WO2012130762A1 - Dispersions aqueuses de polyuréthane acrylate avec une structure de type peigne du polymère - Google Patents

Dispersions aqueuses de polyuréthane acrylate avec une structure de type peigne du polymère Download PDF

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WO2012130762A1
WO2012130762A1 PCT/EP2012/055228 EP2012055228W WO2012130762A1 WO 2012130762 A1 WO2012130762 A1 WO 2012130762A1 EP 2012055228 W EP2012055228 W EP 2012055228W WO 2012130762 A1 WO2012130762 A1 WO 2012130762A1
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weight
components
component
acid
isocyanate
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PCT/EP2012/055228
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Evgeny Avtomonov
Hans Georg Grablowitz
Thomas Feller
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Bayer Materialscience Ag
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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
    • C08G18/28—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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate 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
    • C08G18/28—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
    • C08G18/83—Chemically modified polymers
    • C08G18/833—Chemically modified polymers by nitrogen containing compounds

Definitions

  • the present invention relates to an aqueous dispersion comprising a polymer which is obtainable by the reaction of mixture comprising a polyisocyanate, a polyol and an oligoacrylate telechelic.
  • the invention further concerns a method for the production of such a dispersion and its use in coatings and/or adhesives.
  • Polyurethane acrylate dispersions have been known for some time and are usually used as coatings. These polymers contain polyurethane and polyacrylate polymer chains which generally are immiscible (insoluble within each other). If the properties of the phases in question are tailored with respect to each other, polymers may result whose properties are a synergistic result of the properties of the individual homopolymers.
  • Polyurethanes for example, have advantageous mechanical properties, cold flexibility and abrasion resistance. Advantages of polyacrylates include resistance to chemicals and a comparatively low price.
  • hybrid dispersions are frequently prepared in such a manner that a radical polymerization of the vinylic acrylate monomers is conducted in the presence of a polyurethane dispersion.
  • the compatibility of the polymers may be increased if the polyurethane dispersion contains double bonds so that the polyacrylate polymer chains may be covalently bonded to the polyurethane chains. This may have the effect that the polyurethane and polyacrylate components are no longer phase separable, i. e. phase incompatibilities are at most present on a molecular scale, but the system displays a uniform behavior in optical and in most of macroscopic measurements.
  • EP 0 649 865 Al which relates to aqueous self-cross-linking binders comprising polyhydrazides and carbonyl-containing urethane- vinyl hybrid polymers and optionally conventional additives.
  • aqueous binders for coatings and adhesives many final properties are determined by the molecular weight of the corresponding polymers. High molecular weights are most often associated with favorable properties such as a good solvent resistance and good mechanics. However, too high molecular weight polymers or partially cross-linked polymers are difficult to process and to apply as films because the polymer chains have difficulty in interpenetrating each other. Then no continuous film can be formed. Therefore a great amount of polymer dispersions have been developed that only during or after the film formation raise the molecular weight via a self cross-linking mechanism and therefore display more favorable final properties.
  • a polyfunctional condensation agent such as polyamines or dicarboxylic acid dihydrazides.
  • the oligoacrylate telechelics required for the production of the hybrid polymers may be synthesized by various methods which fall into the categories of free and controlled radical polymerization.
  • the controlled methods such as the atom transfer radical polymerization (ATRP) or the reversible addition fragmentation chain transfer (RAFT) polymerization are rather new and have not been employed widely in industry. In these methods sometimes components are used that need to be removed later such as copper salts in the ARTP.
  • ATRP atom transfer radical polymerization
  • RAFT reversible addition fragmentation chain transfer
  • US 4,818,804 relates to a polycondensable macromonomer containing dihydroxy or dicarboxy groups which is an oligomer having two hydroxy or carboxy groups at the terminal of vinyl polymer chain of the following formula: wherein R is OH or COOH, R 1 , R 2 and R 3 are the same or different and are each a single bond or an alkylene having 1 to 4 carbon atoms, R 4 is hydrogen atom or an alkyl having 1 to 4 carbon atoms, R 5 is hydrogen atom or methyl, X is an alkyloxycarbonyl having 2 to 15 carbon atoms, a substituted alkyloxycarbonyl having 2 to 1 5 carbon atoms in the alkyloxycarbonyl moiety, a cycloalkyloxycarbonyl having 3 to 7 carbon atoms in the cycloalkyl moiety, or phenyl, and n is an integer of from 1 to lxl 0 4 , which is useful as an intermediate for the production of a poly
  • EP 0 896 981 A l (WO 97/23526 A l ) describes macromonomers and carboxyl functional polyurethanes having a high carboxyl content.
  • the application further describes dispersions, coatings and magnetic recording media comprising these polyurethanes, or blends or copolymers of these polyurethanes with quaternary ammonium polymers or compounds.
  • Claimed is a carboxylic acid functional graft carboxyl polyurethane polymer comprising the reaction product of a mixture comprising: (a) one or more polyisocyanates;
  • the reported polymers are dissolved in organic solvents, do not contain carbonyl groups and are especially suited for pigmented systems. No information is given whether these polymers are dispersible in water and whether these polymers are suitable as binders.
