the N-acylpyrrolidine can also be added to a finished polymer dispersion, in particular polyurethane dispersion, that is to say after the dispersion of the polymer, in particular polyurethane, for example, in order to advantageously influence its flow and drying behavior.
  • a finished polymer dispersion in particular polyurethane dispersion
  • preference is given to the addition of the N-acylpyrrolidine before the dispersion.
  • any polyurethane known to the person skilled in the art can be used in the aqueous polyurethane dispersions according to the invention.
  • the aqueous polyurethane dispersions according to the invention comprise at least one polyurethane which is obtainable by reacting a) at least one polyfunctional isocyanate having 4 to 30 carbon atoms, b) diols, of which b1) from 10 to 100 mol%, based on the total amount of Diols (b), have a molecular weight of 500 to 5000, and
  • Suitable monomers in (a) are the polyisocyanates customarily used in polyurethane chemistry, for example aliphatic, aromatic and cycloaliphatic di- and polyisocyanates, where the aliphatic hydrocarbon radicals have, for example, 4 to 12 carbon atoms and the cycloaliphatic or aromatic hydrocarbon radicals, for example 6 to 15 carbon atoms or the Araliphatic hydrocarbon radicals having for example 7 to 15 carbon atoms, with an NCO functionality of at least 1, 8, preferably 1, 8 to 5 and particularly preferably 2 to 4 in question, and their isocyanurates, biurets, allophanates and uretdiones.
  • the diisocyanates are preferably isocyanates having 4 to 20 C atoms.
  • Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, esters of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4-, 1, 3 or 1,2-diisocyanatocyclohexane, the trans / trans, the cis / cis and the cis / trans isomers of 4,4'- or 2,4'-di
  • aliphatic and cycloaliphatic diisocyanates Preference is given to aliphatic and cycloaliphatic diisocyanates, with particular preference being given to isophorone diisocyanate, hexamethylene diisocyanate, meta-tetramethylxylylene diisocyanate (m-TMXDI) and 1,1-methylenebis [4-isocyanato] cyclohexane (H 12 MDI).
  • Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing oxadiazine mononuclear groups, uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylenediisocyanates, cycloaliphatic diisocyanates having a total of from 6 to 20 carbon atoms or aromatic Diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.
  • aliphatic or cycloaliphatic di- and polyisocyanates for example the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.
  • isocyanurate-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particularly preferred in this case are the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on
  • the isocyanurates present are, in particular, tris-isocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 3 to 4.5.
  • uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the uretdione diisocyanates can be used in the preparations as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, especially tris (6-isocyanatohexyl) biuret or its
  • biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 3 to 4.5.
  • Allophanate group-containing polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 3. 5) Oxadiazintrion phenomenon containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide. 6) uretonimine-modified polyisocyanates.
  • the polyisocyanates 1) to 6) can be used in a mixture, if appropriate also in a mixture with diisocyanates.
  • Particularly suitable mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane; in particular, the mixture of 20 mol% of 2,4-diisocyanatotoluene and 80 mol% of 2,6-diisocyanatotoluene is suitable.
  • mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or I PDI are particularly advantageous, wherein the preferred mixing ratio of the aliphatic to aromatic isocyanates 4: 1 to 1: 4 ,
  • isocyanates which, in addition to the free isocyanate groups, carry further blocked isocyanate groups, for example uretdione or urethane groups.
  • isocyanates which carry only one isocyanate group. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers.
  • the monoisocyanates usually carry further functional groups such as olefinic groups or carbonyl groups and serve to introduce functional groups into the polyurethane, which enable the dispersion or the crosslinking or further polymer-analogous reaction of the polyurethane. Suitable for this purpose are monomers such as isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate (TMI).
  • Preferred diols (b) are relatively high molecular weight diols (b1) which have a molecular weight of about 500 to 5,000, preferably about 100 to 3,000, g / mol.
  • the diols (b1) are, in particular, polyester polyols which are known, for example, from "Ullmanns Encyklopadie der ischen Chemie", 4th Edition, Volume 19, pages 62 to 65.
