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WO2014209267A1 - Co-réactifs destinés à des revêtements de polyurée - Google Patents

Co-réactifs destinés à des revêtements de polyurée Download PDF

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Publication number
WO2014209267A1
WO2014209267A1 PCT/US2013/047368 US2013047368W WO2014209267A1 WO 2014209267 A1 WO2014209267 A1 WO 2014209267A1 US 2013047368 W US2013047368 W US 2013047368W WO 2014209267 A1 WO2014209267 A1 WO 2014209267A1
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WIPO (PCT)
Prior art keywords
compound
isocyanate
formula
composition
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/US2013/047368
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English (en)
Inventor
Paul BAUKEMA
Sanjay Luthra
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Sherwin Williams Co
Original Assignee
Valspar Sourcing Inc
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Filing date
Publication date
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Priority to PCT/US2013/047368 priority Critical patent/WO2014209267A1/fr
Priority to US14/572,190 priority patent/US10703933B2/en
Publication of WO2014209267A1 publication Critical patent/WO2014209267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • 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
    • C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl 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
    • C08G18/77—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
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • Two-component, polyurea compositions are useful in making a wide variety of coatings. These coatings are typically hard, abrasion-, weather- and solvent- resistant. Coating compositions of this type typically include polyisocyanate and isocyanate-reactive compounds, typically primary amines and secondary functional amines such as polyaspartic esters, as coreactants. Polyurea compositions of this type are frequently used in protective coatings for steel and concrete substrates. In an emerging area of technology, high solids coatings are now made using a blend of polyaspartic esters with varying reactivity to obtain compositions that balance application properties against viscosity and cure speed, and yet have very low organic volatile content.
  • the present invention provides coating compositions with reduced viscosity and accelerated cure.
  • the coating compositions are multicomponent polyurea coatings with lower initial mixed viscosity relative to compositions known in the art, but also surprisingly demonstrate faster cure speed with improved abrasion resistance and without significant detrimental effect on film hardness and chemical spot resistance.
  • the present invention provides a method to reduce viscosity and/or accelerate cure of a multicomponent polyurea coating system, by combining at least one amino-functional compound with an isocyanate-functional compound, and a compound of formula I:
  • Including the compound of formula I, or replacing a portion of the amino-functional compound with the compound of formula I reduces the initial mixed viscosity of the coating composition and accelerates cure without significant impact on coating hardness after application.
  • a method to reduce the viscosity of a multicomponent polyurea coating composition is provided.
  • a method to accelerate cure of a multicomponent polyurea coating composition is provided. The method includes steps of providing at least one component that is isocyanate-functional, at least one component that is isocyanate-reactive, i.e. capable of reacting with the isocyanate- functional component, and a component that includes the compound of formula I, as shown above. A portion of the isocyanate-reactive component is replaced with a compound of the structure shown in formula I.
  • the coating compositions produced by the methods described herein include multicomponent polyurea coatings that show reduced initial mixed viscosity and accelerated cure without significant loss of performance characteristics such as hardness, abrasion resistance and the like, when compared to compositions made by conventional methods.
  • multicomponent coating means a coating composition that contains two or more components that are mixed together and applied to a substrate prior to curing.
  • a “component” means any compound that includes a particular feature or structure. Examples of components include compounds, monomers, oligomers, polymers, and organic groups contained there. Typically, the coating composition includes two components.
  • the term “coating” refers to a continuous or substantially continuous film of an aliphatic coating composition.
  • aliphatic coating refers to a coating made by curing a composition produced as a result of a reaction between aliphatic reactants, such as, for example, a polyurethane or polyurea coating produced by reaction of aliphatic polyisocyanates with aliphatic polyols.
  • aliphatic refers to saturated or unsaturated, linear or branched hydrocarbons, and within the context of this application, the term also refers to saturated or unsaturated cyclic hydrocarbons.
  • organic group means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, cyclic group, or combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups).
  • aliphatic group means a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.
  • alkyl group means a saturated linear or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.
  • alkenyl group means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group.
  • alkynyl group means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon triple bonds.
  • cyclic group means a closed ring hydrocarbon group that is classified as an alicyclic group or an aromatic group, both of which can include heteroatoms.
  • alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
  • Ar refers to a divalent aryl group (i.e., an arylene group), which refers to a closed aromatic ring or ring system such as phenylene, naphthylene, biphenylene, fluorenylene, and indenyl, as well as heteroarylene groups (i.e., a closed ring hydrocarbon in which one or more of the atoms in the ring is an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.)).
  • Suitable heteroaryl groups include furyl, thienyl, pyridyl, quinolinyl, isoquinolinyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, pyrazinyl, 1-oxidopyridyl, pyridazinyl, triazinyl, tetrazinyl, oxadiazolyl, thiadiazolyl, and so on. When such groups are divalent, they are typically
  • moiety are used to differentiate between chemical species that allow for substitution or that may be substituted and those that do not allow or may not be so substituted.
  • group when the term “group” is used to describe a chemical substituent, the described chemical material includes the unsubstituted group and that group with O, N, Si, or S atoms, for example, in the chain (as in an alkoxy group) as well as carbonyl groups or other conventional substitution.
  • moiety is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be included.
  • alkyl group is intended to include not only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc.
  • alkyl group includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc.
  • the phrase “alkyl moiety” is limited to the inclusion of only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like.
  • crosslinker refers to a molecule capable of forming a covalent linkage between polymers or between two different regions of the same polymer.
  • self-crosslinking when used in the context of a self- crosslinking polymer, refers to the capacity of a polymer to enter into a crosslinking reaction with itself and/or another molecule of the polymer, in the absence of an external crosslinker, to form a covalent linkage therebetween. Typically, this crosslinking reaction occurs through reaction of complimentary reactive functional groups present on the self- crosslinking polymer itself or two separate molecules of the self-crosslinking polymer.
  • homopolymers and copolymers i.e., polymers of two or more different monomers.
  • a coating composition that comprises “an” additive can be interpreted to mean that the coating composition includes “one or more” additives.
  • the present invention includes a method to accelerate cure of a
  • the method includes steps of providing at least one isocyanate-functional component, at least one isocyanate -reactive component, and a compound of formula I:
  • a compound of formula I When a compound of formula I is included, the methods described herein produce a multicomponent coating composition that has reduced initial viscosity for at least one of the components and reduced mixed viscosity, and cures or hardens at a faster rate than a coating that includes only the isocyanate-functional and isocyanate -reactive components.
  • the accelerated cure is demonstrated by various properties including, without limitation, reduced viscosity, reduced set-to-touch time and reduced tack-free dry time.
  • adding a compound of formula I to the composition does not significantly reduce film hardness, or alter performance characteristics such as, for example, abrasion resistance or chemical spot resistance.
  • the present invention provides a method to reduce viscosity and accelerate cure of a multicomponent coating system.
  • Coating systems made by the methods described herein include, for example, polyaspartic coating systems, and the like.
  • the multicomponent coating system typically includes two or more components capable of reacting with one another, i.e. the components are co- reactants.
  • the multicomponent coating system is preferably a two-component coating system, where each of the components is capable of reacting with the other.
  • a two-component polyurethane coating system includes aliphatic polyisocyanate and aliphatic polyols as coreactants.
  • a two-component polyurea coating includes aliphatic polyisocyanate and polyamine.
  • the methods described herein preferably include polyaspartic esters as coreactants for the aliphatic polyisocyanate.
  • the multicomponent coating described herein includes at least one isocyanate-functional component as a coreactant.
  • the isocyanate-functional component is preferably aliphatic polyisocyanate, or blend of polyisocyanates.
  • Suitable polyisocyanate compounds for use in the methods described herein include, without limitation, polymers, semi -polymers or prepolymers made from aliphatic isocyanate-functional compounds, such as for example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like, including derivatives and isomers of the above, mixtures of the above with isomers and higher molecular weight homologues, such as, for example, polyisocyanates obtained by phosgenation of aniline/formaldehyde condensates, etc. Aliphatic polyisocyanates, such as HDI, and isomers, higher molecular weight homologues and mixtures of the above, for example, are preferred.
  • aliphatic polyisocyanates, such as HDI, and isomers, higher molecular weight homologues and mixtures of the above, for example are preferred.
