EP3155029A1 - Dispersions de polymères contenant des acylmorpholines - Google Patents

Dispersions de polymères contenant des acylmorpholines

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Publication number
EP3155029A1
EP3155029A1 EP15725079.6A EP15725079A EP3155029A1 EP 3155029 A1 EP3155029 A1 EP 3155029A1 EP 15725079 A EP15725079 A EP 15725079A EP 3155029 A1 EP3155029 A1 EP 3155029A1
Authority
EP
European Patent Office
Prior art keywords
polyurethane
group
groups
atoms
dispersions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15725079.6A
Other languages
German (de)
English (en)
Inventor
Juergen Mohr
Ulrich Karl
Helfried Scheidl
Manfred Dargatz
Karl Haeberle
Thorsten Pauen
Juan SALGADO VALLE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3155029A1 publication Critical patent/EP3155029A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1866—Catalysts containing secondary or tertiary amines or salts thereof having carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 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
    • C08G18/28—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • 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
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • 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
    • 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
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to aqueous polymer dispersions containing at least one N-acylmorpholine as solvent.
  • the present invention furthermore relates to a process for preparing aqueous polymer dispersions, in particular polyurethane dispersions, using at least one N-acylmorpholine as solvent.
  • the present invention further relates to the use of N-acylmorpholines as solvents for the preparation of aqueous polymer dispersions.
  • 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".
  • polyurethanes are first prepared in an organic solvent, often N-methylpyrrolidone, and then dispersed the resulting solution of the polyurethane in water.
  • the molecular weight of the polyurethane can then be further increased by means of a chain extension.
  • the solvent also remains in the dispersion in a distillative separation to a greater or lesser extent and influences the properties of the polyurethane dispersion.
  • WO 2005/090 430 A1 teaches the use of N- (cyclo) alkylpyrrolidones with (cyclo) alkyl radicals having 2 to 6 C atoms for this purpose.
  • WO 10/142 617 describes substituted N- (cyclo) alkylpyrrolidones as suitable solvents.
  • the object of the present invention was to provide polymer dispersions, in particular polyurethane dispersions, which are toxicologically harmless and exhibit advantageous performance properties.
  • aqueous polymer dispersions in particular polyurethane dispersions containing at least one N-acylmorpholine of the formula (I)
  • R 1 is H or an alkyl group having 1 to 18 carbon atoms and R 2 , R 3 , R 4 and R 5 are each independently H or a (cyclo) alkyl group having 1 to 18 C atoms.
  • Preferred radicals R 1 are H, methyl and ethyl, particularly preferably H or methyl.
  • Substituted N-acylmorpholines which are particularly suitable according to the invention are those having an aliphatic (open-chain), cycloaliphatic (alicyclic, ring-shaped) preferably open-chain, branched or unbranched radical R 1 which has 0 to 5 carbon atoms, preferably 0 to 3, particularly preferably 0 to 2 , in particular 0 to 1 carbon atoms.
  • a "(cyclo) alkyl radical having 1 to 18 C atoms” is understood in the context of this document to mean an aliphatic, open-chain, branched or unbranched hydrocarbon radical having 1 to 18 carbon atoms or a cycloaliphatic hydrocarbon radical having 3 to 18 carbon atoms.
  • Suitable cycloalkyl radicals are cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl.
  • alkyl radicals examples include methyl, ethyl, / so-propyl, n-propyl, n-butyl, / so-butyl, sec-butyl, fer-butyl and n-hexyl.
  • Preferred radicals are cyclohexyl, methyl, ethyl, / so-propyl, n-propyl, n-butyl, / is-butyl, sec-butyl and fer-butyl, particularly preferred are methyl, ethyl and n-butyl, and very particularly preferred Methyl or ethyl.
  • Preferred radicals R 2 , R 3 , R 4 and R 5 are hydrogen, methyl, ethyl, iso-propyl and cyclohexyl, particular preference is given to hydrogen, methyl, ethyl and isopropyl, with very particular preference being given to hydrogen, methyl and ethyl and in particular Hydrogen and methyl.
  • Preferred compounds of the formula (I) are N-formylmorpholine, N-acetylmorpholine and N-propionylmorpholine, more preferably N-formylmorpholine and N-acetylmorpholine.
  • the N-acyl morpholine (I) is formyl morpholine.
  • the N-acyl morpholine (I) is N-acetylmorpholine.
