WO2022184522A1 - Polyisocyanates émulsifiables dans l'eau présentant des propriétés améliorées - Google Patents

Polyisocyanates émulsifiables dans l'eau présentant des propriétés améliorées Download PDF

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Publication number
WO2022184522A1
WO2022184522A1 PCT/EP2022/054525 EP2022054525W WO2022184522A1 WO 2022184522 A1 WO2022184522 A1 WO 2022184522A1 EP 2022054525 W EP2022054525 W EP 2022054525W WO 2022184522 A1 WO2022184522 A1 WO 2022184522A1
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groups
polyisocyanate
diisocyanate
cyclo
water
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PCT/EP2022/054525
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German (de)
English (en)
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Frederic Lucas
Harald Schäfer
Sebastian Roller
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Basf Se
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Priority to EP22714364.1A priority Critical patent/EP4301798A1/fr
Publication of WO2022184522A1 publication Critical patent/WO2022184522A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
    • 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
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds

Definitions

  • the present invention relates to a two-stage process for preparing a water-emulsifiable polyisocyanate preparation in which, in step (A), a dispersing reaction product is prepared from at least one diisocyanate and at least one polyalkylene ether alcohol, and in a second step (B), the reaction product is prepared with a specific aliphatic polyisocyanate mixed in the presence of an allophanatization catalyst.
  • the invention also relates to a polymer dispersion which contains the water-emulsifiable polyisocyanate preparation which can be obtained by the process, and the use of the preparation in aqueous coating compositions and in adhesive dispersions.
  • Water-emulsifiable polyisocyanate preparations are known in principle.
  • Water-dispersible polyisocyanates play a special role as crosslinking components for water-dilutable two-component polyurethane (2K-PUR) paints.
  • 2K-PUR water-dilutable two-component polyurethane
  • they allow the formulation of solvent-free paint systems that cure at room temperature to form high-quality coatings that are in no way inferior to conventional paints in terms of solvent and chemical resistance or mechanical strength.
  • polyisocyanates containing isocyanate groups and based on aliphatic and/or cycloaliphatic diisocyanates are used as polyisocyanate components in such preparations.
  • polyisocyanates In order to achieve emulsifiability in water, it is known, on the one hand, to react the polyisocyanates directly with hydrophilic polyoxyalkylene groups in a suitable manner.
  • EP-A 486 881 discloses a two-stage process in which, in a first step, an emulsifier is first synthesized from a diisocyanate and polyalkylene ether alcohols. In a second step, this emulsifier is mixed with at least one aliphatic polyisocyanate, giving a water-emulsifiable preparation.
  • a two-stage process ultimately allows more targeted control of the properties compared to a step-by-step procedure.
  • the disadvantage is good emulsification, ie the use of a high concentration of polyalkylene ether groups, often at the expense of other properties, for example paint hardness.
  • EP2368928 describes the use of zinc compounds as allophanatization catalysts.
  • WO 2007/063027 describes water-emulsifiable, radiation-curable polyisocyanates.
  • the polyalkylene ether alcohols used are preferably those with a low salt content.
  • WO 2008/116764 describes the preparation of water-emulsifiable polyisocyanates by trimerizing at least one diisocyanate in the presence of a polyalkylene ether alcohol.
  • the polyalkylene ether alcohols used are preferably those with a low salt content.
  • WO 05/97865 describes the stabilization of allophanates, formed from di- or polyisocyanates with polyhydroxy compounds, with Bronsted acids.
  • the allophanates are preferably produced using zinc 2-ethylhexanoate, and the polyhydroxy compounds described explicitly are polyalkylene glycols, produced base-free by DMC catalysis.
  • EP 712 840 describes the production of polyisocyanates containing allophanate groups by reacting urethanes which are essentially free of isocyanate groups and hydroxyl groups to form allophanate groups and then removing the unreacted excess polyisocyanate by distillation.
  • EP 959087 describes aqueous polyisocyanates containing polyethylene glycol with 5-35 EO units bonded via allophanate groups with an allophanate group content of at least 60%.
  • Zinc(II)-n-octanoate, zinc(II)-2-ethyl-1-hexanoate and/or zinc(II) stearate are particularly preferred as allophanatization catalysts (p. 5, para. [0040]).
  • WO 2001/40347 describes the same with an allophanate group content of ⁇
  • US Pat. No. 5,235,018 and EP 524500B1 describe aqueous coating compositions containing non-water-dispersible or water-soluble polyisocyanate with monoisocyanurate:monoallophanate groups in a ratio of 10:1-1:5.
  • the allophanate is based on a monoalcohol with a molecular weight of up to 2500 D.
  • EP 1 061 091 describes lightfast polyurethanes with good solubility in non-polar solvents by reacting (cyclo)aliphatic isocyanates with components containing alkoxy groups with zinc catalysis.