  • Isocyanate-functional compounds, or polyisocyanates, for use in the methods described herein are prepared from low molecular weight polyols, including, without limitation, ethylene glycol, propylene glycol, trimethylol propane, 1,6-dihydroxy hexane, low molecular weight hydroxy- functional esters of these polyols and dicarboxylic acids, low molecular weight ethoxylation and/or propoxylation products of these polyols, mixtures of the polyols, and the like.
  • Suitable polyisocyanates preferably have molecular weight of about 160 to about 200, and NCO content of 5 wt-% to 40 wt-%, preferably 10 wt-% to 30 wt-%, and most preferably 15 wt-%> to 25 wt-%>.
  • Suitable polyisocyanates preferably have viscosity of 10,000 mPa.s, more preferably about 2,000 to 4,000 mPa.s, most preferably about 2,500 to 3,000 mPa.s.
  • Polyisocyanate compounds for use in the methods described herein are prepared from prepolymers and semi -prepolymers of relatively high molecular weight polyhydroxyl compounds with a molecular weight of 300 to about 8000, preferably about 1000 to 5000, as determined from the functionality and the hydroxyl number. These polyhydroxyl compounds have at least two hydroxyl groups per molecule and generally have a hydroxyl group content of about 0.5 to 17% by weight, preferably about 1 to 5% by weight.
  • suitable relatively high molecular weight polyhydroxyl compounds used for the preparation of the prepolymers and semi-prepolymers include, without limitation, polyester polyols based on low molecular weight, monomeric alcohols and polybasic carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexadydrophthalic acid, maleic acid, the anhydrides of these acids and mixtures of these acids and/or acid anhydrides.
  • Hydroxyl group-containing polylactones, especially poly-8-caprolactones are also suitable for the preparation of the prepolymers and semi-prepolymers. Isocyanate-substituted biuret or derivatives thereof, isocyanurate compounds, and the like may also be used.
  • the methods described herein include providing at least one component that is capable of reacting with a polyisocyanate or blend of
  • polyisocyanates i.e. an isocyanate -reactive component or a compound that can be used as a coreactant to produce a multicomponent polyurea coating composition.
  • the coreactant may be a mixture or blend of compounds capable of reacting with a
  • polyisocyanate or blend of polyisocyanates to produce a multicomponent polyurea coating composition is a polyisocyanate or blend of polyisocyanates to produce a multicomponent polyurea coating composition.
  • Suitable isocyanate-reactive components or coreactants include those containing active hydrogen groups or active basic groups neutralized with an acid such as for example, aliphatic, cycloaliphatic and heterocyclic amino alcohols, diols, triols, amines, diamines, triamines, tetramines and amides.
  • suitable compounds for reaction with a polyisocyanate also include for example, organic acids such as formic acid and acetic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and ethylenically unsaturated monomers and their derivatives, such as polyacrylates, for example.
  • Hydroxy- functional copolymers of ethylenically unsaturated are particularly preferred, including copolymers with number average molecular weight (M n ) of preferably about 800 to about 50,000, more preferably about 1000 to about 20,000, and most preferably about 5000 to about 10,000.
  • M n number average molecular weight
  • the hydroxy- functional copolymers have hydroxyl group content of about 0.1%> to about 12% by weight, preferably about 1% to about 10%) by weight, and most preferably about 2% to about 6% by weight.
  • Suitable ethylenically unsaturated monomers used to prepare the hydroxy- functional copolymers include, for example, vinyl and vinylidene monomers such as styrene, a-methyl styrene, o- and p-chloro styrene, o-, m- and p-methyl styrene, p-tert.
  • butyl styrene acrylic acid; (meth)acrylonitrile; acrylic and methacrylic acid esters of alcohols containing 1 to 8 carbon atoms such as ethyl acrylate, methyl acrylate, n- and isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, iso- octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and iso-octyl methacrylate; diesters of fumaric acid, itaconic acid or maleic acid having 4 to 8 carbon atoms in the alcohol component; (meth)acrylic acid amide; vinyl esters of alkane monocarboxylic acids having 2 to 5 carbon atoms such as vinyl acetate or vinyl propionate; and hydroxyalkyl esters of acrylic acid or methacrylic acid having
  • aliphatic or cycloaliphatic compounds with secondary amine functionality are preferred as co-reactants for the polyisocyanate.
  • cycloaliphatic polyamines are particularly preferred.