  • Polyester polyols are preferably used which are prepared by reacting Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and, if appropriate, for Examples being halogen atoms, substituted and / or unsaturated, examples being: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acids.
  • dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.
  • Suitable polyhydric alcohols are, for example, ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane 1, 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1, 4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1, 3-diol, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, Dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration.
  • x is a number from 1 to 20, preferably an even number from 2 to 20.
  • examples of these are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol.
  • polycarbonate diols as can be obtained, for example, by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyesterpolyols.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Preferred lactones are those derived from hydroxycarboxylic acids of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20, preferably an odd number from 3 to 19, are derived, for example ⁇ -caprolactone, ß-propiolactone, ⁇ -butyrolactone and / or methyl-s-caprolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as a builder component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
  • suitable monomers (b1) are polyether diols. They are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF 3 or by addition of these compounds, optionally in admixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, For example, water, ethylene glycol, propane-1, 2-diol, propane-1, 3-diol, 2,2-bis (4-hydroxydiphenyl) propane or aniline available. Particularly preferred is polytetrahydrofuran having a molecular weight of 500 to 5000 g / mol, and especially 1000 to 4500 g / mol.
  • polyester diols and polyether diols can also be used as mixtures in the ratio 0, 1: 1 to 1: 9.
  • diols (b) in addition to the diols (b1), it is also possible to use low molecular weight diols (b2) having a molecular weight of about 50 to 500, preferably from 60 to 200, g / mol.
  • the monomers (b2) used are, in particular, the short-chain alkanediols mentioned for the preparation of polyester polyols, preference being given to the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms and pentanediol-1, 5 and neopentyl glycol.
  • the proportion of the diols (b1), based on the total amount of the diols (b) is 10 to 100 mol% and the proportion of the diols (b2), based on the total amount of the diols (b) 0 to 90 mol%.
  • the ratio of the diols (b1) to the diols (b2) is particularly preferably from 0.2: 1 to 5: 1, particularly preferably from 0.5: 1 to 2: 1.
  • the monomers (c) other than the diols (b) generally serve for crosslinking or chain extension. They are generally more than divalent non-aromatic alcohols, amines having two or more primary and / or secondary amino groups, and compounds containing one or more alcoholic alcohols Hydroxyl groups carry one or more primary and / or secondary amino groups.
  • Alcohols with a value of more than 2, which can serve to establish a certain degree of branching or crosslinking are, for example, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, sugar alcohols, such as, for example, sorbitol, mannitol, diglycerol, threitol, erythritol, Adonite (ribite), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt, or sugar.
  • sugar alcohols such as, for example, sorbitol, mannitol, diglycerol, threitol, erythritol, Adonite (ribite), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt, or sugar
  • monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group
  • monoalcohols having one or more primary and / or secondary amino groups for example monoethanolamine.
  • Polyamines having two or more primary and / or secondary amino groups can be used in the prepolymer mixing process, especially when the chain extension or crosslinking in the presence of water to take place (step III), since amines usually faster than alcohols or water with Isocyanates react. This is often required when aqueous dispersions of high molecular weight crosslinked polyurethanes or polyurethanes are desired. In such cases, prepolymers having isocyanate groups are prepared, these are rapidly dispersed in water and then chain-extended or crosslinked by addition of compounds having a plurality of isocyanate-reactive amino groups.
  • Amines suitable for this purpose are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two primary, two secondary or at least one primary and one secondary amino group.
  • diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1 , 4-diaminocyclohexane, aminoethyl ethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1, 8-diamino-4-aminomethyloctan or higher amines such as triethylenetetramine, tetraethylenepentamine or polymeric amines such as polyethyleneamines, hydrogenated polyacrylnitriles or at least partially hydrolyzed poly-N -Vinylformamide each having a molecular weight up to 2000, preferably up to 1000 g
  • the amines may also be in blocked form, for example in the form of the corresponding ketimines (see, for example, CA-1 129 128), ketazines (see, for example, US-A 4,269,748) or amine salts (see US-A 4,292,226 ) are used.
  • oxazolidines as used for example in US-A 4,192,937 provide Capped polyamines, which can be used for the preparation of the polyurethanes for chain extension of the prepolymers. When using such capped polyamines they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or a part of the dispersion water, so that the corresponding polyamines are hydrolytically released.