  • US 5,277,945 discloses a resin composition for coating, comprising as main components: (A) a graft polymer obtained by reacting (a) at least one polymer polyol selected from polyester polyols, polyether polyols and polyether polyester polyols having a number-average molecular weight of 500- 6,000, (b) a polymer having two hydroxyl one end, and (c) a polyisocyanate compound, and (B) a cross-linking agent selected from polyisocyanate compounds and amino resins.
  • This composition gives a coating film excellent in flexibility, hardness, stain resistance, etc.
  • the reported polymers do not contain hydrophilic groups and are dissolved in N-methylpyrrolidone as a solvent which is undesirable from an ecological and labor hygiene perspective.
  • US 2003/004264 Al on the other hand is concerned with a method for the production of self- emulsifiable, aqueous polyurethane resins having improved characteristics in which: a) first a premix of polyol component (A), consisting of 5 to 25 parts by weight of at least one diol (A) (i) having a molar mass of 500 to 5000 Dalton, 0.5 to 5 parts by weight of at least one polyhydroxyalkane (A) (ii) and 0 to 5 parts by weight of at least one anionically modifiable dihydroxyalkanecarboxylic acid (A) (iii), and 0 to 9 parts by weight of a solvent component (B) is prepared, b) 5 to 50 parts by weight of a polyisocyanate component (C) is reacted with 1 1 to 39 parts by weight of the premix from stage a) to give a polyurethane preadduct, c) the polyurethane preadduct from stage b) is reacted with
  • EP 105 6814 Al discloses pigmented inks comprising a liquid medium, a pigment, and a polyurethane dispersant, the pigment being stabilized by the polyurethane dispersant, and the ink being suitable for use in an ink jet printer.
  • the acrylate telechelics as described in some of the examples may possess hydrophilic groups, making them suitable for dispersion in water.
  • a disadvantage of the dispersions described in this patent application is that the reported solids contents between 15% and 20% render their use as binder uneconomical.
  • the present invention has the object of providing such dispersions. According to the invention this object is achieved by an aqueous dispersion comprising a polymer which is obtainable by the reaction of:
  • the polymers present in the dispersions according to the invention display a mostly comb-like structure and can be cross-linked via the carbonyl groups of the oligoacrylate telechelic side chains and a suitable cross-linking agent in a subsequent reaction or subsequent reactions during or after the film formation.
  • Suitable polyisocyanates of component A) are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates that are known as such to a person skilled in the art.
  • Suitable polyisocyanates include, without being limited to, 1,4-butylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6- hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and/or 2,4,4- trimethylhexamethylene diisocyanate, the isomeric bis(4,4'-isocyanatocyclohexyl)methanes or mixtures thereof with arbitrary isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-
  • Polyisocyanates with a functionality > 2 may also be used proportionately. These include modified diisocyanates with uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure and also non-modified polyisocyanates with more than 2 NCO groups per molecule, for example 4-isocyanatomethyl-l,8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4-4'-4"-triisocyanate.
  • the polyisocyanates of component 1) may be used alone or as mixtures of each other.
  • Their hydroxyl value amounts to 22 mg KOH/g to 1800 mg KOH/g, preferably 30 mg KOH/g to 1800 mg KOH/g and particularly preferably 40 mg KOH/g to 1800 mg KOH/g, and they exhibit an OH functionality from 1.5 to 6, preferably from 1.8 to 3 and particularly preferably from 1.9 to 2.1.
  • Polyols in the sense of the present invention are the organic polyhydroxyl compounds known in polyurethane-lacquer technology, such as, without being limited to, the customary linear or branched polyalkylene dialcohols with 2 to 30 C atoms such as 1,2-ethylene glycol, 1,3-propane diol, 1,4- butane diol, 1,5-pentane diol, l,3-(3-methyl)pentane diol, 1,6-hexane diol, 1,7-heptane diol, 1,8- octane diol, 1,9-nonane diol, 1, 10-decane diol, 1, 11-undecane diol, 1, 12-dodecane diol, polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and also polyurethane polyacrylate polyols
  • polyether polyols By way of polyether polyols, mention may be made, for example, of the polyaddition products of the styrene oxides, of ethylene oxide, propylene oxide, tetrahydrofurane, butylene oxide, of epichlorohydrin and also their mixed-addition products and graft products, and also the polyether polyols obtained by condensation of polyhydric alcohols or mixtures of the same, and the polyether polyols obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols.
  • Suitable hydroxyl-functional polyethers 2 exhibit OH functionalities from 1.8 to 6.0, preferably 2.0 to 4.0, OH values from 50 mg KOH/g to 700 mg KOH/g, preferably from 100 mg KOH/g to 600 mg KOH/g solids, and number average molecular weights M n from 106 g/mol to 4000 g/mol, preferably from 200 g/mol to 3500 g/mol, such as, for example, alkoxylation products of hydroxyl- functional initiator molecules such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, glycerin, pentaertythritol, sorbitol or mixtures of these and also of other hydroxyl-functional compounds with propylene oxide or butylene oxide.
  • polyether component B Preferred by way of polyether component B) are polypropylene oxide polyols with a molecular weight from 300 g/mol to 4000 g/mol.