  • Suitable polyamines include high molecular weight amines with number average molecular weight (M n ) of about 400 to about 10,000, preferably about 500 to about 6,000; or low molecular weight amines with
  • M n less than about 400.
  • aliphatic or cycloaliphatic diamino-functional esters are preferred as coreactants for the polyisocyanate, and esters or derivatives of polyaspartic acid, i.e. polyaspartic ester particularly preferred.
  • Polyaspartic esters are prepared by conventional methods known to those of skill in the art, including for example, by the reaction of primary polyamines with esters of dicarboxylic acids.
  • Suitable polyamines used in the preparation of polyaspartic acid derivatives such as polyaspartic ester include, without limitation, 1 ,4-diaminobutane, 1,6- diaminohexane, 2,2,4-trimethyl-diaminohexane, 2,4,4-diaminohexane, l-amino-3,4,4- trimethyl-5-aminomethylcyclohexane, 4,4'-diamino-dicyclohexylmethane, and the like.
  • Suitable esters of dicarboxylic acids include, without limitation, unsubstituted esters of ethylenically unsaturated dicarboxylic acids such as, for example, maleic acid, fumaric acid, alkyl- or alkenyl-substituted esters of maleic acid, fumaric acid, and the like.
  • the multicomponent coating described herein includes a two-component formed by the reaction of at least one isocyanate-functional component, i.e. a polyisocyanate with at least one isocyanate-reactive component, i.e. a coreactant as described above, preferably a polyaspartic ester.
  • Polyaspartic esters are known in the art as co-reactants for aliphatic polyisocyanates in the preparation of low-VOC and zero-VOC high solids polyurea coatings. Coatings of this type are hard, elastic, abrasion resistant, solvent resistant and weather resistant.
  • the properties of the coating composition described herein can tailored to specific applications by varying the ratio of polyisocyanate to the isocyanate-reactive co-reactant, effectively the ratio of NCO groups in the polyisocyanate and to isocyanate-reactive groups, in the coreactant.
  • the properties of the coating composition are varied by altering the ratio of NCO groups in the polyisocyanate with -NH groups in the polyaspartic ester, i.e. NCO:NH ratio.
  • suitable NCO:NH ratios are from about 0.8: 1 to about 2.25: 1, preferably from about 0.8: 1 to about 1.5: 1, more preferably from about 0.8: 1 to about 1.2: 1, and most preferably from about 0.8: 1 to about 1.1 : 1.
  • the NCO:NH ratio of the co-reactants in a two-component coating composition as described herein is 1.05: 1.
  • compositions may have shorter useful work-life, with the viscosity becoming too high to achieve desired surface appearance and film properties.
  • the methods of the present invention include providing an additional coreactant.
  • the coreactant is combined with the isocyanate-functional component and isocyanate-reactive component to produce the coating composition.
  • the compound of formula I is non-reactive, and has relatively low VOC and low molecular weight. Suitable compounds have low number average molecular weight (M n ) of no more than about 750, more preferably no more than about 500.
  • the compound to be included in the methods described herein is a compound of the general formula:
  • A is a divalent organic group, preferably having 2 to 20 carbon atoms, more preferably 3 to 5 carbon atoms.
  • A is a divalent organic group of formula C -
  • Cio alkyl, C 2 -Cio alkylene or C 3 -C 10 cycloalkyl, and R and R are independently hydrogen or an organic group, preferably a group having less than 100 carbon atoms.
  • R and R 4 are independently hydrogen or an organic group, preferably a group having less than 100 carbon atoms.
  • R 3 and R 4 are independently H, substituted or unsubstituted Ci-C 6 alkyl, substituted or unsubstituted C 3 -C 6 cycloalkyl, -OR 5 or - C(0)OR 5 , where R 5 is hydrogen or an organic group, preferably a group having less than 100 carbon atoms.
  • R 5 is hydrogen, substituted or unsubstituted Ci-C 6 alkyl, substituted or unsubstituted C 3 -C 6 cycloalkyl, or Ci-C 6 alkoxy.
  • m is 0 or 1 ; preferably 1
  • n is 0 or 1 , preferably 1.
  • Suitable compounds of formula (I) include, for example, compounds where is a divalent carbon atom (i.e. -C— ), R 1 and R 2
  • A are each independently C 1 -C 4 alkyl, preferably -(CH 2 ) 3 CH 3 .