  • the proportion of polyamines may be up to 10, preferably up to 8 mol% and particularly preferably up to 5 mol%, based on the total amount of components (b) and (c).
  • the polyurethane prepared in step I can generally have up to 10% by weight, preferably up to 5% by weight, of unreacted NCO groups.
  • the molar ratio of NCO groups in the polyurethane produced in step I to the sum of primary and secondary amino groups in the polyamine is generally selected in step III to be between 3: 1 and 1: 3, preferably 2: 1 and 1 : 2, more preferably 1, 5: 1 and 1: 1.5; most preferably at 1: 1.
  • monoalcohols can be used. They serve mainly to limit the molecular weight of the polyurethane. Examples are methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, n-hexanol, n- Heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol) and 2-ethylhexanol.
  • the polyurethanes besides components (a), (b) and (c), are monomers (d) which are different from components (a), (b) and (c) and have at least one isocyanate group or at least one group which is reactive toward isocyanate groups and moreover at least one hydrophilic group or a group which can be converted into hydrophilic groups.
  • hydrophilic groups or potentially hydrophilic groups is abbreviated to "(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react with isocyanates much slower than the functional groups of the monomers used to build up the polymer backbone serve.
  • the (potentially) hydrophilic groups may be nonionic or preferably ionic, that is to say cationic or anionic, hydrophilic groups or potentially ionic hydrophilic groups and more preferably anionic hydrophilic groups or potentially anionic hydrophilic groups.
  • the proportion of components with (potentially) hydrophilic groups in the total amount of components (a), (b), (c) and (d) is generally such that the molar amount of (potentially) hydrophilic groups, based on the amount by weight of all monomers (a) to (b), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.
  • Suitable nonionic hydrophilic groups are, for example, mixed or pure polyethylene glycol ethers of preferably 5 to 100, preferably 10 to 80, repeating units of ethylene oxide.
  • the polyethylene glycol ethers may also contain propylene oxide units. If this is the case, the content of propylene oxide units should not exceed 50% by weight, preferably 30% by weight, based on the mixed polyethylene glycol ether.
  • the content of polyethylene oxide units is generally 0 to 10, preferably 0 to 6 wt.%, Based on the weight of all monomers (a) to (d).
  • Preferred monomers with nonionic hydrophilic groups are the polyethylene glycol and diisocyanates which carry a terminally etherified polyethylene glycol radical. Such diisocyanates and processes for their preparation are disclosed in US Pat. Nos. 3,905,929 and 3,920,598.
  • Ionic hydrophilic groups are especially anionic groups such as the sulfonate, the carboxylate and the phosphate group in the form of their alkali metal or ammonium salts and cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • Suitable monomers with potentially anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic mono- and dihydroxycarboxylic acids which carry at least one alcoholic hydroxyl group or one primary or secondary amino group.
  • Such compounds are represented, for example, by the general formula RG-R 4 -DG, in which RG at least one isocyanate-reactive group
  • R 4 is an aliphatic, cycloaliphatic or aromatic radical containing 1 to 20 carbon atoms.
  • RG examples include -OH, -SH, -NH 2 or -NHR 5 , in which R 5 is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, fer-butyl, Cyclopentyl or cyclohexyl can be.
  • Such components are, for example, mercaptoacetic acid, mercaptopropionic acid, thiolactic acid, mercaptosuccinic acid, glycine, iminodiacetic acid, sarcosine, alanine, ⁇ -alanine, leucine, isoleucine, aminobutyric acid, hydroxyacetic acid, hydroxypivalic acid, lactic acid, hydroxysuccinic acid, hydroxydecanoic acid, dimethylolpropionic acid, Dimethylolbutyric acid, ethylenediaminetriacetic acid, hydroxydodecanoic acid, hydroxyhexadecanoic acid, 12-hydroxystearic acid, aminonaphthalenecarboxylic acid, hydroxethanesulfonic acid, hydroxypropanesulfonic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, aminomethanesulfonic acid, taurine, aminopropanesulfonic
  • HO-R 1 -CR 3 (COOH) -R 2 -OH in which R 1 and R 2 is a C 1 to C 4 alkanediyl moiety and R 3 is a C to C 4 alkyl moiety.