  • the particularly low-molecular polyether polyols with appropriately high OH contents may be water-soluble.
  • Particularly preferred, however, are water-insoluble polypropylene oxide polyols and polytetramethylene oxide polyols, polycarbonate polyols and also mixtures thereof.
  • polyester polyols are the poly condensates, known as such, formed from diols and also optionally triols and tetraols and dicarboxylic and also optionally tricarboxylic and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of low alcohols may also be used for producing the polyesters.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3 -propanediol, butanediol(l,3), butanediol(l,4), hexanediol(l,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester, the three last-named compounds being preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3 -propanediol, butanediol(l,3), butanediol(l,4), hexanediol(l,6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester
  • polyols to be optionally employed concomitantly are, for example, trimethylolpropane, glycerin, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • dicarboxylic acids By way of dicarboxylic acids, the following enter into consideration, for example: phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2- methylsuccinic acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid.
  • phthalic acid isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid,
  • Anhydrides of these acids can likewise be used, to the extent that they exist For the purposes of the present invention, the anhydrides are consequently encompassed by the expression "acid”.
  • Monocarboxylic acids such as benzoic acid and hexanecarboxylic acid, may also be used, provided that the average functionality of the polyol is > 2.
  • Saturated aliphatic or aromatic acids are preferred, such as adipic acid or isophthalic acid.
  • trimellitic acid may be mentioned here.
  • Hydroxycarboxylic acids that can be used concomitantly as co-reactants in the preparation of a polyester polyol having terminal hydroxyl groups are, for example, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and such like.
  • Usable lactones are, inter alia, caprolactone, butyrolactone and homologues.
  • polyester polyols 2) based on butanediol and/or neopentyl glycol and/or hexanediol and/or ethylene glycol and/or diethylene glycol with adipic acid and/or phthalic acid and/or isophthalic acid.
  • Particularly preferred are polyester polyols 2) based on butanediol and/or neopentyl glycol and/or hexanediol with adipic acid and/or phthalic acid.
  • the polycarbonate polyols entering into consideration are obtainable by reaction of carbonic-acid derivatives, for example diphenyl carbonate, dimethyl carbonate or phosgene, with diols.
  • the diol component preferably contains 40 weight-% to 100 weight-% 1,6-hexanediol and/or hexanediol derivatives, preferentially those which exhibit ether groups or ester groups in addition to terminal OH groups, for example products that are obtained by conversion of 1 mol hexanediol with at least 1 mol, preferably 1 mol to 2 mol, ⁇ - caprolactone, or by etherification of hexanediol with itself so as to yield dihexylene glycol or trihexylene glycol.
  • Polyether polycarbonate polyols may also be employed.
  • polycarbonate polyols as component 2) based on dimethyl carbonate or diethyl carbonate and hexanediol and/or pentanediol and/or butanediol and/or caprolactone.
  • polycarbonate polyols 2) based on dimethyl carbonate and 1,4-butanediol and/or 1,5-pentanediol and/or l,5-(3-methyl)pentane diol and/or hexanediol and/or caprolactone.
  • a telechelic oligomer or polymer is a di-end-functional polymer where both ends possess the same functionality.
  • Suitable oligoacrylate telechelics 3) are produced in a free radical polymerization of double bond- containing monomers in a solvent or in substance together with a thio-functionalized diol as a molecular weight regulator.
  • Suitable monomers include the known vinyl group containing monomers such as acrylic or methacrylic esters and other vinyl-containing compounds.
  • (meth)acrylate denotes acrylates, methacrylates and their mixtures.
  • Suitable methacrylic esters include in particular methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-octyl methacrylate, ethyl hexylmethacrylate, nonyl methacrylate, 2-methyloctyl methacrylate, 2-tert.-butylheptyl methacrylate, 3-iso-propylheptyl methacrylate, decyl methacrylate, undecyl methacrylate, 5-methylundecyl
  • the methacrylic acid derivatives may also be employed in form of the corresponding nitriles or amides such as methacrylic nitrile or methacrylic amide.
  • Suitable esters of acrylic acid include in particular methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl-acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-octyl acrylate, ethylhexyl acrylate, nonyl acrylate, 2- methyl-octyl acrylate, 2-tert.-butylheptyl acrylate, 3-iso-propylheptyl-acrylat, decyl acrylate, undecyl acrylate, 5-methylundecyl acrylate, dodecyl acrylate, 2-methyldodecyl acrylate, tridecyl acrylate, 5- methyltridecyl acrylate, tetrade
  • vinyl esters of organic acids such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl esters of the so-called versatic acid (branched carboxylic acids with 9 to 10 C-atoms) which are sold under the trade mark Veova® 9 and Veova® 10 (Momentive Specialty Chemicals).
  • Suitable vinylic aromatics with up to 20 C-atoms include styrene, vinyl toluene, o- and p-methylstyrene, a-butyl styrene, 4-n-butyl styrene, 4-n-decyl styrene, halogenated styrenes such as monochloro styrene, dichloro styrenes, tribromo styrenes, and tetrabromo styrenes. Styrene is preferred.
