EP2440593A1 - Utilisation de nouveaux solvants pour la préparation de dispersions de polyuréthane - Google Patents

Utilisation de nouveaux solvants pour la préparation de dispersions de polyuréthane

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Publication number
EP2440593A1
EP2440593A1 EP10724780A EP10724780A EP2440593A1 EP 2440593 A1 EP2440593 A1 EP 2440593A1 EP 10724780 A EP10724780 A EP 10724780A EP 10724780 A EP10724780 A EP 10724780A EP 2440593 A1 EP2440593 A1 EP 2440593A1
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EP
European Patent Office
Prior art keywords
polyurethane
cyclo
groups
substituted
mol
Prior art date
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Application number
EP10724780A
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German (de)
English (en)
Inventor
Gerd BÜLOW
Manfred Dargatz
Karl Häberle
Maria Teresa Hechavarria Fonseca
Karl Ott
Juan Salgado-Valle
Tobias Wabnitz
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BASF SE
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BASF SE
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Priority to EP10724780A priority Critical patent/EP2440593A1/fr
Publication of EP2440593A1 publication Critical patent/EP2440593A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to substituted N- (cyclo) alkylpyrrolidones as solvents for use in processes for the preparation of polyurethane dispersions.
  • Polyurethane dispersions are frequently produced industrially by the so-called "prepolymer mixing process". Therein, polyurethanes are first prepared in an organic solvent, often N-methylpyrrolidone, and the resulting solution of the polyurethane is subsequently dispersed 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 then affects there 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. Other than N-substituted pyrrolidones are not disclosed. However, there are indications that it might be suspected that N- (cyclo) alkylpyrrolidones, in particular N-ethylpyrrolidone, could lead to adverse toxicological effects, especially if it were taken by oral route. There is therefore a further need for solvents for the synthesis of polyurethane dispersions.
  • the object of the present invention was to provide solvents for the preparation of polyurethane dispersions by means of the "prepolymer mixing process" which positively influence the properties of the resulting polyurethane dispersion.
  • This object according to the invention is achieved by a process for the preparation of polyurethane dispersions, in which the polyurethane before dispersion in the presence of a substituted N- (cyclo) alkylpyrrolidone (SCAP) according to formula 1
  • SCAP substituted N- (cyclo) alkylpyrrolidone
  • R 1 is a (cyclo) alkyl radical having 1 to 18 C atoms and R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 'are each a hydrogen atom or a (cyclo) alkyl radical having 1 to 18 C With the proviso that at least one of R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 'is other than an H atom.
  • N- (cyclo) alkylpyrrolidones which are suitable according to the invention are those having an aliphatic (open-chain) or cycloaliphatic (alicyclic, ring-shaped), preferably open-chain, branched or unbranched, hydrocarbon radical R 1 having 1 to 6 carbon atoms, preferably 1 to 4, particularly preferably 1 to 3, in particular 1 to 2 and especially 1 carbon atom and with at least one, for example one to six, preferably one to three, more preferably one to two and most preferably exactly one aliphatic or cycloaliphatic, preferably aliphatic hydrocarbon radical as R 2 , R radicals 2 ', R 3 , R 3 ', R 4 and R 4 '.
  • R 1 having 1 to 6 carbon atoms, preferably 1 to 4, particularly preferably 1 to 3, in particular 1 to 2 and especially 1 carbon atom and with at least one, for example one to six, preferably one to three, more preferably one to two and most preferably exactly one aliphatic or cycl
  • 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, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-hexyl.
  • Preferred radicals are cyclohexyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-
  • butyl, sec-butyl and tert-butyl, particularly preferred are methyl, ethyl and n-butyl and very particularly preferred are methyl or ethyl, especially methyl.
  • Preferred radicals R 1 are methyl, ethyl and cyclohexyl, more preferably methyl and ethyl, and most preferably methyl.
  • R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 ' are hydrogen, methyl, ethyl, iso-propyl and cyclohexyl, particular preference is given to hydrogen, methyl, ethyl and isobutyl.