  • mixtures are mixtures of up to four different substituted N-acylmorpholines, preferably up to three and more preferably two.
  • the two N-acylmorpholines 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, comprise N-formylmorpholine and N-acetylmorpholine in a weight ratio of from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, more preferably from 3: 1 to 1: 3 and very particularly preferably 2: 1 to 1: 2.
  • the amount of N-acylmorpholines based on the polymer, in particular the polyurethane is generally 0.01-100% by weight, preferably 1-100% by weight.
  • N-acylmorpholines used according to the invention can be used alone, mixed with one another or else mixed with one or more other suitable solvents.
  • suitable 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 positional isomers and diastereoisomers.
  • the exact composition of the isomer mixtures does not play a role according to the invention. As a rule, this is the major isomer R-OCH 2 CH (CH 3) OCH 2 CH (CH 3) OR, where R is the (cyclo) alkyl radical.
  • 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 especially 1 or 2 carbon atoms.
  • N- (cyclo) -alkylcaprolactams are, for example, N-methylcaprolactam, N-ethylcaprolactam, Nn-propylcaprolactam, N-so-propylcaprolactam, Nn-butylcaprolactam, N- / so-butylcaprolactam, N-se / butylcaprolactam, N-ferric Butylcaprolactam, N-cyclopentylcaprolactam or N-cyclohexylcaprolactam, preferably N-methylcaprolactam or N-ethylcaprolactam.
  • aqueous polymer dispersions according to the invention are preferably aqueous polyurethane dispersions.
  • Aqueous polymer dispersions according to the invention also contain at least one polymer.
  • aqueous polymer dispersions according to the invention contain 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 90 to 25% by weight of water, based on the dispersion, the proportions of polymer, N-acylmorpholine, other additives and water supplementing to 100% by weight.
  • Aqueous polyurethane dispersions according to the invention furthermore contain at least one polyurethane.
  • aqueous polyurethane dispersions according to the invention contain 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 mixture process, in particular those as described below process according to the invention for the preparation of polyurethane dispersions are described.
  • aqueous polyurethane dispersions according to the invention contain 90 to 25% by weight of water, based on the dispersion.
  • the N-acylmorpholine 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-acylmorpholine before the dispersion.
  • Another object of the present invention is a process for the preparation of polyurethane dispersions, wherein the aqueous polyurethane dispersions are prepared as follows: I. Preparation of a polyurethane by reacting a) at least one polyfunctional isocyanate having 4 to 30 carbon atoms, b) diols, from b1) from 10 to 100 mol%, based on the total amount of the diols (b), have a molecular weight of 500 to 5000, and b2) 0 to 90 mol%, based on the total amount of the diols (b), a molecular c) optionally further polyhydric compounds other than the diols (b), having reactive groups which are alcoholic hydroxyl groups or primary or secondary amino groups, and d) the monomers (a) , (b) and (c) various monomers having at least one isocyanate group or at least one isocyanate group-reactive group further having at least one hydrophilic group or carrying a potentially hydro
  • Suitable monomers in (a) are the polyisocyanates customarily used in polyurethane chemistry, for example aliphatic, aromatic and cycloaliphatic diisocyanates and polyisocyanates, where the aliphatic hydrocarbon radicals contain, 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, for example, have 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-iisocyanate, 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'-
  • diisocyanates there may also be mixtures of said diisocyanates.
  • Suitable polyisocyanates are polyisocyanates having isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates of straight-chain or branched one
  • C4-C20-alkylene diisocyanates cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof in consideration.
  • aliphatic or cycloaliphatic di- and polyisocyanates e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.
  • the isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs containing 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, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues.
  • These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 3 to 4.5.
  • aliphatically or cycloaliphatically bonded preferably aliphatically or cycloaliphatically bonded isocyanate groups, as obtained, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with polyvalent alcohols, for example trimethylolpropane, neopentylglycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol,
  • polyvalent alcohols for example trimethylolpropane, neopentylglycol, pentaerythritol, 1,4-butanediol, 1,6-hexanediol, 1,3-propanediol,
  • Ethylene glycol, diethylene glycol, glycerol, 1, 2-dihydroxypropane or mixtures thereof can be obtained.
  • These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
  • oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.
  • the polyisocyanates 1) to 6) can be used in a mixture, if appropriate also mixed with diisocyanates.
  • mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane, in particular the mixture of 20 mol% 2,4 diisocyanatotoluene and 80 mol%
  • 2,6-diisocyanatotoluene suitable.