  • Suitable olefinically unsaturated, acid-functionalized monomers for the production of 3) are sulphonic, phosphonic or carboxylic acid functionalized monomers, preferably carboxylic acid functionalized monomers such as acrylic acid, methacrylic acid, ⁇ -carboxyethyl acrylate, crotonic acid, fumaric acid, malic acid anhydride, itaconic acid or monoalkyl ester of dicarboxylic acids or their anhydrides such as maleic acid monoalkyl esters. Particularly preferred are acrylic or methacrylic acid, most preferred is acrylic acid.
  • the functionalization of the acrylate 3) with carbonyl groups take place via the copolymerization with carbonyl containing monomers.
  • carbonyl containing monomers include diacetone acrylic amide, acetoacetoxyethyl methacrylate and acetoactetoxyethyl acrylate.
  • Carbonyl functionalized compounds are those in which a carbonyl group is present in form of a keto or aldehyde group.
  • Preferably 1-50 weight-%, particularly 5-30 weight-% of the carbonyl-containing monomer is used with respect to the acrylate phase.
  • Suitable isocyanate-reactive mercapto compounds for building the telechelics include 2-mercapto- 1,3 -propanediol, 1 -mercapto- 1, 1-methanediol, 1 -mercapto- 1, 1-ethanediol, 2 -mercapto- 1,2- propanediol, 2-mercapto-2 -methyl- 1,2-propanediol, 2-mercapto-2 -ethyl- 1,2-propanediol, 3- mercapto- 1 ,2-propanediol, 1 -mercapto-2,2-propanediol, 2-mercaptomethyl-2 -methyl- 1,3- propanediol, 2-mercaptoethyl-2-ethyl-l,3-propanediol, 2-mercaptomethyl-2-methyl-l,3-propanediol, etc.
  • 3 -mercapto- 1,2-propanediol is used
  • the initiation of the polymerization is undertaken by means of initiators known for the free radical polymerization.
  • initiators known for the free radical polymerization.
  • These include hydrogen peroxide, hydroperoxides such as tert. -butyl hydroperoxide, dialkyl peroxides such as di-tert. -butyl peroxide, diacylperoxides, peroxy esters, peroxy carbonates, peroxy dicarbonates and peroxyketals.
  • water-soluble inorganic persulfates such as ammonium or sodium persulfate.
  • azo initiators such as azodiisobutyronitrile can be used.
  • the initiators can be used as redox initiators by the addition of suitable reducing agents.
  • Suitable reducing agents include sodium disulphite, sodium formaldehyde or isoascorbic acid.
  • the polymerization is performed in the presence of 0.05 to 5 weight-% of initiator with respect to the solids. More preferred are 0.2 to 3.0 weight-%.
  • the polymerization takes place at elevated temperatures and in substance or in solution.
  • Solvents known to the skilled person such as alcohols, ethers, ketones, aldehydes, chloroalkanes, aromatic and aliphatic hydrocarbons may be used.
  • the polymerization is performed in substance or in a solvent which can be removed by distillation after the graft polymers have been formed.
  • solvents with a boiling point at standard pressure 56 to 140 °C, preferably 56 to 100 °C, more preferred 56 to 82 °C.
  • Particularly preferred solvents include acetone, THF and methyl ethyl ketone.
  • the solvents can be used in pure form or as mixtures.
  • Suitable hydrophilic isocyanate-reactive compounds 4) are ionic or potentially ionic and/or non-ionic compounds.
  • Suitable compounds 4) having a non-ionic hydrophilising action are, for example, polyoxyalkylene ethers which contain at least one hydroxy or amino group. These poly ethers contain an amount of from 30 to weight- % structural units derived from ethylene oxide.
  • poly ethers having a linear structure and a functionality of from 1 to 2, but also compounds of the general formula HO-R ⁇ C ⁇ iR ⁇ -R ⁇ OH, in which R 1 and R 2 each independently of the other denotes a divalent aliphatic, cycloaliphatic or aromatic radical having from 1 to 18 carbon atoms, which can be interrupted by oxygen and/or nitrogen atoms, and R 3 represents an alkoxy-terminated polyethylene oxide radical.
  • Compounds 4) having a non-ionic hydrophilising action are, for example, also monovalent polyalkylene oxide polyether alcohols having in the statistical mean from 5 to 70, preferably from 7 to 55 ethylene oxide units per molecule, as are obtainable by alkoxylation of suitable starter molecules (cf. Ullmans Encyclopedia of Technical Chemistry, 4th edition, volume 19, Verlag Chemie, Weinheim, pages 31-38).
  • Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n- propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, for example diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1, 1-dimethylallyl alcohol or
  • Suitable alkylene oxides for the alkoxylation reaction are in particular ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any desired sequence or in admixture.
  • the number average molecular mass M n of these structural units amounts to 300 g/mol to 6000 g/mol, preferably 500 g/mol to 4000 g/mol and particularly preferably 750 g/mol to 3000 g/mol with a functionality of 1.