  • Propyl very particularly preferably hydrogen, methyl and ethyl and especially hydrogen and methyl.
  • At least one of the radicals R 2 , R 2 ', R 3 , R 3 ', R 4 and R 4 ' is preferably hydrogen, more preferably one to three, very preferably one to two and in particular exactly one.
  • Preferred compounds of formula 1 are N-methyl-3-methylpyrrolidone, N-methyl-4-methylpyrrolidone, N-ethyl-3-methylpyrrolidone and N-ethyl-4-methylpyrrolidone, more preferably N-methyl-3-methylpyrrolidone and N-methyl-4-methylpyrrolidone and mixtures thereof.
  • mixtures are mixtures of up to four different substituted N- (cyclo) alkylpyrrolidones, preferably up to three and particularly preferably two.
  • the two substituted N- (cyclo) alkylpyrrolidones 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 before.
  • the amount of the substituted N- (cyclo) alkylpyrrolidones based on the polyurethane is generally 1 to 100% by weight, preferably 10 to 100% by weight.
  • substituted N- (cyclo) alkylpyrrolidone employed 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 any role according to the invention. As a rule, this is the major isomer
  • R is the (cyclo) alkyl radical.
  • Dipropylene glycol dimethyl ether is commercially available as such a mixture of isomers and is usually denoted by the CAS No. 11 11 109-77-4.
  • Dipropylene glycol dimethyl ether is commercially available in high purity, usually 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-isopropylpropylcaprolactam, Nn-butylcaprolactam, N-isobutylcaprolactam, N-sec-butylcaprolactam, N-tert-butylcaprolactam, N Cyclopentylcaprolactam or N-cyclohexylcaprolactam, preferably N-methylcaprolactam or N-ethylcaprolactam.
  • substituted N- (cyclo) alkylpyrrolidone can also be added to a finished polyurethane dispersion, ie after the dispersion of the polyurethane, for example to influence its flow and drying behavior.
  • preference is given to the addition of the substituted N- (cyclo) alkylpyrrolidone before the dispersion.
  • the aqueous polyurethane dispersions are prepared by
  • 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 up to 15 carbon atoms or the araliphatic see 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, trans / trans, the cis / cis and the cis / trans isomers of 4,4'- or 2,4'-di (is
  • aliphatic and cycloaliphatic diisocyanates Preference is given to aliphatic and cycloaliphatic diisocyanates, particular preference being given to isophorone diisocyanate, hexamethylene diisocyanate, meta-tetramethylxylylene diisocyanate (m-TMXDI) and 4,4'-di (isocyanatocyclohexyl) methane (H12MDI).
  • 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 C 4 -C 20 -alkylene diisocyanates, cycloaliphatic diisocyanates having a total of from 6 to 20 ° C. -Atomen or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.
  • isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanurates present are, in particular, trisisocyanatoalkyl 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 from 10 to 30% by weight, in particular from 15 to 25% by weight, and an average NCO functionality of from 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).
  • Isocyanate groups in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologs.
  • These biuret polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 3 to 4.5. 4) containing urethane and / or allophanate polyisocyanates having aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bound isocyanate groups, as for example by reaction of excess amounts of hexamethylene diisocyanate or
  • Isophorone diisocyanate with polyhydric alcohols e.g. Trimethylolpropane, neopentyl glycol, 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 urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 3.
  • oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • oxadiazinitrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.
  • the polyisocyanates 1) to 6) can be used in a mixture, if appropriate also in a mixture 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 the aliphatic to aromatic isocyanates 4: 1 to 1 : 4.
  • isocyanates which, in addition to the free isocyanate groups, contain further blocked isocyanate groups, eg uretdione or urethane groups. bear.
  • 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 make possible the dispersion or crosslinking or further polymer-analogous reaction of the polyurethane.
  • Suitable monomers for this are, for example, 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. Preference is given to using polyesterpolyols 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 acid anhydrides or corresponding polycarboxylic acid 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.
  • 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.
  • 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) ⁇ -COOH, where z is a number from 1 to 20, preferably an odd number from 3 to 19, e.g. ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone and / or methyl- ⁇ -caprolactone and mixtures thereof.