  • EP 1 445 271 describes certain polyisocyanate compositions containing mono- and polyallophanates with 20-60 percent by weight of products with a molecular weight of less than 700 D and a proportion of 40-80 percent by weight of products with a molecular weight of more than 700 D, and a molar ratio of allophanate to isocyanurate groups of 100:0 - 75:25.
  • a two-stage process for the production of a water-emulsifiable polyisocyanate preparation in which, in a first process step (A) a dispersing reaction product (E) of at least one diisocyanate selected from the group consisting of hexamethylene diisocyanate, 4,4'-di-(isocyanato-cyclohexyl)-methane, 1-isocyanato-3,3,5-trimethyl-5- (Isocyanomethyl)cyclohexane, 2,4- and 2,6-tolylene diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate, 2,4'- and 4,4'-di
  • step (B) mixed with at least one (cyclo)aliphatic polyisocyanate containing iminooxadiazinedione groups and having an average NCO functionality of from 2.2 to 5.0, preferably from 2.5 to 4.0, step (B) being carried out in the presence of a Allophanatization catalyst and selects the conditions so that phanate groups are formed from (E) and the polyisocyanate, the (cyclo)aliphatic polyisocyanate having a proportion of iminooxadiazinedione groups based on the total amount of isocyanurate and iminooxadiazinedione groups of >20 mol % having.
  • water-emulsifiable polyisocyanate preparations obtainable by the process according to the invention were found, as was their use in aqueous coating compositions and adhesive dispersions.
  • the preparations according to the invention have improved dispersibility.
  • step (A) of the process according to the invention the reaction product (E) with dispersing activity is first synthesized from at least one diisocyanate and at least one polyalkylene ether alcohol.
  • (E) or its reaction product with the polyisocyanate to form the allophanate, serves as an emulsifier when the non-aqueous preparation is emulsified or dispersed in an aqueous medium for use.
  • the diisocyanate is at least one selected from the groups of 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 4,4'-di- (isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane, 2,4- and 2,6-toluylene diisocyanate, tetramethylxylylene diisocyanate, p-xylylene diisocyanate or 2,4'- and 4,4'-diisocyanatodiphenylmethane.
  • MDI 2,4'- and 4,4'-diisocyanatodiphenylmethane
  • HMDI 4,4'-di-(isocyanatocyclohexyl)-methane
  • TDI 2,4- and 2,6-tolylene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane
  • IPDI 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane
  • the diisocyanate component is reacted with a polyalkylene ether alcohol.
  • the alkylene group in the polyalkylene ether alcohol usually has 2 to 4 carbon atoms, typical are -CH2-CH(CH3)-, -(CH2)4- and preferably -(CH2)2-.
  • the polyalkylene ether alcohols can be prepared in a known manner by alkoxylating suitable starters, for example alcohols. Polyfunctional starters or preferably monofunctional starters can be used, and accordingly the polyalkylene ether alcohol is also polyfunctional or preferably monofunctional.
  • starter molecules examples include glycol hexanol, 3-methyl-3-hydroxymethyloxethane, phenol, ethylene glycol, propylene glycol, aniline, pentaerythritol, trimethylolpropane or glycerol.
  • CrC 6 alkanols are preferred, of which methanol, ethoxymethanol, ethanol, n-propanol or n-butanol are particularly preferred, and methanol is very particularly preferred.
  • the production usually takes place under acidic or basic catalysis. Subsequent desalination of the products is common for many applications of the polyalkylene ether alcohols.
  • the polyalkylene ether alcohol used it is advantageous for the polyalkylene ether alcohol used to have an acid number of less than 5 mmol/kg, preferably less than 4, more preferably less than 3, most preferably less than 2 and in particular less than less than 1 mmol/kg.
  • the polyalkylene ether chains can be mixed, for example made up of ethylene oxide and propylene oxide units.
  • the chains generally comprise 8 to 70, preferably 10 to 20, ethylene oxide units.
  • Good results are achieved when the polyalkylene ether alcohol contains at least 60% by weight, preferably at least 80% by weight, of ethylene oxide units. Pure polyethylene oxide chains are particularly preferred.
  • the number ratio of OH groups to NCO groups in step (A) is usually 0.6 to 1.2, preferably 0.8 to 1.2, particularly preferably 0.9 to 1.1 and very particularly preferably approx .1:1.
  • This reaction of the polyalkylene ether alcohol with the diisocyanate is known per se and usually takes place at temperatures of from 10 to 150.degree. C., preferably from 20 to 100.degree .
  • the reaction time is generally such that at least 90 mol % of the groups of the polyalkylene ether alcohol which are reactive with isocyanate groups have reacted with isocyanate.
  • the reaction can be accelerated by using known, catalytically active substances. Possible catalysts are metal salts.
  • metal salts preferably contain Li, Na, K, Ba, Cs, Sb, Al, Fe, Bi, Ge, Sn, Hg, Ti, Zr or Zn cations as the metal cation.
  • the metal salts particularly preferably contain Al, Cs, Bi, Sn, Zr or Zn cations.