  • Suitable non-ionically hydrophilising, monofunctional compounds of such a type are, for example, monofunctional alkoxypolyethylene glycols such as, for example, methoxypolyethylene glycols (MPEG Carbowax® 2000 or Methoxy PEG-40, molecular-weight range 1800 to 2200, The Dow Chemical Company), monofunctional polyether monoalkyl ethers such as, for example, LB 25 synthesized from butanol and ethylene oxide and also propylene oxide, with an average molecular mass M n of 2250 g/mol from Bayer Material Science, monofunctional polyether amines (Jeffamine® M 1000, PO/EO molar ratio 3/19 and M 2070, PO/EO molar ratio 10/31, Huntsman Corp.).
  • monofunctional alkoxypolyethylene glycols such as, for example, methoxypolyethylene glycols (MPEG Carbowax® 2000 or Methoxy PEG-40, molecular-weight range 1800 to 2200, The Dow Chemical Company
  • MPEG Carbowax® 2000, LB 25 or Jeffamine® M 2070 Preferably employed are MPEG Carbowax® 2000, LB 25 or Jeffamine® M 2070. Particularly preferred are MPEG Carbowax® 2000 or LB 25.
  • Component 4) comprises ionic groups, which can be of either cationic or anionic nature, and/or non- ionic hydrophilic groups.
  • Compounds having a cationic, anionic or non-ionic dispersing action are those which contain, for example, sulfonium, ammonium, phosphonium, carboxylate, sulfonate, phosphonate groups or groups which can be converted into the above-mentioned groups by salt formation (potentially ionic groups), or polyether groups, and which can be incorporated into the macromolecules by isocyanate-reactive groups that are present.
  • Preferred isocyanate-reactive groups that are suitable are hydroxyl and amine groups.
  • Suitable anionic or potentially anionic compounds are, for example, mono- and di- hydroxycarboxylic acids, mono- and di-aminocarboxylic acids, mono- and di-hydroxysulfonic acids, mono- and di-aminosulfonic acids, mono- and di-hydroxyphosphonic acids, mono- and di- aminophosphonic acids and their salts, such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N-(2-aminoethyl)-alanine, 2-(2-amino-ethylamino)-ethanesulfonic acid, ethylenediamine-propyl- or -butyl-sulfonic acid, 1,2- or 1,3-propylenediamine-ethylsulfonic acid, 3- (cyclohexylamino)propane-l -sulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, tau
  • Suitable cationic structural units or structural units which can be converted into cationic groups are, for example, ethanolamine, diethanolamine, triethanolamine, 2-propanolamine, dipropanolamine, tripropanolamine, N-methylethanolamine, N-methyldiethanolamine and N,N- dimethylethanolamine .
  • Particularly preferred ionic or potentially ionic compounds are those which contain carboxyl and/or sulfonate and/or ammonium groups as ionic groups and have a functionality of 1.9 to 2.1.
  • Preferred ionic compounds have an amine functionality of 1.9 to 2.1 and contain sulfonate groups as ionic or potentially ionic groups, such as the salts of N-(2-aminoethyl)- -alanine, 2-(2-amino-ethylamino-) ethanesulfonic acid or the addition product of isophoronediamine and acrylic acid (EP 916 647 Al, Example 1).
  • the chain extender compounds 5) generally have a functionality between 1 and 2 and are, for example, di- or polyamines or hydrazides.
  • Examples include ethylenediamine, 1,2- and 1,3- propylenediamine, 1,4-butylenediamine, 1,6-hexam ethylenediamine, isophoronediamine, isomer mixtures of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, 1,3- and 1,4-xylylenediamine, a,a,a',a'-tetramethyl-l,3- and 1,4-xylylenediamine and 4,4'-dicyclohexylmethanediamine, dimethylethylenediamine, hydrazine or adipic acid dihydrazide.
  • compounds 5 are in principle compounds that contain active hydrogen with varying reactivity with respect to NCO groups, such as compounds that exhibit, in addition to a primary amino group, also secondary amino groups or, in addition to an amino group (primary or secondary), also OH groups.
  • Examples of these are primary/secondary amines, such as 3-amino-l-methylaminopropane, 3-amino-l-ethylaminopropane, 3 -amino- 1- cyclohexylaminopropane, 3-amino-l-methylaminobutane, furthermore alkanolamines such as N- aminoethylethanolamine, ethanolamine, 3-aminopropanol or neopentanolamine.
  • Preferred are diethanolamine and/or hydrazine and/or isophoronediamine (IPDA) and/or ethylenediamine.
  • IPDA isophoronediamine
  • ethylenediamine Particularly preferred are hydrazine and/or isophoronediamine and/or ethylenediamine.
  • a mixture of hydrazine and IPDA is a mixture of hydrazine and IPDA.
  • the chain extension of NCO-group containing polyurethane polyacrylate polymer may be undertaken in situ by reaction with water. Then water from the dispersion may react with the free NCO groups of the prepolymer under formation of the corresponding carbamic acid groups, liberation of carbon dioxide and formation of amino groups. These in turn can react with further NCO groups of the prepolymer and thus lead to a chain extension.
  • Suitable polyfunctional components 6) are such compounds that react with the carbonyl groups from component 3) under mild conditions. At least two such reactive functional groups need to be present for a cross-linking reaction to take place.
  • the component 6) should be at least partially soluble in water so that the cross-linking reaction occurs while or during drying.