  • R 1 and R 2 is a C 1 to C 4 alkanediyl moiety
  • R 3 is a C to C 4 alkyl moiety.
  • dimethylol butyric acid and especially dimethylolpropionic acid (DMPA) are preferable.
  • corresponding dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid
  • corresponding acids in which at least one hydroxyl group has been replaced by an amino group for example those of the formula
  • suitable diols are dihydroxy compounds having a molecular weight above 500 to 10,000 g / mol with at least 2 carboxylate groups which are known from DE-A 4,140,486. They are obtainable by reacting dihydroxyl compounds with tetracarboxylic dianhydrides, such as pyromellitic dianhydride or cyclopentane-tetracarboxylic dianhydride, in a molar ratio of 2: 1 to 1:05 in a polyaddition reaction. Particularly suitable dihydroxy compounds are the monomers (b2) listed as chain extenders and the diols (b1).
  • Potentially ionic hydrophilic groups are, above all, those which can be converted by simple neutralization, hydrolysis or quaternization reactions into the abovementioned ionic hydrophilic groups, that is to say, for example, acid groups, anhydride groups or tertiary amino groups.
  • Ionic monomers (d) or potentially ionic monomers (d) are described in detail, for example, in “Ullmanns Encyklopadie der ischen Chemie", 4th Edition, Volume 19, pp. 1-313, and for example in DE-A 1 495 745 ,
  • Particularly preferred monomers for cationic monomers (d) are monomers having tertiary amino groups, for example: tris (hydroxyalkyl) amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyalkyl-dialkylamines, tris ( aminoalkyl) amines, N, N'-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, wherein the alkyl radicals and alkanediyl moieties of these tertiary amines independently of one another consist of 2 to 6 carbon atoms.
  • tertiary nitrogen atoms containing polyether having preferably two terminal hydroxyl groups such as, for example, by alkoxylation of two amine-bound hydrogen atoms containing amines, for example methylamine, aniline, or ⁇ , ⁇ '-dimethylhydrazine, are accessible in a conventional manner in consideration.
  • Such polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, strong organic acids such as formic, acetic or lactic acid, or by reaction with suitable quaternizing agents such as C to C 6 alkyl halides, for example bromides or Chlorides, or di-Ci- to C 6 -alkyl sulfates or di-Ci- to C 6 alkylcarbonates converted into the ammonium salts.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, strong organic acids such as formic, acetic or lactic acid
  • suitable quaternizing agents such as C to C 6 alkyl halides, for example bromides or Chlorides, or di-Ci- to C 6 -alkyl sulfates or di-Ci- to C 6 alkylcarbonates converted into the ammonium salts.
  • Suitable monomers (d) with isocyanate-reactive amino groups are aminocarboxylic acids such as lysine, ⁇ -alanine, the adducts of aliphatic diprimary diamines mentioned in DE-A2034479 to ⁇ , ⁇ -unsaturated carboxylic acids such as N- (2-aminoethyl) -2- aminoethanecarboxylic acid and the corresponding N-aminoalkyl aminoalkylcarboxylic acids, wherein the alkanediyl units consist of 2 to 6 carbon atoms, into consideration.
  • aminocarboxylic acids such as lysine, ⁇ -alanine, the adducts of aliphatic diprimary diamines mentioned in DE-A2034479 to ⁇
  • ⁇ -unsaturated carboxylic acids such as N- (2-aminoethyl) -2- aminoethanecarboxylic acid and the corresponding N-aminoalkyl aminoalky
  • the anionic hydrophilic groups are particularly preferably in the form of their salts with an alkali ion or an ammonium ion as the counterion.
  • Hydroxycarboxylic acids are preferred among these compounds, with particular preference being given to dihydroxyalkylcarboxylic acids, with particular preference being given to ⁇ , ⁇ -bis (hydroxymethyl) -carboxylic acids, in particular dimethylolbutyric acid and dimethylolpropionic acid, and especially dimethylolpropionic acid.