  • the water-emulsifiable polyisocyanate preparations according to the invention advantageously have improved emulsifiability with the same amount of reaction product (E).
  • reaction product (E) is mixed with an aliphatic polyisocyanate containing iminooxadiazinedione groups and reacted to form the allophanate, the (cyclo)aliphatic polyisocyanate having a proportion of iminooxadiazinedione groups based on the total amount of isocyanurate and iminooxadiazinedione groups of >20 mol -% having.
  • the (cyclo)aliphatic polyisocyanate preferably has a proportion of iminooxadiazine dione groups, based on the total amount of isocyanurate and iminooxadiazine dione groups, of from 30 to 70 mol %, particularly preferably from 40 to 50 mol %.
  • Step (B) preferably follows directly after step (A); however, it is also possible to first store (E) and then to react it with the polyisocyanate at a later point in time.
  • the aliphatic polyisocyanate containing iminooxadiazinedione groups generally has an NCO content of 10 to 30% by weight, preferably 15 to 27% by weight, very particularly preferably 15 to 25% by weight.
  • Cyclo(aliphatic) polyisocyanates containing iminooxadiazinedione groups within the meaning of the invention are:
  • Polyisocyanates containing iminooxadiazinedione groups and based on aliphatic and/or cycloaliphatic diisocyanates are based on aliphatic and/or cycloaliphatic diisocyanates.
  • Polyisocyanates containing iminooxadiazinedione groups generally have an NCO content of 10 to 30, preferably 15 to 25 % by weight and an average NCO functionality of from 2.2 to 5.0, preferably from 2.5 to 4.0.
  • the viscosity is preferably in the range from 600 mPa*s to 2500 mPa*s, preferably from 700 to 1000 mPa*s at 23°C.
  • the (cyclo)aliphatic polyisocyanate containing iminooxadiazinedione groups preferably comprises compounds of the formula where R 1 , R 2 , R 3 are identical or different radicals, such as those formed by removal of an isocyanate group from monomeric or oligomeric isocyanates of the general formula (OCN-CH2)X, where X is an optionally branched, optionally cyclic , optionally further heteroatoms and heteroatom groups (NCO, O, Si, S) or a point of attachment to a C3-C20 substituent containing an NCO secondary product.
  • R 1 , R 2 , R 3 are identical or different radicals, such as those formed by removal of an isocyanate group from monomeric or oligomeric isocyanates of the general formula (OCN-CH2)X, where X is an optionally branched, optionally cyclic , optionally further heteroatoms and heteroatom groups (NCO, O, Si, S) or a point of attachment to a
  • Polyisocyanates containing isocyanurate groups and based on aliphatic and/or cycloaliphatic diisocyanates are particularly preferred.
  • the corresponding isocyanato-isocyanurates based on 1,6-diisocyanatohexane, 1,5-pentamethylene diisocyanate and/or 1-isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate, IPDI) are particularly preferred ).
  • polyisocyanates containing isocyanurate groups are described, for example, in DE-A 2616416, EP-A 3765, EP-A 10 589, EP-A 47452, US-A 4288586 or US-A 4324879.
  • inventive Polyisocyanate preparation not only these particularly preferred Verbindun gene, but any polyisocyanates having isocyanurate groups are present on Ba sis aliphatic and / or cycloaliphatic diisocyanates.
  • Suitable isocyanato-isocyanurates are, in particular, simple tris-isocyanatoalkyl (or -cycloalkyl) isocyanurates of the formula or mixtures thereof with their higher homologues containing more than one isocyanurate ring, where in this formula Xi, X2 and X3 are identical or different radicals and are the hydrocarbon radical on which the starting diisocyanate is based.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, preferably 15 to 25% by weight, and an average NCO functionality of 2.2 to 5.0, preferably 2.5 to 4.0 .
  • Aliphatic polyisocyanates in the context of the invention are also: polyisocyanates containing biuret groups with aliphatically bonded isocyanate groups, in particular tris-(6-isocyanatohexyl)-biuret or mixtures thereof with its higher homologues.
  • These polyisocyanates containing biuret groups generally have an NCO content of 18 to 26% by weight, preferably 20 to 23% by weight, and an average NCO functionality of 3 to 4, preferably 3 to 3.5 on.
  • Aliphatic polyisocyanates in the context of the invention are also: polyisocyanates containing urethane and/or allophanate groups with aliphatically or cycloaliphatically bonded isocyanate groups, such as are produced, for example, by reacting excess amounts of hexamethylene diisocyanate or of IPDI with simple polyhydric alcohols such as trimethylolpropane, 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 from 2.5 to 3. These mixtures usually contain relevant proportions of polyisocyanates containing isocyanurate groups.
  • the cyclo)aliphatic polyisocyanate containing iminooxadiazinedione groups preferably knows compounds of the iminooxadiazinedione structure type (formula A) or mixtures of isocyanurate (formula B) and iminooxadiazinedione structure types (formula A) with >20 mol % of A based on the total amount A and B, and the molar ratio of trimers (sum of A and B) to dimers (uretdione) is greater than 4:1, and that the (cyclo)aliphatic polyisocyanate has a total content of carbodiimides and/or uretone imines below 10 mol% based on the total amount of NCO secondary products.