  • these compounds include bishydrazides of carboxylic acids like oxalic acid, adipic acid, pimelic acid, suberic acid,vestic acid, sebacic acid, or the isomers of phthalic acid.
  • bishydrazines such as ⁇ , ⁇ -diaminopiperazine and bishydrazides of diketones and dialdehydes.
  • Further suitable compounds 6) are polyamines with a functionality of 2 or higher.
  • adipic acid dihydrazide, oxalic acid dihydrazide and isophorone diamine are used.
  • the PUA dispersions according to the invention may be produced by all methods known in the art such as the prepolymer mixing process, acetone process or melt dispersion process. Preference is given to the acetone process.
  • the components 1) to 6) are present in the following amounts:
  • the components 1) to 6) are present in the following amounts: 1) > 8 weight-% to ⁇ 44 weight-% of a polyisocyanate;
  • the telechelic 3 has a number- average molecular weight of > 250 g/mol to ⁇ 8000 g/mol.
  • the molecular weight can be determined by gel permeation chromatography against a polystyrene standard with THF as the eluent at a flow rate of 0.6 mL/min at 25 °C.
  • the ratio of initiator to monomers and molecular weight regulators can determine the molecular weight of the final product. In general, higher concentrations of initiators and molecular weight regulators lead to lower molecular masses.
  • Preferred number-average molecular weights M n are > 500 g/mol to ⁇ 5000 g/mol.
  • the telechelic 3 has a glass transition temperature of > -50 °C to ⁇ 100 °C, the glass transition temperature being determined by differential scanning calorimetry according to DIN 65467 at a heating rate of 20 K min.
  • the glass transition temperature is >—30 °C to ⁇ 100 °C.
  • the glass transition temperature in the telechelics is controlled by the type and amount of monomers used.
  • glass transition temperature is to be understood in the conventional meaning: as the temperature at which the polymer transitions from a glass-like state into a state with a higher segment mobility in the polymer chain.
  • the glass transition temperature can also be calculated according to the Fox equation (Bulletin of the American Physical Society 1 , 2, page 123, 1956):
  • the polyisocyanate 1) is isophorone diisocyanate and/or hexamethylene diisocyanate and wherein the polyol 2) is a mixture comprising polyester polyol obtainable by the reaction of adipic acid, hexane diol and neopentyl glycol and comprising a polyether polyol obtainable by the reaction of ethylene oxide and propylene oxide with a monofunctional starter compound.
  • the telechelic 3 is obtainable by the reaction of a mixture comprising n-butyl methacrylate, diacetone acrylic amide, thioglycerine and a radical initiator.
  • the polyfunctional component 6) which can react with the carbonyl groups of telechelic 3) is adipic acid dihydrazide.
  • a further aspect of the present invention is a method for the production of a dispersion according to the invention, comprising the steps of: reacting the components 1) to 4) to yield an isocyanate group containing prepolymer; adding an Nt1 ⁇ 4- or NH-functional component 5) to yield a chain-extended polymer; - dispersing the resulting polymer in water; and adding component 6) to the aqueous dispersion obtained in the previous step.
  • the constituents 2), 3), and 4 which must not exhibit any primary or secondary amino groups
  • the polyisocyanate component 1) for producing an isocyanate-functional polyurethane prepolymer are charged wholly or partially and optionally diluted with a solvent that is miscible with water but inert with respect to isocyanate groups and are heated up to temperatures within the range from 50 °C to 120 °C.
  • the catalysts known in polyurethane chemistry may be employed. Dibutyltin dilaurate is preferred.
  • Suitable solvents are the customary aliphatic, keto-functional solvents such as, for example, acetone, butanone, tetrahydroiurane, methyl acetate or ethyl acetate which may be added not only at the start of the production but optionally also later in portions. Preferred are acetone and butanone. Mixtures of solvents may also be used. Subsequently constituents 1) to 6) optionally not yet added at the start of the reaction are added in metered amounts.
  • the mole ratio of isocyanate groups to groups reactive with isocyanate amounts to 1.0 to 3.5, preferably 1.05 to 3.0, particularly preferably 1.1 to 2.5.
  • the conversion of components 1), 2), 3) and 4) to the prepolymer is effected partially or totally, but preferably totally. In this way, polyurethane prepolymers that contain free isocyanate groups are obtained in bulk or in solution.
  • the prepolymer obtained is dissolved with the aid of solvents that are inert towards NCO groups, if this has not yet happened or has only partially happened.
  • chain lengthening/termination may be carried out either in solvent prior to the dispersing, during the dispersing, or in water after the dispersing.
  • the chain lengthening is preferably carried out prior to the dispersal in water.
  • the degree of chain lengthening-that is to say, the equivalent ratio of NCO-reactive groups of the compounds employed for chain lengthening to free NCO groups of the prepolymer- is between 40% and 100%, preferably between 60% and 100%, particularly preferably between 70% and 100%.
  • the components 4) and 5) may optionally be employed individually or in mixtures in water-diluted or solvent-diluted form in the process according to the invention, whereby in principle any sequence of addition is possible. If water or organic solvents is/are used concomitantly as diluent(s), the diluent content preferably amounts to 70 weight-% to 95 weight-%.