  • the polyurethanes may contain both nonionic hydrophilic and ionic hydrophilic groups, preferably simultaneously nonionic hydrophilic and anionic hydrophilic groups.
  • the molecular weight of the polyurethanes can be adjusted by selecting the proportions of the monomers reactive with one another and the arithmetic mean of the number of reactive functional groups per molecule. Normally, the components (a), (b), (c) and (d) and their respective molar amounts are chosen so that the ratio A: B with
  • the ratio A: B is as close as possible to 1: 1.
  • monomers having only one reactive group are generally added in amounts of up to 15 mol%, preferably up to 8 mol%, based on the total amount of the components (a), (b), (c) and (d) used.
  • the polyaddition of components (a) to (d) is generally carried out at reaction temperatures of 20 to 180 ° C, preferably 50 to 150 ° C under atmospheric pressure.
  • the required reaction times can range from a few minutes to a few hours. It is known in the field of polyurethane chemistry how the reaction time is affected by a variety of parameters such as temperature, concentration of monomers, reactivity of the monomers.
  • the conventional catalysts can be used.
  • all catalysts commonly used in polyurethane chemistry come into consideration. These are, for example, organic amines, in particular tertiary aliphatic, cycloaliphatic or aromatic amines, and / or Lewis acidic organic metal compounds.
  • Suitable Lewis acidic organic metal compounds are tin compounds, for example tin (II) salts of organic carboxylic acids, for example tin (II) acetate, tin (II) octoate, tin (II) ethyl hexoate and tin (II) -Iaurate and the dialkyltin (IV) salts of organic carboxylic acids, for example dimethyltin diacetate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin diacetate.
  • tin (II) salts of organic carboxylic acids for example tin (II) acetate, tin (II) octoate, tin (II)
  • Metal complexes such as acetylacetonates of iron, titanium, aluminum, zirconium, manganese, nickel and cobalt are also possible.
  • Other metal catalysts are described by Blank et al. in “Progress in Organic Coatings", 1999, Vol. 35, pages 19-29.
  • Preferred Lewis-acidic organic metal compounds are dimethyltin diacetate, dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, diocytotin dilaurate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3, 5-heptanedionate.
  • Suitable cesium salts are those compounds in which the following anions are used: F, C, CIO “ , CI0 3 ⁇ CI0 4 ⁇ Br, J-, J0 3 " , CN-, OCN-, NO 2 -, N0 3 -, HC0 3 -, C0 3 2 -, S 2 " , SH “ , HS0 3 “ , S0 3 2” , HS0 4 " , S0 4 2” , S 2 0 2 2 -, S 2 0 4 2 “ , S 2 0 5 2 " , S 2 0 6 2” , S 2 0 7 2 -, S 2 0 8 2 -, H 2 P0 2 “ , H 2 P0 4 “ , HP0 4 2 “ , P0 4 3” , P 2 0 7 4 " , (OC n H 2n + 1 ) -, (C n H 2
  • Cesium carboxylates in which the anion conforms to the formulas (C n H 2n _ 1 O 2 ) _ and (C n + 1 H 2n _ 2 O 4 ) 2_ with n equal to 1 to 20 are preferred.
  • Particularly preferred cesium salts have as anions monocarboxylates of the general formula (C n H 2n _ 1 0 2 ) _ , where n is the numbers 1 to 20.
  • Rhackkessel come into consideration as polymerization, especially when provided by the concomitant use of solvents for a low viscosity and good heat dissipation. If the reaction is carried out in bulk, extruders, in particular self-cleaning multi-screw extruders, are particularly suitable because of the usually high viscosities and the usually short reaction times.
  • prepolymer which carries isocyanate groups
  • the components (a) to (d) are selected in this case such that the ratio A: B defined is greater than 1.0 to 3, preferably 1 , 05 to 1, 5.
  • the prepolymer is first dispersed in water and crosslinked simultaneously and / or subsequently by reaction of the isocyanate groups with amines containing more than two isocyanate-reactive amino groups, or with amines the two isocyanate-reactive amino groups Chain extension also takes place when no amine is added, in which case isocyanate groups are hydrolyzed to amino groups which react with remaining isocyanate groups of the prepolymers to chain extend.