  • the reaction product (E) is usually used in such an amount that the water-emulsifiable polyisocyanate preparation contains 1 to 25% by weight, preferably 5-20% by weight and particularly preferably 10-20% by weight thereof.
  • step (B) is carried out in the presence of a suitable allophanatization catalyst.
  • the allophanatization catalyst can be added here before or during step (B). However, it is also possible to add the allophanatization catalyst before or during step (A). Since the NCO groups react preferentially with existing OH groups, the formation of allo phanate groups in step (A) are generally negligible due to the stoichiometry chosen.
  • Allophanatization catalysts suitable for carrying out the process according to the invention are, for example, zinc compounds, such as zinc(II) n-octanoate, zinc(II) 2-ethyl-1-hexanoate or zinc(II) acetylacetonate and in particular zinc(II). )-neodecanoate.
  • zinc compounds such as zinc(II) n-octanoate, zinc(II) 2-ethyl-1-hexanoate or zinc(II) acetylacetonate and in particular zinc(II). )-neodecanoate.
  • Salts consisting of a metal cation and at least one dithiophosphate or carboxylate anion are preferred.
  • the metal cation is particularly preferably a monovalent or divalent metal cation.
  • the metal cation are Li, Cs, Na, K, Sb, Fe, Bi, Ge, Sn, Ba, Hg, Ti, Zr and Zn.
  • Particularly preferred metal cations are Zn and Bi.
  • Examples of the at least one dithiophosphate anion are, for example, O,O-diethyl dithiophosphate, 0,0-di-2-ethylhexyl dithiophosphate, 0,0-di-2-propylheptyl dithiophosphate, 0,0-diisobutyl dithiophosphate, 0,0-dicyclohexyl dithiophosphate and O,O-bis-2,4,4-trimethylpentyl dithiophosphate and mixtures thereof.
  • O,O-dithiophosphate anion are O,O-diisobutyl dithiophosphate, O,O-diethyl dithiophosphate and 0,0-di-2-ethylhexyl dithiophosphate and mixtures thereof.
  • mixtures are mixed 0,0-bis(2-ethylhexyl and isobutyl)dithiophosphates, mixed 0,0-bis(1,3-dimethylbutyl and isopropyl)dithiophosphates, mixed 0,0-bis(2-ethylhexyl and isobutyl and isopropyl)dithiophosphates, mixed 0,0-bis(2-ethylhexyl and isobutyl and pentyl)dithiophosphates, mixed 0,0-bis(2-ethylhexyl and isobutyl)dithiophosphates, mixed 0,0-bis(2-ethylhexyl and isopro - pyl)dithiophosphates, mixed 0,0-bis(branched and linear pentyl and isobutyl)dithiophosphates, mixed 0,0-bis(ethyl and hexyl and isopropyl)dithiophosphates, mixed 0,0-0-
  • This structural unit can be present one or more times within a catalyst molecule, for example one to six times, preferably one to four times, very particularly preferably one to three times, in particular one to two times and specifically once.
  • Allophanatization catalysts are particularly preferably a salt of the formula wherein
  • M Li, Na, Cs, K, Sb, Fe, Al, Bi, Ge, Sn, Ba, Hg, Ti, Zr or Zn, particularly preferably Al, Cs, Bi, Zr, Sn or Zn,
  • R 1 and R 2 can each independently be the same or different and represent a straight-chain or branched C 1 to C 20 alkyl group, an optionally substituted C s to C 2 cycloalkyl group, an optionally substituted C 7 to C io aralkyl group, an optionally substituted C 6 -Ci2-aryl group, hydrogen, or an optionally interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted amino groups or by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, hete- Roatome and / or heterocycles substituted Ci-C2o-alkyl group or C 6 to C12 aryl group, and n is a positive integer.
  • a straight-chain or branched C 1 -C 20 -alkyl group means, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1,1-dimethylpropyl, hexyl, 1, 1-dimethylbutyl, 1,3-dimethylbutyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, neodecyl, decyl or dodecyl, an optionally substituted C5 - to Ci2-cycloalkyl group, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl
  • R 1 and R 2 are independently hydrogen, methyl, ethyl, n-propyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2-propylheptyl, phenyl, a- or ⁇ -naphthyl, benzyl, cyclopentyl, cyclohexyl, hydroxymethyl, 2-hydroxyethyl, 2-carboxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2,4,4-trimethylpentyl, 1,3- dimethylbutyl or 2-cyanoethyl.