  • the mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of aliphatic to aromatic isocyanates 4: 1 to 1: 4 is.
  • isocyanates which, in addition to the free isocyanate groups, contain further blocked isocyanate groups, e.g. Wear uretdione or urethane groups.
  • 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.
  • 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, polyesterpolyols which are known, for example, from Ullmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Before- kart be polyester polyols are used, which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples which may be mentioned are: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic 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.
  • polyhydric alcohols examples include 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, further diethyl englykol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol , Polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration. Neopentyl glycol and alcohols of the general formula are preferred
  • HO- (CH 2) x -OH where 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 e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • lactone-based polyesterdiols which are homopolymers or mixed polymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Preferred lactones are those which are 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, for example ⁇ -caprolactone, ß-propiolactone, ⁇ -butyrolactone and / or methyl ⁇ -caprolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis 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 corresponding, chemically equivalent polycondensates of the hydroxides corresponding to the lactones can also be used. roxycarboxylic acids are used.
  • suitable monomers (b1) are polyether diols.
  • they are by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, e.g. in the presence of BF3 or by addition of these compounds, optionally in admixture or sequentially, to starting components having reactive hydrogen atoms, such as alcohols or amines, e.g. 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 a ratio of 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 synthesis components of the short-chain alkanediols mentioned for the preparation of polyesterpolyols, the unbranched diols having 2 to 12 C atoms and an even number of C atoms and pentanediol-1, 5 and Ne - Opentylglykol be preferred.
  • the proportion of the diols (b1), based on the total amount of the diols (b), is preferably 10 to 100 mol% and the proportion of the diols (b2) is 0 to 90 mol%, based on the total amount of the diols (b).
  • 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 2 or more primary and / or secondary amino groups and compounds which carry one or more primary and / or secondary amino groups in addition to one or more alcoholic hydroxyl groups.
  • Alcohols of higher valency than 2, which can serve to set a certain degree of branching or crosslinking are e.g. Trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, sugar alcohols, such as e.g. Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol or isomalt, or sugar.
  • sugar alcohols such as e.g. Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol
  • monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group, such as monoalcohols having one or more primary groups and / or secondary amino groups, for example monoethanolamine.
  • Polyamines having 2 or more primary and / or secondary amino groups can be used in the prepolymer mixing process above all when the chain extension or crosslinking is to take place in the presence of water (step III), since amines are generally faster than alcohols or Water react with isocyanates. This is often required when aqueous dispersions of high molecular weight crosslinked polyurethanes or polyurethanes are desired. In such cases, the procedure is to prepare prepolymers with isocyanate groups, to rapidly disperse them in water and then to chain extend or crosslink them by adding compounds containing several 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, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane or higher amines such as triethylenetetramine, tetraethylenepentamine or polymeric amines such as polyethyleneamines, hydrogenated polyacrylonitriles or at least partially hydrolyzed poly-N-vinylformamide each having a molecular weight of up to 2000, preferably up to 1000 g / mol
  • the amines may also be in blocked form, e.g. 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
  • Oxazolidines as used for example in US Pat. No. 4,192,937, also represent blocked polyamines which can be used for the preparation of the polyurethanes for chain extension of the prepolymers.
  • 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 portion of the dispersion water, so that the corresponding polyamines are hydrolytically released.
  • the proportion of polyamines can 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 prepared 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.
  • chain termination in minor amounts, i. preferably in amounts of less than 10 mol%, based on the components (b) and (c), monoalcohols are 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 n-dodecanol (lauryl alcohol)
  • 2-ethylhexanol 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 much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain.
  • the (potentially) hydrophilic groups may be nonionic or, preferably, ionic, i. 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.
  • nonionic hydrophilic groups are mixed or pure polyethylene glycol ethers of preferably from 5 to 100, preferably from 10 to 80, 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
  • 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, in particular, anionic groups such as the sulfonate, the carboxylate and the phosphate groups in the form of their alkali metal or ammonium salts, and also cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • Suitable monomers having 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.
  • RG-R 4 -DG wherein RG is at least one isocyanate-reactive group
  • R 4 is an aliphatic, cycloaliphatic or aromatic radical containing 1 to 20 carbon atoms.
  • RG are -OH, -SH, -NH 2 or -NHR 5, wherein R 5 is methyl, ethyl, / 'so-propyl, n-propyl, n-butyl, / so-butyl, s / butyl, feri Butyl, cyclopentyl or cyclohexyl can be.