  • the mean particle size (z average), measured by dynamic light scattering with the Malvern® Autosizer 2 C, the dispersions according to the invention is not essential to the invention and is generally ⁇ 1000 nm, preferably ⁇ 500 nm, more preferably ⁇ 200 nm, and most preferably between 20 and under 200 nm.
  • the dispersions generally have a solids content of 10 to 75, preferably from 20 to 65 wt .-% and a viscosity of 10 to 500 mPas (measured at a temperature of 20 ° C and a shear rate of 250 s _1 .
  • the dispersions prepared according to the invention can be mixed with other components typical of the applications mentioned, for example surfactants, detergents, dyes, pigments, dye transfer inhibitors and optical brighteners.
  • the dispersions may be subjected to physical deodorization after preparation, if desired.
  • a physical deodorization may consist in that the dispersion with water vapor, an oxygen-containing gas, preferably air, nitrogen or supercritical carbon dioxide, for example, in a stirred tank, as described in DE-AS 12 48 943, or in a countercurrent column, as in the 5 DE -A 196 21 027, is stripped.
  • the amount of the N-acylpyrrolidine (I) according to the invention in the preparation of the polyurethane is generally chosen so that the proportion in the final aqueous polyurethane dispersion, that is, after step II and optionally step III, does not exceed 10 30% by weight, preferably not more than 25, more preferably not more than 20 and most preferably not more than 15 wt .-%.
  • the proportion of N-acylpyrrolidine (I) in the finished aqueous polymer dispersion, in particular polyurethane dispersion, is generally at least 0.01% by weight, preferably at least 0.1, more preferably at least 0.2, very particularly preferably at least 0, 5 and in particular at least 1 wt .-%.
  • a further subject of the present invention is a process for preparing an aqueous polymer dispersion according to the above definitions, comprising the following steps I) and II):
  • R 1 to R 9 are independently H or Ci-Ci 8 alkyl
  • step II) subsequent dispersion of the polymer contained in step I) in water.
  • the polymer prepared in step I) described above is at least one polyurethane (as defined above).
  • the process according to the invention for the preparation of an aqueous polymer dispersion be specified so that a corresponding aqueous Polyurethane dispersion is prepared, wherein the method comprises the steps I), II) and optionally III):
  • Diols of which b1) have 10 to 100 mol%, based on the total amount of diols (b), of a molecular weight of 500 to 5000, and b2) 0 to 90 mol%, based on the total amount of diols (b) , have a molecular weight of 60 to 500 g / mol, optionally further, other than the diols (b), polyvalent compounds having reactive groups which are alcoholic hydroxyl groups or primary or secondary amino groups and of the monomers (a), (b) and (c) various monomers having at least one isocyanate group or at least one isocyanate group-reactive group further carrying at least one hydrophilic group or a potentially hydrophilic group, whereby the water-dispersibility of the polyurethanes is effected, a polyurethane and
  • step II subsequent dispersion of the polyurethane in water, III) optional addition of at least one polyamine after or during step II).
  • N-acylpyrrolidine according to the general formula (I) being selected from the group consisting of N-formylpyrrolidine, N-acetylpyrrolidine and N-propionylpyrrolidine.
  • Another object of the present invention is the use of polymer dispersions (according to the definitions described above) for coating, impregnating and / or bonding of wood, wood veneer, paper, cardboard, textile, leather, artificial leather, fleece, plastic, clothing, furniture Automotive interiors, vehicles, glass, ceramics, mineral building materials, metals or coated metals. It is preferred that the corresponding surfaces of these materials are coated, impregnated and / or glued.
  • the aqueous polymer dispersions according to the invention in particular polyurethane dispersions, are advantageously suitable for coating and bonding substrates.
  • Suitable substrates are wood, wood veneer, paper, cardboard, textiles, leather, artificial leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, clothing, vehicle interiors, vehicles, metals or coated metals. They are used, for example, in the production of films or films, for impregnating textiles or leather, as dispersants, as pigment driers, as primers, as adhesion promoters, as water repellents, as detergent additive or as additive in cosmetic preparations or for the production of moldings or hydrogels.