  • the production of the polyurethane-acrylate dispersion from the prepolymers is undertaken subsequent to the chain lengthening.
  • the dissolved and chain-lengthened polyurethane polymer-optionally subject to strong shear such as, for example, vigorous stirring-is either charged into the dispersing water or, conversely, the dispersing water is stirred into the prepolymer solutions.
  • strong shear such as, for example, vigorous stirring-is either charged into the dispersing water or, conversely, the dispersing water is stirred into the prepolymer solutions.
  • the water is preferably added into the dissolved prepolymer.
  • the solids content of the dispersion according to the invention is between 20 weight-% and 70 weight-%, preferably between 30 weight-% and 65 weight-% and particularly preferably between 35 weight-% and 62 weight-%.
  • the present invention is furthermore concerned with the use of a dispersion according to the invention for the manufacture of coatings and/or adhesives.
  • Substrates for the coatings may be, for example, wood, plastics, metal, glass, textiles, leather, paper and fibers such as glass fibers, polymer fibers and graphite fibers.
  • Adhesives may be useful, for example, in the case of substrates such as woven and non-woven textiles, leather, paper, fiberboard, straw, paper-like materials, wood, glass, all sorts of plastics, ceramics, stone, concrete, bitumen, porcelain, metal or glass fibers.
  • aqueous coatings and/or adhesives comprising a dispersion according to the invention may contain auxiliary substances and additives as a further component. These may be co-binders, thickeners, adhesion-promoters, lubricants, wetting agents, defoamers, antistatic agents, but also the lacquer additives well known as such to a person skilled in the art, such as dyestuffs, pigments, flow- control agents, light-screening agents and anti-ageing agents, as well as UV absorbers.
  • the dispersions according to the invention may be used as a component in water-based lacquers and adhesive formulations for the coating of surfaces and for joining substrates.
  • the dispersions according to the invention are combined with further components such as aqueous dispersions based on polyesters, polyurethanes, polyurethane-polyacrylates, alkyd resins, polymerisates, polystyrene-butadienes, polyacrylonitrile-butadienes, polyvinyl acetates, polyethylene vinylacetates, polypropylenes, polyamides/polyimides or polyepoxides.
  • the coatings can be applied by various means such as air pressure, airless or electrostatic spraying with one- or two-component spraying systems. Other suitable methods include brushing, rolling, dipping, printing or doctor blading.
  • Desmophen® PE 170 HN Polyester polyol based on adipic acid, hexane diol and neopentyl glycol with an OH number of 66 mg KOH/g and a molecular mass M n of 1700 g/mol (Bayer MaterialScience AG, DE
  • Polyether LB 25 Monoiunctional polyether polyol based on ethylene oxide/propylene oxide with an ethylene oxide content of 84%, an OH number of 25 mg KOH/g and a molecular mass M n of 2250 g/mol (Bayer MaterialScience AG, DE)
  • Desmodur® I IPDI, Isophorone diisocyanate (Bayer Materialscience AG, DE)
  • Desmodur® H HDI, 1,6-hexamethylene diisocyanate (Bayer MaterialScience AG, DE)
  • IDPA Isophorone diamine (Bayer MaterialScience AG, DE)
  • AAS Diamino sulphonate, 45% in water, H 2 N-CH2-CH2-NH-CH2-CH 2 -S0 3 Na (Bayer MaterialScience AG, DE)
  • HyHy Hydrazine hydrate, CAS 302-01-2 (Aldrich, DE)
  • AIBN Azobisisobutyro nitrile, CAS 764-28-3 (Aldrich, DE)
  • DAAM Diacetone acrylic amide, CAS 2873-97-4 (Aldrich, DE)
  • nBMA n-Butyl methacrylate, CAS 97-88-1 (Aldrich, DE)
  • Molecular weight The determination of the molecular weight was carried out by gel permeation chromatography against a polystyrene standard with THF as the eluent at a flow rate of 0.6 mL/min at 25 °C. Detectors were a UV and an RI detector by ERC.
  • Particle size The mean particle size was determined by laser correlation spectroscopy with a Malvern Zetasizer 1000 (Malvern Instruments, Ltd.) and expressed as mean in Z.
  • Solids content The solids content was determined according to DIN EN ISO 3251.
  • the OH number was determined according to DIN 53240/2.
  • NCO content The NCO content was determined according to DIN EN ISO 11 909.
  • a 2 L reaction vessel was equipped with a stirrer and a reflux condenser and charged with 600 g acetone, 300 g nBMA, 100 g DAAM, 6 g TGLY and 6 g AIBN. The reaction mixture was refluxed for six hours. A product with a resin content of 40.7 weight-% and a number average molecular weight M n of 1000 g/mol was obtained.
  • Example 1 was repeated, the difference being that 300 g of acetone were used instead of 600 g. A product with a resin content of 57.9 weight-% and a number average molecular weight M n of 3100 g/mol was obtained.
  • Example 3 Synthesis of a polyurethane acrylate dispersion according to the invention
  • Chain lengthening was effected by addition of 13.3 g of IPDA in 23.6 g of acetone within five minutes, followed by 7.1 g AAS salt 0.5 g hydrazine in 27.5 g of water within 20 minutes.