  • Preference is given to hydrogen, methyl, ethyl, n-propyl, n-butyl, tert-butyl, cyclohexyl, phenyl, 2-carboxyethyl, 2,4,4-trimethylpentyl, 2-hydroxyethyl, 2-ethylhexyl and 1,3- dimethylbutyl are particularly preferred hydrogen, methyl, ethyl, n-butyl, tert-butyl, 2-ethylhexyl, 2-propylheptyl, cyclohexyl, 2,4,4-trimethylpentyl and phenyl, very particularly preferred are hydrogen, methyl, ethyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2-propylheptyl and n-butyl and especially 2-ethylhexyl and n-butyl.
  • radicals R 1 and R 2 form a ring, they can be, for example, 1,4-butylene or 1,5-pentylene.
  • M is very particularly preferably Zn and R 1 and R 2 , independently of one another, are a straight-chain or branched C 1 to C 20 alkyl group.
  • These catalysts are used in the process according to the invention in an amount of 0.001 to 5% by weight, preferably 0.005 to 1% by weight, based on the total weight of the reactants.
  • reaction step (B) is carried out at a reaction temperature which is at least 10° C. higher than reaction step (A), preferably at least 15° C. higher and particularly preferably at least 20° C. higher.
  • reaction step (A) is preferably carried out at a temperature of 40 to 85° C., preferably 50 to 65° C., and reaction step (B) is correspondingly higher.
  • the course of the reaction can be followed, for example, by titrimetric determination of the NCO content.
  • the degree of allophanatization is determined by the person skilled in the art depending on the desired properties of the water-emulsifiable preparation. It has proven useful that at least 10 mol % of the urethane groups of the reaction product (E) formed in step (A) are converted into allophanate groups.
  • the degree of conversion is preferably from 20 to 100 mol % and particularly preferably from 40 to 100 mol %.
  • the polyisocyanate preparation produced in this way is preferably used in bulk.
  • small amounts, ie for example 1 to 40% by weight based on the solvent-free preparation, of an organic solvent such as ethyl acetate, butyl acetate, acetone, methoxypropyl acetate, propylene carbonate, 3-methoxy-n-butyl acetate can also be added to the preparation before use , [2-(2-butoxy- ethoxy)-ethyl] acetate, dipropylene glycol n-butyl ether, propylene glycol diacetate, dipropy- Add ethylene glycol dimethyl ether, butyl glycol acetate, butyl diglycol acetate, ethyl ethoxy propionate, or methyl ethyl ketone to reduce viscosity.
  • mixtures of the solvents mentioned can also be used. It is also possible to process the polyisocyanate preparations according to the invention to give
  • the polyisocyanate preparations according to the invention can preferably be dispersed in water to produce aqueous dispersions; the polyisocyanate preparations according to the invention are particularly preferably mixed into aqueous NCO-reactive or NCO-inreactive, preferably NCO-reactive, dispersions.
  • the polyisocyanate preparation according to the invention is suitable for modifying aqueous coating materials (varnish, protective coatings) for e.g. Wood, wood veneer, paper, cardboard, textiles, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials such as cement blocks and fiber cement panels, metals or coated metals, adhesives or impregnating agents, e.g. for dyeing, based on aqueous dispersions or solutions with a solids content of 5 to 40% by weight, preferably 5 to 20% by weight.
  • aqueous dispersions of homo- and copolymers of olefinically unsaturated monomers or polyurethanes or also solutions of natural substances such as casein can be considered as coating materials.
  • the polyisocyanate preparations of the invention are generally added to the aqueous coating compositions in an amount of from 1 to 25% by weight, preferably from 2.5 to 20% by weight, based on the solids content of the coating composition.
  • the polymer dispersions are preferably aqueous solutions, emulsions or dispersions of polyols: polyacrylateol, polyesterol, polyurethaneol, polyetherol, polycarbonateol dispersions and their hybrids and/or mixtures of the polyols mentioned.
  • Hybrids means graft copolymers and other chemical reaction products that contain chemically bound parts of the molecule with different (or the same) groups mentioned.
  • suitable dispersions of homopolymers or copolymers of olefinically unsaturated monomers are known dispersions of homopolymers or copolymers based on vinyl esters of carboxylic acids having 2 to 18, preferably 2 to 4 carbon atoms, such as in particular vinyl acetate, optionally with up to 70% by weight on the total amount of olefinically unsaturated monomers, of other olefinically unsaturated monomers and/or of homo- or copolymers of (meth)acrylic acid, (meth)acrylic esters of alcohols having 1 to 18, preferably 1 to 8 carbon atoms, such as in particular (meth)acrylic , -methyl, -ethyl, -propyl, butyl, 2-ethylhexyl, -hydroxyethyl or -hydroxypropyl, - glycidyl esters, acetoacetoxyethyl (meth)acrylate), optionally together with up to 70 %
  • ethylenically unsaturated compounds such as (meth)acrylic acid alkyl esters, for example methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-propylheptyl (meth)acrylate as Mono mers are used.
  • a,b-monounsaturated monocarboxylic acids or dicarboxylic acids e.g. acrylic acid, methacrylic acid can be used as monomers.