  • the polymer dispersions in particular polyurethane dispersions, in particular as primers, fillers, pigmented topcoats and clearcoats in the field of car repair or large vehicle painting can be used.
  • Particularly suitable are the coating compositions for applications in which a particularly high application safety, outdoor weather resistance, optics, solvent, chemical and water resistance are required, such as in the car repair and large vehicle painting.
  • Another object of the present invention is also the use of at least one N-acylpyrrolidine according to the general formula (I)
  • R 1 to R 9 independently of one another are H or C 1 -C 18 -alkyl, as solvents for the preparation of polymers, in particular as solvents for the preparation of polyurethanes.
  • a coating composition, adhesive or impregnating composition containing at least one aqueous polymer dispersion as described above.
  • the aqueous polymer dispersion an aqueous polyurethane dispersion according to the above.
  • Example 1 is repeated, but with 50 g of NMP instead of N-formylpyrrolidine.
  • the NCO content is determined to be 0.01% by weight (calculated: 0.00%).
  • Example 1 is repeated but with 50 g of NEP instead of N-formylpyrrolidine.
  • the NCO content is determined to be 0.02% by weight (calculated: 0.00%).

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Abstract

La présente invention concerne des dispersions polymères aqueuses contenant au moins une N-acylpyrrolidine selon la formule générale (I). L'invention concerne également un procédé de fabrication de dispersions polymères aqueuses, notamment de dispersions de polyuréthane, à l'aide d'au moins une N-acylpyrrolidine en tant que solvant. L'invention concerne en outre l'utilisation de N-acylpyrrolidines en tant que solvants pour la préparation de dispersions polymères aqueuses, ainsi que l'utilisation de ces dispersions polymères aqueuses pour revêtir, imprégner ou coller par exemple du bois ou du cuir. La présente invention concerne encore des matières de revêtement, des matières adhésives ou des matières d'imprégnation contenant une dispersion polymère aqueuse selon l'invention.
PCT/EP2016/056417 2015-04-07 2016-03-23 Dispersions polymères contenant de la n-acylpyrrolidine WO2016162215A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019145170A1 (fr) 2018-01-24 2019-08-01 Basf Se Dispersion aqueuse d'un polyuréthane comprenant un composé cycloaliphatique avec deux groupes amino secondaires comme allongeur de chaîne

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758104A (en) * 1951-11-13 1956-08-07 Du Pont Polyvinyl chloride dissolved in mixtures of a cyclic ether and an amide
DE1248943B (de) 1965-07-20 1967-08-31 Basf Ag Verfahren und Vorrichtung zur diskontinuierlichen Entfernung von Geruchs-stoffen auswaessrigen Polymerisatdispersionen
US3412054A (en) 1966-10-31 1968-11-19 Union Carbide Corp Water-dilutable polyurethanes
DE1495745A1 (de) 1963-09-19 1969-06-04 Bayer Ag Verfahren zur Herstellung waessriger,emulgatorfreier Polyurethan- Latices
DE2034479A1 (de) 1970-07-11 1972-01-13 Bayer Polyurethan Kunststoffe und Verfahren zu ihrer Herstellung
US3905929A (en) 1973-03-23 1975-09-16 Bayer Ag Aqueous dispersions of polyurethane having side chain polyoxyethylene units
US3920598A (en) 1973-03-23 1975-11-18 Bayer Ag Non-ionic polyurethane dispersions having side chains of polyoxyethylene
US4192937A (en) 1977-07-15 1980-03-11 Bayer Aktiengesellschaft Process for the preparation of isocyanate polyaddition products which have hydroxyl groups in side chains
US4269748A (en) 1978-03-15 1981-05-26 Bayer Aktiengesellschaft Process for the preparation of aqueous polyurethane dispersions and solutions