  • such components are e.g. 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, aminopropa
  • HO-R 1 -CR 3 (COOH) -R 2 -OH in which R 1 and R 2 is a C 1 to C 4 alkanediyl unit and R 3 is a C 1 to C 4 alkyl unit.
  • R 1 and R 2 is a C 1 to C 4 alkanediyl unit
  • R 3 is a C 1 to C 4 alkyl unit.
  • dimethylol butyric acid and especially dimethylolpropionic acid (DMPA) are preferable.
  • Dihydroxysulfonsauren and Dihydroxyphosponsauren such as 2,3-dihydroxypropanephosphonic acid and the corresponding acids in which at least one hydroxy group is replaced by an amino group, for example those of the formula
  • 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 cyclopentanetetracarboxylic 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 into the abovementioned ionic hydrophilic groups by simple neutralization, hydrolysis or quaternization reactions, that is, e.g. Acid groups, anhydride groups or tertiary amino groups.
  • Ionic monomers (d) or potentially ionic monomers (d) are e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 311-313 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, ⁇ , ⁇ '-bis (hydroxyalkyl) -alkylamines, N-hydroxyalkyl-dialkylamines, tris ( aminoalkyl) -amines, ⁇ , ⁇ '-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, where the alkyl radicals and alkanediyl Units of these tertiary amines independently 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 amines bound to amine nitrogen hydrogen atoms containing amines, eg methylamine, aniline, or ⁇ , ⁇ '-dimethylhydrazine, are accessible in per se 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 1 to C 6 alkyl halides, e.g. Bromides or chlorides, or di-Cd-C6-alkyl sulfates or di-d- to C6-alkyl carbonates in 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 1 to C 6 alkyl halides, e.g. Bromides or chlorides, or di-Cd-C6-alkyl sulfates or di-d- to C6-alkyl carbonates in 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-amin
  • 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, with particular preference being given to dihydroxyalkylcarboxylic acids, which are very particularly preferred
  • a-bis (hydroxymethyl) carboxylic acids in particular dimethylol butyric 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 each other and the arithmetic mean of the number of reactive functional groups per molecule.
  • the components (a), (b), (c) and (d) and their respective molar amounts are chosen so that the ratio A: B with A) the molar amount of isocyanate groups and
  • 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.
  • 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.
  • Lewis acidic organic metal compounds e.g. Tin compounds, such as tin (II) salts of organic carboxylic acids, e.g.
  • organic carboxylic acids eg dimethyltin diacetate, dibutyltin diacetate, Dibutyltin dibutyrate, dibutyltin bis (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin maleate, dioctyltin dilaurate and dioctyltin
  • 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, diocyttin dilaurate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3, 5-heptanedionate. Also bismuth and cobalt catalysts and cesium salts can be used as catalysts.
  • 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, N0 2 -, N0 3 -, HCOs-, CO 3 2 -, S 2 -SH-HSO 3 -, SO 3 2 -, HSO 4 -, S0 4 2 -, S2O 2 2 -, S2O4 2 -, S2O5 2 -, S 2 0 6 2 -, S2O7 2 -,
  • Rlickkessel come into consideration as polymerization, especially when provided by the concomitant use of solvents for a low viscosity and good heat dissipation.
  • extruders in particular self-cleaning multi-screw extruders, are particularly suitable because of the usually high viscosities and the usually short reaction times.
  • a prepolymer which carries isocyanate groups.
  • the components (a) to (d) are in this case chosen so that the ratio A: B is greater than 1, 0 to 3, preferably 1, 05 to 1, 5.
  • the prepolymer is first dispersed in water and simultaneously and / or chain-extended by reaction of the isocyanate groups with amines carrying more than 2 isocyanate-reactive amino groups, or with amines containing 2 isocyanate-reactive amino groups, chain extended. Chain extension also occurs when no amine is added. In this case, isocyanate groups are hydrolyzed to amine groups, which react with remaining isocyanate groups of the prepolymers with chain extension.
  • 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 deodorizing 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, such as in DE-A 196 21 027 described, is stripped.
  • an oxygen-containing gas preferably air, nitrogen or supercritical carbon dioxide
  • the amount of N-acylmorpholine (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 30% by weight not more than 25, more preferably not more than 20, and most preferably not more than 15% by weight.