  • Hydroxy-functional a,b-monounsaturated compounds such as hydroxyalkyl acrylates and/or methacrylates, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, can be used as monomers.
  • monomers with cycloaliphatic structural elements such as isobornyl methacrylate or cyclohexyl methacrylate and vinyl aromatic compounds such as styrene or alpha-methyl styrene can be used.
  • monomers are: ethylenically unsaturated nitriles such as acrylonitrile; vinyl esters of carboxylic acids such as vinyl acetates; vinyl halides such as vinyl chloride or vinylidene chloride; vinyl ethers of alcohols; furthermore other functionalized unsaturated compounds such as 2-(2-oxoimidazolidin-1-yl)ethyl methacrylate (ureido(meth)acrylate), (acetoacetoxy)ethyl methacrylate or diacetone acrylamide, in addition to the epoxy-functional methacrylates such as glycidyl methacrylate and furthermore acrylamide.
  • ethylenically unsaturated nitriles such as acrylonitrile
  • vinyl esters of carboxylic acids such as vinyl acetates
  • vinyl halides such as vinyl chloride or vinylidene chloride
  • vinyl ethers of alcohols furthermore other functionalized unsaturated compounds
  • An example of a commercially available polyacrylate secondary emulsion is Bayhydrol® A 145 (a product from Covestro AG).
  • Examples of a polyacrylate primary emulsion are Bayhydrol® VP LS 2318 (a product from Covestro AG) and Luhydran® grades from BASF SE.
  • Other examples are Macrynal® VSM 6299w/42WA from Allnex, and Setalux® AQ grades from Nuplex Resins such as Setalux® 6510 AQ-42, Setalux® 6511 AQ-47, 30 Setalux® 6520 AQ-45, Setalux® 6801 AQ -24, Setalux® 6802 AQ-24, and Joncryl® from BASF SE.
  • Dispersions can contain internal and external emulsifiers, protective colloids and amines for solubilization, e.g. as ammonium carboxylate.
  • aqueous dispersions of copolymers of 90 to 99.5% by weight of acrylates or methacrylates of 1 to 4 carbon atom-containing alkanols and 0.5 to 10% by weight, based in each case on the copolymer, of hydroxyalkyl acrylates and methacrylates with 2 to 20 C atoms in the hydroxyalkyl radical, such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate.
  • styrene also possible as a monomer.
  • Such dispersions are known per se and can be prepared in the usual way by emulsion polymerization (see Houben-Weyl, Methods of Organic Chemistry,
  • Suitable aqueous polyurethane dispersions are those of the type known per se, such as are described in EP 469389 (US 559805). They are marketed, for example, under the brand name Daotan® by Allnex.
  • polyester oils for aqueous applications are WorleePol grades from WorleeChemie GmbH, Necowel® grades from Ashland-Südchemie-Kernfest GmbH, and Setalux® 6306 SS-60 from Nuplex Resins.
  • Emulsions, e.g., based on polyester, can also be used.
  • Polyesters/polyacrylates are described, for example, in EP 678536 (US Pat. No. 5,654,391).
  • polyester/polyacrylate secondary emulsion is Bayhydrol® VP LS 2139/2 (a product from Covestro AG).
  • Polyols for aqueous applications are otherwise known under the following brand names: Macrynal®, Viacryl®, Daotan® (polyester, polycarbonate, fatty acid-based, polyester-urethane-acrylic hybrids) from Allnex; Bayhydrol® from Covestro AG (polyacrylate, polyurethane, polyester/polyacrylate, polyester/polyurethane, fatty acid-modified polyester/polyacrylate, polycarbonate dispersions), Alberdingk® and Al Berdur® from Alberdingk Boley, Plusaqua® ( Alkyd, polyester, silicone polyester) from Omya, Necowel® from Ashland-Südchemie-Kernfest GmbH (alkyd resins), Neocryl® (e.g. AF-10: acrylic fluorocopolymer) from DSM Coating Resins
  • the aqueous dispersions used can contain the customary auxiliaries and additives. These include, for example, fillers such as quartz flour, quartz sand, highly disperse silicic acid, barite, calcium carbonate, chalk, dolomite or talc, which are often used together with suitable wetting agents such as polyphosphates such as sodium hexamethaphosphate, naphthalenesulfonic acid, ammonium or sodium polyacrylic acid salts Wetting agents are generally added in amounts of 0.2 to 0.6% by weight, based on the filler.
  • fillers such as quartz flour, quartz sand, highly disperse silicic acid, barite, calcium carbonate, chalk, dolomite or talc, which are often used together with suitable wetting agents such as polyphosphates such as sodium hexamethaphosphate, naphthalenesulfonic acid, ammonium or sodium polyacrylic acid salts
  • wetting agents are generally added in amounts of 0.2 to 0.6% by weight,
  • auxiliaries are, for example, organic thickeners to be used in amounts of 0.01 to 1% by weight, based on the dispersion, such as cellulose derivatives, alginates, starch or starch derivatives or polyacrylic acid, or in amounts of 0.05 to 5% by weight.