US4292226A (en) 1978-10-06 1981-09-29 Bayer Aktiengesellschaft Process for the production of aqueous dispersions or solutions of polyurethane polyureas, and dispersions or solution obtainable by this process and their use
CA1129128A (fr) 1977-06-07 1982-08-03 Josef Pedain Procede pour la preparation de dispersions et de solutions aqueuses de polyurethanne
DE4140486A1 (de) 1991-12-09 1993-06-17 Basf Ag Waessrige polyurethandispersionen
EP0697424A1 (fr) 1994-08-19 1996-02-21 Basf Aktiengesellschaft Mélanges contenant des isocyanates émulsionnables dans l'eau
DE19621027A1 (de) 1996-05-24 1997-11-27 Basf Ag Verfahren zur Abtrennung flüchtiger organischer Komponenten aus Suspensionen oder Dispersionen
WO2005090430A1 (fr) 2004-03-15 2005-09-29 Basf Aktiengesellschaft Nouveaux solvants utilises dans la production de dispersions de polyurethanne
WO2010142617A1 (fr) 2009-06-10 2010-12-16 Basf Se Utilisation de nouveaux solvants pour la préparation de dispersions de polyuréthane

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758104A (en) * 1951-11-13 1956-08-07 Du Pont Polyvinyl chloride dissolved in mixtures of a cyclic ether and an amide
DE1495745A1 (de) 1963-09-19 1969-06-04 Bayer Ag Verfahren zur Herstellung waessriger,emulgatorfreier Polyurethan- Latices
DE1248943B (de) 1965-07-20 1967-08-31 Basf Ag Verfahren und Vorrichtung zur diskontinuierlichen Entfernung von Geruchs-stoffen auswaessrigen Polymerisatdispersionen
US3412054A (en) 1966-10-31 1968-11-19 Union Carbide Corp Water-dilutable polyurethanes
DE2034479A1 (de) 1970-07-11 1972-01-13 Bayer Polyurethan Kunststoffe und Verfahren zu ihrer Herstellung
US3905929A (en) 1973-03-23 1975-09-16 Bayer Ag Aqueous dispersions of polyurethane having side chain polyoxyethylene units
US3920598A (en) 1973-03-23 1975-11-18 Bayer Ag Non-ionic polyurethane dispersions having side chains of polyoxyethylene
CA1129128A (fr) 1977-06-07 1982-08-03 Josef Pedain Procede pour la preparation de dispersions et de solutions aqueuses de polyurethanne
US4192937A (en) 1977-07-15 1980-03-11 Bayer Aktiengesellschaft Process for the preparation of isocyanate polyaddition products which have hydroxyl groups in side chains
US4269748A (en) 1978-03-15 1981-05-26 Bayer Aktiengesellschaft Process for the preparation of aqueous polyurethane dispersions and solutions
US4292226A (en) 1978-10-06 1981-09-29 Bayer Aktiengesellschaft Process for the production of aqueous dispersions or solutions of polyurethane polyureas, and dispersions or solution obtainable by this process and their use
DE4140486A1 (de) 1991-12-09 1993-06-17 Basf Ag Waessrige polyurethandispersionen
EP0697424A1 (fr) 1994-08-19 1996-02-21 Basf Aktiengesellschaft Mélanges contenant des isocyanates émulsionnables dans l'eau
DE19621027A1 (de) 1996-05-24 1997-11-27 Basf Ag Verfahren zur Abtrennung flüchtiger organischer Komponenten aus Suspensionen oder Dispersionen
WO2005090430A1 (fr) 2004-03-15 2005-09-29 Basf Aktiengesellschaft Nouveaux solvants utilises dans la production de dispersions de polyurethanne
WO2010142617A1 (fr) 2009-06-10 2010-12-16 Basf Se Utilisation de nouveaux solvants pour la préparation de dispersions de polyuréthane
US8575244B2 (en) * 2009-06-10 2013-11-05 Basf Se Solvents in the preparation of polyuretherane dispersions

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Ullmanns Encyklopädie der technischen Chemie, 4. Auflage,", vol. 19, pages: 311 - 313
"Ullmanns Encyklopädie der technischen Chemie, 4. Auflage,", vol. 19, pages: 62 - 65
BLANK ET AL., PROGRESS IN ORGANIC COATINGS, vol. 35, 1999, pages 19 - 29

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019145170A1 (fr) 2018-01-24 2019-08-01 Basf Se Dispersion aqueuse d'un polyuréthane comprenant un composé cycloaliphatique avec deux groupes amino secondaires comme allongeur de chaîne

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