  • the proportion of N-acylmorpholine (I) in the finished aqueous polymer dispersion, in particular polyurethane dispersion, is generally at least 0.01% by weight, preferably at least 0.1, particularly preferably at least 0.2, very particularly preferably at least 0.5 and in particular at least 1% by weight.
  • aqueous polymer dispersions according to the invention 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
  • the polymer dispersions can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of car repair or large-vehicle painting.
  • 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.
  • 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 because less incrustations or impurities are deposited on injection tools,
  • the prepolymer solutions have a lower viscosity.
  • the rheological behavior of the polyurethane dispersions is improved.
  • the wetting behavior of substrates or additives is improved.
  • N-acylmorpholines to polymer dispersions, either before, during or after the preparation and / or dispersion of the polymer or polyurethane, improves the adhesion of the coating, which is 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.
  • Another object of the invention is the use of N-Acylmorpholinen according to formula (I) as a solvent in the preparation of polymers, in particular polyurethanes, in particular of aqueous polyurethane dispersions, preferably by the prepolymer mixing method.
  • Another object of the invention are aqueous polyurethane dispersions prepared by the process according to the invention.
  • Another object of the present invention are coating compositions comprising at least one inventive polymer dispersion, in particular polyurethane dispersion, as well as objects coated therewith.
  • Another object of the invention is the use of polymer dispersions of the invention, in particular polyurethane dispersions for coating or impregnation of surfaces such as leather, wood, textile, synthetic leather, metal, plastics, clothing, furniture, automotive interiors, vehicles, paper, organic polymers, in particular polyurethane ,
  • Another object of the invention are coating compositions containing aqueous polymer dispersions, which have been prepared from polymer dispersions of the invention, as well as objects coated therewith.
  • Example 1 was repeated but with 50 g of NMP instead of N-formylmorpholine.
  • the NCO content was determined to be 0.01% by weight (calculated: 0.00%).
  • Example 1 was repeated but with 50 g of NEP instead of N-formylmorpholine.
  • the NCO content was determined to be 0.02% by weight (calculated: 0.00%).
  • the viscosities were determined using a rotation viscometer from the company Paar Physica according to DI N 53019.
  • the particular polymer dispersion to be examined is measured in aqueous dilution in a cuvette with a cuvette of edge length 2.5 cm with light of wavelength 600 nm and compared with the corresponding permeability of water under the same measurement conditions.
  • the permeability of water is given as 100%.
  • the finer the dispersion the higher the LD value measured by the method described above.
  • the LD values were determined in 0.1% strength aqueous solution of the dispersion to be determined using a device from Hach DR / 2010 at a wavelength of 600 nm.
  • the mean particle sizes were determined by dynamic light scattering in a Malvern Zetasizer APS.
  • Film hardnesses were determined according to DIN EN ISO 868.
  • the Lepton colors N are caseinfree Lederdeckmaschine.
  • Lepton® Filier FCG is a sizing agent based on aqueous wax dispersions, matting agents and additives. Astacin® Finish SUSI TF
  • Astacin® Finish SUSI TF is a very soft primer based on an aliphatic polyester urethane dispersion.
  • Astacin® Finish PS is a soft primer based on an aliphatic polyetherurethane dispersion.
  • Astacin® Finish PTM is a hard and matt primer based on an aliphatic polyetherurethane dispersion and matting agent.
  • Corial® Binder DN is a soft and very cold flexible primer binder based on an acrylate polymer dispersion.
  • Astacin® Novomatt GG is a medium hard, matt and flexible top coat binder based on an aliphatic polyester urethane dispersion and matting agent.
  • Astacin® Matting HS is a hard, matte and flexible top coat binder based on a polycarboant dispersion and matting agent.
  • Astacin® Novomatt GG is a medium-hard, very matt and flexible Top Coat binder based on an aliphatic polyetherurethane dispersion, matting agents and additives.
  • Lepton® Protector SR is a medium-hard, very matt and flexible Top Coat binder based on an aliphatic polyetherurethane dispersion, matting agents and additives.
  • Lepton® Protector SR is an anti-soiling additive based on a modified acrylate polymer dispersion and additives.
  • Lepton® Matting AL is a silicate-free polymeric matting agent.
  • Lepton® Wax WN is a silicate-free polymeric matting agent.
  • Lepton® Wax WN is a silicone emulsion based on high molecular weight poly-siloxanes.