  • organic thickeners to be used such as bentonites.
  • Fungicides for preservation can also be added to the dispersions. These are generally used in amounts of 0.02 to 1% by weight, based on the dispersion. Suitable fungicides are, for example, phenol and cresol derivatives or organotin compounds.
  • Substrates for impregnations are, for example, synthetic or non-synthetic fibers or their woven or non-woven fabrics.
  • polyisocyanate preparations according to the invention can be dispersed in very finely divided form in aqueous dispersions.
  • less additional quantity of the water-emulsifiable polyisocyanate is required in order to set the desired properties of the dispersion or to achieve them in use.
  • the polyisocyanate preparations according to the invention can, of course, be admixed with the usual auxiliaries and additives used in paint technology. This includes for example defoamers, thickeners, leveling agents, pigments, emulsifiers, dispersing agents and also solvents.
  • the desired processing viscosity is set by adding water.
  • the coating compositions containing the polyisocyanate preparations according to the invention can be used in particular as primers, fillers, pigmented topcoats and clearcoats in the field of automotive refinishing or large vehicle finishing.
  • the coating compositions are particularly suitable for applications in which particularly high application safety, outdoor weather resistance, optics, solvent, chemical and water resistance are required, such as in car repairs and large vehicle coatings.
  • the coating compositions containing the polyisocyanate preparations according to the invention can be applied by a wide variety of spraying processes, such as air pressure, airless or electrostatic spraying processes using one- or two-component spraying systems, but also by spraying, spatula, doctor blade, brush, roller, Rolling, casting, laminating, back-injection molding or co-extrusion can be applied.
  • spraying processes such as air pressure, airless or electrostatic spraying processes using one- or two-component spraying systems, but also by spraying, spatula, doctor blade, brush, roller, Rolling, casting, laminating, back-injection molding or co-extrusion can be applied.
  • the water-emulsifiable polyisocyanate preparations according to the invention can advantageously be used as hardener components in addition to at least one binder in polyurethane coatings.
  • reaction with binders can optionally take place after a long period of time, which requires appropriate storage of the water-emulsifiable polyisocyanate preparation.
  • the binders can be, for example, polyacrylate polyols, polyester polyols, polyether polyols, polyurethane polyols; polyurea polyols; polyester polyacrylate polyols; polyester polyurethane polyols; polyurethane polyacrylate polyols; polyurethane-modified alkyd resins; fatty acid modified polyester polyurethane polyols; copolymers with allyl ethers; Graft polymers from the groups mentioned with For example, different glass transition temperatures, and mixtures of said binders act. Polyacrylate polyols, polyester polyols and poly urethane polyols are preferred.
  • the polyisocyanate preparation according to the invention is also suitable for modifying aqueous adhesives, for example based on aqueous dispersions with a solids content corresponding to a binder content of 10 to 65% by weight, preferably 20 to 60% by weight, such as natural latex, aqueous dispersions of homo or Copolymers of olefinically unsaturated monomers and the known aqueous polyurethane dispersions.
  • Suitable dispersions of homo- or copolymers of olefinically unsaturated monomers are, for example, known dispersions of homo- or copolymers based on vinyl esters of carboxylic acids having 2 to 18, preferably 2 to 4 carbon atoms, such as in particular vinyl acetate, optionally with up to 70% by weight on the total amount of olefinically unsaturated monomers, of other olefinically unsaturated monomers and/or of homo- or copolymers of (meth)acrylic acid, (meth)acrylic esters of alcohols having 1 to 18, preferably 1 to 8 carbon atoms, such as in particular (meth)acrylic , -methyl, -ethyl, -propyl, butyl, 2-ethylhexyl, -hydroxyethyl or -hydroxypropyl, - glycidyl esters, acetoacetoxyethyl (meth)acrylate), optionally together with up to 70 %
  • aqueous dispersions of copolymers of 90 to 99.5% by weight of acrylates or methacrylates of 1 to 4 carbon atom-containing alkanols and 0.5 to 10% by weight, based in each case on the copolymer, of hydroxyalkyl acrylates and methacrylates with 2 to 20 carbon atoms in the hydroxyalkyl radical, such as hyd roxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate.
  • Such dispersions are known per se and can be produced in the usual way by emulsion polymerization (see Houben-Weyl, Methods of Organic Chemistry, 4th edition, Vol. E 20,
  • Suitable aqueous polyurethane dispersions are those of the type known per se, as described, for example, in EP 469389 (US Pat. No. 5,598,05) or US Pat. No. 3,479,310.
  • the aqueous adhesives used can contain the auxiliaries and additives customary in adhesives technology. These include, for example, fillers such as quartz powder, quartz sand, highly dispersed silicic acid, heavy spar, calcium carbonate, chalk,
  • Dolomite or talc which are often used together with suitable wetting agents such as, for example, polyphosphates such as sodium hexametaphosphate, naphthalene sulfonic acids, ammonium or sodium polyacrylic acid salts, the wetting agents generally being used in amounts of 0.2 to 0.6% by weight, based on the filler, be added.