  • Suitable starter components are e.g. 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 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 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-hydroxy-diphenyl) 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) it is possible, in addition to the diols (b1), 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 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 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 a higher valence than 2, which may serve to establish a certain degree of branching or crosslinking, are known, for example.
  • Sorbitol Sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol or isomalt, or sugar.
  • monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group, such as monoalcohols having one or more primary and / or secondary amino groups, e.g. Monoethanolamine.
  • Polyamines having 2 or more primary and / or secondary amino groups can be used in the prepolymer mixing process, especially when 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, 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 one primary and one secondary amino group.
  • diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane .
  • 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 (see US-A 4,292,226).
  • 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. 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 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.
  • monohydric alcohols 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 (lauryl alcohol) and 2-ethylhexanol.
  • the polyurethanes in addition to 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 a group which is reactive toward isocyanate groups and moreover has 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, ie 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 amount by 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 exemplified by the general formula
  • RG is at least one isocyanate-reactive group
  • DG is at least one dispersive 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 , wherein R 5 is methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, cyclopentyl or cyclohexyl.
  • 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
  • R 1 and R 2 is a C 1 -C 4 -alkanediyl unit and R 3 is a C 1 -C 4 -alkyl unit.
  • dimethylol butyric acid and especially dimethylolpropionic acid (DMPA) are preferred.
  • corresponding dihydroxysulfonic acids and dihydroxyphosphonic acids such as 2,3-dihydroxypropanephosphonic acid
  • the corresponding acids in which at least one hydroxyl group has been replaced by an amino group for example example, those of the formula
  • R 1 , R 2 and R 3 may have the same meanings as stated above.
  • 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 acid 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 by simple neutralization, hydrolysis or quaternization reactions into the above-mentioned ionic hydrophilic groups, e.g. Acid groups, anhydride groups or tertiary amino groups.
  • Ionic monomers (d) or potentially ionic monomers (d) are e.g. in Ullmann's Encyklopadie der ischen Chemie, 4th edition, volume 19, pp. 311-313 and for example in DE-A 1 495 745.
  • Monomers having tertiary amino groups are of particular practical importance as potential cationic monomers (d), 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.
  • polyethers having tertiary nitrogen atoms and having preferably two terminal hydroxyl groups are used. by the alkoxylation of two amines attached to Am in nitrogen-bonded hydrogen atoms, e.g. Methylamine, aniline, or N, N'-dimethylhydrazine, in a conventional manner are accessible, into 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 such as C 1 to C 6 alkyl halides, eg bromides or chlorides , or di-Cr to C ⁇ -alkyl sulfates or di-Cr to C ⁇ -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 such as C 1 to C 6 alkyl halides, eg bromides or chlorides , or di-Cr to C ⁇ -alkyl sulfates or di-Cr to C ⁇ -alkyl carbonates in the ammonium salts.
  • Suitable monomers (d) with isocyanate-reactive amino groups are amino carboxylic 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-aminoalkylamino-alkylcarboxylic acids, wherein the alkanediyl units consist of 2 to 6 carbon atoms, into consideration.
  • amino carboxylic 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-amino
  • 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, very particular preference 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.
  • 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 18O 0 C, preferably 50 to 15O 0 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 customarily used in polyurethane chemistry are suitable.
  • 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 dioctyl
  • 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 include those compounds come into consideration, in which the following anions are used: F, Ch, CIO, "CIO3-, CI (V, Br, J, IO3-, CN, OCN, NO 2 -, NO 3 -, HCO 3 -, CO 3 2 " , S 2" , SH “ , HSO 3 -, SO 3 2" , HSO 4 " , SO 4 2” , S 2 O 2 2 " , S 2 O 4 2” , S 2 O 5 2 -, S 2 O 6 2 " , S 2 O 7 2" , S 2 O 8 2 " , H 2 PO 2 -, H 2 PO 4 -, HPO 4 2” , PO 4 3 " , P 2 O 7 4 " , (OC n H 2n + -I) -, (C n H 2n _i0 2 ) -, (C n H 2n H 2n _i0 2 ) -, (C n H 2n ,
  • Cesium carboxylates in which the anion conforms to the formulas (C n H 2n _iO 2 ) - as well as (C n + iH 2n _ 2 O 4 ) 2 - where n is 1 to 20, are preferred.