  • R 3 is -OR 5 , preferably -OH
  • R 4 is -C(0)OR 5 , preferably -C(0)0(CH 2 ) 3 CH 3 .
  • m and n are each independently 1.
  • A is a divalent carbon atom (i.e. -C— ), R and R are each independently C 1 -C 4 alkyl, preferably -(CH 2 ) 3 CH 3 .
  • R 4 is -C(0)OR 5 , preferably -C(0)0(CH 2 ) 3 CH 3 .
  • m and n are each independently 1.
  • the compounds of formula (I) include, for example, compounds where A is a divalent organic group of the formula -(CH 2 ) X — , where x is
  • R and R are each independently C 1 -C 4 alkyl, preferably -(CH 2 ) CH , R 3 and R 4 are independently each H, and m and n are each independently 1.
  • the compounds of formula (I) include, for example, compounds where A is a divalent organic group of the formula - C— CH 2 — , R 1 is (CH 3 ) 2 CHCH(OH), R 2 is -(CH 2 ) 3 CH 3 , R 3 and R4 are each independently -CH , m is 0 and n is 1.
  • compounds of formula (I) include, for example, alkyl esters of polycarboxylic acids, preferably dicarboxylic acids, alkyl esters of hydroxy acids and hydroxy polyacids, including hydroxy-substituted dicarboxylic acids.
  • Suitable compounds of formula (I) include, without limitation, tributyl citrate, tributyl acetyl citrate, dibutyl adipate, dibutyl sebacate and the like, or mixtures thereof.
  • the methods described herein include replacing at least a portion of the isocyanate -reactive component of the multicomponent coating composition with a component including a compound of formula (I).
  • a component including a compound of formula (I) preferably about 5% to 30%, more preferably about 10%> to 25%, and most preferably, about 15% to 20%> of the amino-functional component is replaced with a compound of formula (I).
  • the replacement of at least a portion of the amino-functional component of the coating composition with the compound of formula (I) produces a coating with reduced initial mixed viscosity, reduced set-to-touch time and reduced tack-free dry time.
  • replacement of up to 20% of the amino-functional compound is believed to increase the overall crosslink density as measured by MEK double rub. Surprisingly, the replacement of up to 20% of the amino-functional compound with the compound of formula (I) did not significantly reduce film hardness.
  • a coating composition that includes a compound of formula I may be made by combining the isocyanate-reactive component with the isocyanate-functional component in the presence of the compound of formula I.
  • the isocyanate-reactive component i.e. a polyaspartic acid or blend may be made in the presence of a compound of formula I, and then combined with the isocyanate- functional component, i.e., a polyisocyanate compound to produce the polyurea coating composition.
  • the incorporation of a compound of formula I leads to a decrease in dry time. Without being limited to theory, this effect is more pronounced at higher NCO:NH ratios.
  • a coating composition that includes a compound of formula (I) shows improved adhesion to the substrate (as measured by standard dry and wet adhesion tests known in the art), and lower shrinkage of the cross-linked coating over time. This leads to increased durability of the coating.
  • a compound of formula I reduces polyisocyanate demand in a two-component coating system, leading to reduced cross-linking, which benefits wetting of the substrate and improves adhesion.
  • the coatings also show improved flexibility, as measured by standard methods known in the art.
  • the methods described herein may be performed in the presence of a catalyst.
  • a compound of formula I is added along with a catalyst to a polyisocyanate or blend of polyisocyanates and an isocyanate -reactive component to produce the coating composition.
  • Suitable catalysts include, for example, alkyl substituted esters of maleic acid, succinic acid and the like. Dialkyl maleates and dialkyl succinates are preferred.
  • Adhesion testing is performed to assess whether the coating adheres to the coated substrate.
  • the adhesion test was performed either according to ASTM D 3359 (Standard Test Method for Measuring Adhesion by Tape Test) or DIN 53151 (Testing of Paints by Cross-cut). Set-to -Touch Testing
  • Set-to-touch time is a reference to the time it takes for a film of a coating composition is still tacky, but no film is removed on contact with a finger. STT is typically measured by the methods described in ASTM D1640 (Drying, Curing or Film Formation of Coatings at Room Temperature). Tack-free, dry-to-touch, dry hard and dry through may also be used to describe cure or dry time of films.