  • suitable wetting agents such as, for example, polyphosphates such as sodium hexametaphosphate, naphthalene sulfonic acids, ammonium or sodium polyacrylic acid salts
  • auxiliaries are, for example, organic thickeners to be used in amounts of 0.01 to 1% by weight, based on the adhesive, such as cellulose derivatives, alginates, starch or starch derivatives or polyacrylic acid, or in amounts of 0.05 to 5% by weight.
  • organic thickeners to be used in amounts of 0.01 to 1% by weight, based on the adhesive, such as cellulose derivatives, alginates, starch or starch derivatives or polyacrylic acid, or in amounts of 0.05 to 5% by weight.
  • inorganic thickeners such as bentonites:
  • Fungicides for preservation can also be added to the adhesives. These are generally used in amounts of 0.02 to 1% by weight, based on the adhesive. Examples of suitable fungicides are phenol and cresol derivatives or organotin compounds.
  • Tackifying resins such as natural or modified resins such as rosin or synthetic resins such as phthalate resins can also be present in the adhesive in known amounts.
  • Solvents such as toluene, xylene, butyl acetate, methyl ethyl ketone, ethyl acetate, dioxane or mixtures thereof or plasticizers such as those based on adipate, phthalate or phosphate can also be added to the aqueous adhesive dispersions.
  • the polyisocyanate preparations according to the invention are generally added to the aqueous adhesives in an amount of from 1 to 20% by weight, preferably from 2 to 10% by weight, based on the binder of the aqueous adhesive dispersion.
  • the nonaqueous polyisocyanate preparation according to the invention can be stirred into the adhesive dispersion in a known manner.
  • good results are achieved by first preparing an aqueous dispersion and mixing this with the adhesive dispersion.
  • aqueous adhesives modified in this way are suitable for bonding any materials of the same or different types, e.g. for bonding wood, paper, plastics, textiles, leather and inorganic materials such as ceramics, stoneware or asbestos cement.
  • the polymer dispersions can contain at least one further polyisocyanate component, in particular one based on a polyisocyanate containing a further ionic, nonionic, internal or external emulsifier. Internal, ionic emulsifiers are preferred.
  • HDI-based iminooxadiazinedione (produced analogously to example 3/1 in EP0962455) with an NCO content of 23.5% and a viscosity of 700 mPa*s at 23° C. (Basonat ®
  • HDI isocyanurate with an NCO content of 22.2% and a viscosity of 2800 mPa*s at 23° C. Basonat® HI 100 NG from BASF SE.
  • Monofunctional polyethylene oxide with an OH number of 112 (according to DIN 53240) and a molecular weight of 500 g/mol, started on methanol and produced with potassium hydroxide catalysis. The basic catalyst residues still present were then neutralized with acetic acid and the product was desalinated. This also removed potassium acetate formed.
  • the weight-average particle diameters were determined by light scattering measurements using an Autosizer 2c from Malven
  • polyisocyanate A leads to lower viscosity and thus smaller particle size in water (better dispersibility)

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Abstract

L'invention concerne un procédé de préparation d'une préparation de polyisocyanates émulsifiables dans l'eau, dans lequel, au cours d'une première étape de procédé (A), un produit de réaction de dispersion (E) est préparé à partir des composé suivants : au moins un diisocyanate, choisi dans le groupe comprenant le 1,6-hexaméthylène diisocyanate, le 1,5-pentaméthylène diisocyanate, le 4,4'-di(isocyanatocyclohexyl)méthane, le 1-isocyanato-3,3,5-triméthyl-5-(isocyanatométhyl) le 2,4 et le 2,6-toluylène diisocyanate, le tétraméthylxylylène diisocyanate, le p-xylylène diisocyanate et le 2,4' et le 4,4'-di(isocyanatodiphényl)méthane ; et au moins un alcool d'éther de polyalkylène mono ou polyvalent ayant 2 à 4 atomes de C dans les groupes alkylène et ayant une chaîne polyéther contenant au moins 8 motifs oxyde d'éthylène. Le produit de réaction résultant (E) est mélangé, lors d'une seconde étape de procédé (B), avec au moins un composé contenant un groupe iminooxadiazinedione, l'étape (B) étant réalisée en présence d'un catalyseur d'allophanation et les conditions étant choisies de telle sorte que les groupes allophanate sont formés à partir de (E) et du polyisocyanate, le procédé étant caractérisé en ce que le polyisocyanate (cyclo)aliphatique a une proportion de groupes iminooxadiazinedione, sur la base de la quantité totale de groupes isocyanurate et iminooxadiazine dione, supérieure ou égale à 20 % en moles.
PCT/EP2022/054525 2021-03-02 2022-02-23 Polyisocyanates émulsifiables dans l'eau présentant des propriétés améliorées WO2022184522A1 (fr)

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