  • Lepton® Wax DS is a low film-forming silicone emulsion based on high molecular weight poly-siloxanes.
  • Amollan® SW is a low film-forming silicone emulsion based on high molecular weight poly-siloxanes.
  • Amollan® SW is a flow control agent based on a low-viscosity silicone-polyether fluid.
  • Astacin® Hardener CA is a crosslinking agent for leather finishing based on polycarbonate and emulsifiers.
  • Astacin® Hardener CN is a leather conditioning crosslinker based on an aliphatic polyisocyanate and organic solvent.
  • a leather suitable for automotive interior applications was primed with a liquor containing a roll coater
  • the liquor is adjusted by the addition of 30 parts of water to an outlet viscosity of 40 sec in a 4 mm cup according to DIN EN ISO 2431: 201 1.
  • the wet coat weight was 8.0 ⁇ 0.5 g / ft 2 .
  • the leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.
  • the liquor is adjusted by the addition of 130 parts of water to an outlet viscosity of 24 sec in a 4 mm cup according to DIN EN ISO 2431: 201 1.
  • the wet coat weight was 2.4 + - 0.2 g / ft 2 .
  • the leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.
  • the primed leather was stored overnight, embossed at a temperature of 140 ° C / a pressure of 210 bar / and a residence time of 3 seconds, stored for 3 hours and milled for 3 hours.
  • the double-primed leather was spray-applied for the first time with a
  • Astacin® matting HS 200 T. Astacin® matting HS
  • the liquor is adjusted by addition of 220 parts of water to an outlet viscosity of 20 sec in the mm cup according to DIN EN ISO 2431: 201 1.
  • the wet job weight was 2.0 + - 0.2 g / ft 2 .
  • the leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.
  • the simply finished leather was spray finished for the second time with a
  • Astacin® matting HS 350 T. Astacin® matting HS
  • Astacin® Hardener CN 120 T. Astacin® Hardener CN.
  • the liquor is adjusted by adding 330 parts of water to an outlet viscosity of 28 seconds in a 4 mm cup according to DIN EN ISO 2431: 201 1.
  • the coating weight was wet 2.0 + - 0.2 g / ft 2 .
  • the leathers were dried at 80 ° C. for 1.5 minutes in a forced-air drying tunnel.
  • the primed and finished leather was stored overnight. example
  • Steps 1 and 2 of the comparative example were repeated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne des N-acylmorpholines utilisés comme solvant d'application et un procédé de production de dispersions de polymères.
EP15725079.6A 2014-06-10 2015-06-03 Dispersions de polymères contenant des acylmorpholines Withdrawn EP3155029A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14171793 2014-06-10
PCT/EP2015/062421 WO2015189084A1 (fr) 2014-06-10 2015-06-03 Dispersions de polymères contenant des acylmorpholines

Publications (1)

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EP3155029A1 true EP3155029A1 (fr) 2017-04-19

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US (1) US20170121537A1 (fr)
EP (1) EP3155029A1 (fr)
JP (1) JP2017523263A (fr)
KR (1) KR20170018892A (fr)
CN (1) CN106459361A (fr)
WO (1) WO2015189084A1 (fr)

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US20190329183A1 (en) * 2016-06-23 2019-10-31 Basf Se Use of a solution of polysulfone in n-acyl-morpholine for the fabrication of uf membranes
US11542360B2 (en) * 2017-06-26 2023-01-03 Advansix Resins & Chemicals Llc Methods and compositions for polyurethane dispersions using caprolactam-derived solvents
JP7340323B2 (ja) * 2017-12-27 2023-09-07 株式会社レゾナック・パッケージング 蓄電デバイス用外装材及び蓄電デバイス
EP3775138A1 (fr) * 2018-03-30 2021-02-17 AdvanSix Resins & Chemicals LLC Compositions et procédés de nettoyage et de décapage
JP7262956B2 (ja) * 2018-09-25 2023-04-24 株式会社ミマキエンジニアリング インクジェット用水系インク組成物
CN109575205B (zh) * 2018-11-20 2021-06-15 山东阳谷华泰化工股份有限公司 一种4-叔烷基苯酚-（吗啉基）甲醛树脂及其制备方法和应用

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US20170121537A1 (en) 2017-05-04
JP2017523263A (ja) 2017-08-17
CN106459361A (zh) 2017-02-22
KR20170018892A (ko) 2017-02-20
WO2015189084A1 (fr) 2015-12-17

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