  • Especially preferred te cesium salts have monocarboxylate anions of the general formula (C n H2n-i ⁇ 2) ", where n stands for the numbers 1 to 20. Of these, particular mention formate, acetate, propionate, hexanoate, and 2-ethylhexanoate.
  • 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 selected 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 average particle size (z- middle I value), 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 completely more preferably between 20 and below 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 m Pas (measured at a temperature of 2O 0 C and a shear rate of 250 S " 1 .
  • dispersions may be adjusted to another, preferably a lower, solids content, for example by dilution.
  • 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 DE-A 196 21 027 described, is stripped.
  • an oxygen-containing gas preferably air, nitrogen or supercritical carbon dioxide
  • the amount of the substituted N- (cyclo) alkylpyrrolidone according to the invention in the preparation of the polyurethane is generally chosen so that the proportion in the finished dispersion does not exceed 30% by weight, preferably not more than 25, particularly preferably not more than 20 and most preferably not more than 15% by weight.
  • the proportion of substituted N- (cyclo) alkylpyrrolidone in the finished 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 polyurethane preparations according to the invention are advantageously suitable for coating and bonding substrates.
  • Suitable substrates are wood, wood veneer, paper, cardboard, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, metals or coated metals. They are used, for example, in the production of films or foils, 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 polyurethane dispersions can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of car repair or large vehicle painting.
  • the coating compositions are particularly suitable for applications in which particularly high application safety, outdoor weathering resistance, appearance, solvent resistance, chemical resistance and water resistance are required, such as in car repair and large vehicle painting.
  • 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, less yellowing under light and / or heat influence, higher frost resistance of the dispersions.
  • N-alkylpyrrolidones While the subsequent addition of N-alkylpyrrolidones, as known in the art, is only for adjusting physical parameters of the finished dispersion, the preparation according to the invention of polyurethanes in the presence of substituted N- (cyclo) alkylpyrrolidone leads to advantages the production of polyurethanes, which would not be achieved by subsequent addition. The reason for this could be assumed that the polyurethanes produced according to the invention absorb the substituted N- (cyclo) alkylpyrrolidone, for example, by swelling in the entire cross section, whereas at a later addition at best a superficial absorption can take place.
  • Another object of the present invention are coating compositions comprising at least one inventive polymer dispersion and coated articles therewith.
  • Example A1 was repeated but with 80 g of NMP instead of the DMP.
  • the NCO content was determined to be 1.44% by weight (calculated: 1.43%).
  • a finely divided PUD with a solids content of 36.7% was obtained.
  • Example A1 was repeated but with 80 g NEP instead of the DMP.
  • the NCO content was determined to be 1.42% by weight (calculated: 1.43%).
  • a finely divided PUD with a solids content of 36.7% was obtained.
  • the examples were tested as a varnish on wood with the following results:
  • Example B1 was repeated but with 79 g of NMP instead of the DMP.
  • the NCO content was determined to be 2.19% by weight (calculated: 2.26%) to obtain a finely divided PUD having a solids content of 30%.
  • Example B2 was repeated but with 40 g of NMP instead of the DMP.
  • the NCO content was determined to be 4.50% by weight (calculated: 4.72%) to give a finely divided PUD with 30% solids content.

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Abstract

La présente invention concerne l'utilisation de N-(cyclo)alkylpyrrolidones substituées comme solvants dans des procédés de préparation de dispersions de polyuréthane.
EP10724780A 2009-06-10 2010-06-07 Utilisation de nouveaux solvants pour la préparation de dispersions de polyuréthane Withdrawn EP2440593A1 (fr)

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US20120076932A1 (en) 2012-03-29
US8575244B2 (en) 2013-11-05
RU2543894C2 (ru) 2015-03-10

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