  • the dispersion step was undertaken by adding 792 g water within 30 minutes. To this dispersion was added 7 g ASDH. The final product was a dispersion with a solids content of 31.5% and a mean particle size of 235 nm.
  • Example 4 Comparative example Example 3 was repeated, the difference being that no ASDH was added.
  • Example 5 Gel contents The gel content of the polymer according to example 3 was determined to be 94%, whereas the gel content in the polymer of the comparative example was 76%. An interpretation is that the polyurethane acrylate dispersions of the invention cross-link during film formation, giving rise to the high gel content.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une dispersion aqueuse comprenant un polymère qui peut être obtenu par la réaction de : 1) ≥ 1 % en poids à ≤ 97,5 % en poids d'un polyisocyanate; 2) ≥ 0 % en poids à ≤ 75 % en poids d'un polyol ; 3) ≥ 1 % en poids à ≤ 97,5 % en poids d'un polymère téléchélique d'oligoacrylate difonctionnel qui peut être obtenu par une polymérisation radicalaire de monomères contenant un groupe carbonyle par transfert de chaîne en utilisant un thiol à fonction dihydroxy ; 4) ≥ 1 % en poids à ≤ 15 % en poids d'un agent hydrophilisant ionique et/ou non ionique réactif avec les isocyanates ; 5) ≥ 0 % en poids à ≤ 10 % en poids d'un composé réactif avec les isocyanates différent des composants 1) à 4) ; 6) ≥ 0,5 % en poids à ≤ 10 % en poids d'un composant polyfonctionnel capable de réagir avec les groupes carbonyle du composant 3) ; les pourcentages pondéraux des composants 1) à 6) s'additionnant pour atteindre ≤ 100 % en poids. L'invention concerne en outre un procédé de production d'une telle dispersion et son utilisation dans des revêtements et/ou des adhésifs.
PCT/EP2012/055228 2011-03-28 2012-03-23 Dispersions aqueuses de polyuréthane acrylate avec une structure de type peigne du polymère WO2012130762A1 (fr)

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WO2016016286A1 (fr) * 2014-08-01 2016-02-04 Basf Se Procédé de production et d'utilisation de dispersions aqueuses hybrides polyuréthane-polyacrylate ainsi que leur utilisation dans des produits de revêtement
CN107722187A (zh) * 2017-10-23 2018-02-23 广东华斓汽车材料研究院 一种丙烯酸酯改性聚氨酯水分散体的制备方法及其应用
CN108467471A (zh) * 2018-04-04 2018-08-31 优美特（北京）环境材料科技股份公司 一种梳状多支化水性聚氨酯分散体及其制备与应用
CN110564228A (zh) * 2019-07-25 2019-12-13 安徽沃尔德新材料有限公司 一种可快速干燥的高分子水性静电涂膜材料及其制备方法
US10662273B2 (en) 2016-12-19 2020-05-26 Celanese International Corporation Waterborne acrylic dispersions with high biorenewable content
CN115044008A (zh) * 2022-06-01 2022-09-13 武汉中科先进材料科技有限公司 一种亲水型阳离子光固化树脂及其制备方法和应用

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WO2016016286A1 (fr) * 2014-08-01 2016-02-04 Basf Se Procédé de production et d'utilisation de dispersions aqueuses hybrides polyuréthane-polyacrylate ainsi que leur utilisation dans des produits de revêtement
CN106795266A (zh) * 2014-08-01 2017-05-31 巴斯夫欧洲公司 制备和使用水性聚氨酯/聚丙烯酸酯复合分散体的方法和所述水性聚氨酯/聚丙烯酸酯复合分散体在涂层剂中的用途
US10336912B2 (en) 2014-08-01 2019-07-02 Basf Se Methods for producing and using aqueous polyurethane/polyacrylate hybrid dispersions and use of said aqueous polyurethane/polyacrylate hybrid dispersions in coating agents
CN106795266B (zh) * 2014-08-01 2021-03-09 巴斯夫欧洲公司 制备和使用水性聚氨酯/聚丙烯酸酯复合分散体的方法和所述水性聚氨酯/聚丙烯酸酯复合分散体在涂层剂中的用途
US10662273B2 (en) 2016-12-19 2020-05-26 Celanese International Corporation Waterborne acrylic dispersions with high biorenewable content
CN107722187A (zh) * 2017-10-23 2018-02-23 广东华斓汽车材料研究院 一种丙烯酸酯改性聚氨酯水分散体的制备方法及其应用
CN108467471A (zh) * 2018-04-04 2018-08-31 优美特（北京）环境材料科技股份公司 一种梳状多支化水性聚氨酯分散体及其制备与应用
CN110564228A (zh) * 2019-07-25 2019-12-13 安徽沃尔德新材料有限公司 一种可快速干燥的高分子水性静电涂膜材料及其制备方法
CN115044008A (zh) * 2022-06-01 2022-09-13 武汉中科先进材料科技有限公司 一种亲水型阳离子光固化树脂及其制备方法和应用
CN115044008B (zh) * 2022-06-01 2024-01-05 武汉中科先进材料科技有限公司 一种亲水型阳离子光固化树脂及其制备方法和应用

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