  • the hardness of a film of the coating composition is determined by the
  • the initial and mixed viscosity of the coating composition is determined by the Gardner method, as described in ASTM D1725 (Standard Test Method for Viscosity of Resin Solutions).
  • a first component of a coating composition was prepared by combining a commercially available polyaspartic ester or blend (DESMOPHEN 1520, Bayer) with tributyl citrate at either 15% or 20% of the total weight of the component.
  • a control composition containing no TBC was also prepared. This first component was designated “Part A.”
  • a second component, an HDI isocyanurate trimer, TOLONATE HDT (Perstorp, Toledo OH) was prepared as described in Example 1. This second component was designated "Part B.” Parts A and B were then combined to a constant NCO:NH ratio of 1.05 : 1 to produce the coating composition.
  • Various properties of the composition including dry time, abrasion resistance, adhesion and chemical spot resistance were measured. Results are shown in Table 2.
  • Parts A and B of the coating composition were prepared as described in Example 2. In combining parts A and B, the NCO:NH levels are maintained at a constant ratio of 1 : 1.2. Tack free time and dry time were measured, and results are shown in Table
  • a first component of a coating composition was prepared by combining a commercially available polyaspartic ester or blend (DESMOPHEN 1420, Bayer) with tributyl citrate at either 15% or 20% of the total weight of the component.
  • a control composition containing no TBC was also prepared. This first component was designated “Part A.”
  • a second component, an HDI isocyanurate trimer, TOLONATE HDT (Perstorp, Toledo OH) was prepared and reduced to 75% non- volatile content as described in Example 1. This second component was designated "Part B.” Parts A and B were then combined to a constant NCO:NH ratio of 1.05 : 1 to produce the coating composition.
  • Various properties of the composition including dry time, abrasion resistance, adhesion and chemical spot resistance were measured. Results are shown in Table 4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé pour accélérer le durcissement d'une composition de revêtement à plusieurs composants, comprenant les étapes consistant à utiliser un isocyanate et un composé réactif avec un isocyanate, et remplacer une partie du composé réactif avec un isocyanate par un composé de formule I :
PCT/US2013/047368 2012-06-26 2013-06-24 Co-réactifs destinés à des revêtements de polyurée Ceased WO2014209267A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2013/047368 WO2014209267A1 (fr) 2013-06-24 2013-06-24 Co-réactifs destinés à des revêtements de polyurée
US14/572,190 US10703933B2 (en) 2012-06-26 2014-12-16 Coreactants for polyurea coatings

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2013/047368 WO2014209267A1 (fr) 2013-06-24 2013-06-24 Co-réactifs destinés à des revêtements de polyurée

Related Child Applications (1)

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US14/572,190 Continuation US10703933B2 (en) 2012-06-26 2014-12-16 Coreactants for polyurea coatings

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WO2014209267A1 true WO2014209267A1 (fr) 2014-12-31

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7968197B2 (en) * 2005-08-25 2011-06-28 Ppg Industries Ohio, Inc. Polyurea coating comprising an amine/(meth)acrylate oligomeric reaction product
WO2011126562A2 (fr) * 2010-04-09 2011-10-13 Bayer Materialscience Llc Compositions de revêtement bi-composants à base de polyaspartate
US8137813B2 (en) * 2006-12-18 2012-03-20 Ppg Industries Ohio, Inc. Triamine/aspartate curative and coatings comprising the same
US20130116379A1 (en) * 2010-07-20 2013-05-09 Bayer Intellectual Property Gmbh Binder combinations for structural drinking water pipe coatings

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7968197B2 (en) * 2005-08-25 2011-06-28 Ppg Industries Ohio, Inc. Polyurea coating comprising an amine/(meth)acrylate oligomeric reaction product
US8137813B2 (en) * 2006-12-18 2012-03-20 Ppg Industries Ohio, Inc. Triamine/aspartate curative and coatings comprising the same
WO2011126562A2 (fr) * 2010-04-09 2011-10-13 Bayer Materialscience Llc Compositions de revêtement bi-composants à base de polyaspartate
US20130116379A1 (en) * 2010-07-20 2013-05-09 Bayer Intellectual Property Gmbh Binder combinations for structural drinking water pipe coatings

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