US20060011295A1 - Aspartic ester functional compounds - Google Patents

Aspartic ester functional compounds Download PDF

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Publication number
US20060011295A1
US20060011295A1 US10/890,873 US89087304A US2006011295A1 US 20060011295 A1 US20060011295 A1 US 20060011295A1 US 89087304 A US89087304 A US 89087304A US 2006011295 A1 US2006011295 A1 US 2006011295A1
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substrate
branched
linear
composition
acid
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US10/890,873
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Inventor
Karsten Danielmeier
Douglas Wicks
Karen Henderson
Evan Minnich
John McLafferty
Stephanie Strazisar
Kurt Frisch
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Covestro LLC
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Priority to US10/890,873 priority Critical patent/US20060011295A1/en
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Assigned to BAYER MATERIAL SCIENCE LLC reassignment BAYER MATERIAL SCIENCE LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FRISCH, KURT C., JR., MCLAFFERTY, JOHN J., STRAZISAR, STEPHANIE A., MINNICH, EVAN RANDALL, HENDERSON, KAREN MARIE, WICKS, DOUGLAS A., DANIELMEIER, KARSTEN
Assigned to BAYER MATERIAL SCIENCE LLC reassignment BAYER MATERIAL SCIENCE LLC DOCUMENT RE-RECORDED TO CORRECT ERRORS CONTAINED IN PROPERTY NUMBER 10890893 PREVIOUSLY RECORDED ON REEL 015879 FRAME 0411 (ASSIGNMENT OF ASSIGNOR' INTEREST) Assignors: WICKS, DOUGLAS A., STRAZISAR, STEPHANIE A., DANIELMEIER, KARSTEN, MCLAFFERTY, JOHN J., MINNICH, EVAN RANDALL, FRISCH, KURT C., JR., HENDERSON, KAREN MARIE
Priority to DE200560003882 priority patent/DE602005003882T2/de
Priority to EP20050014361 priority patent/EP1627868B1/en
Priority to CA 2511793 priority patent/CA2511793C/en
Priority to MXPA05007526A priority patent/MXPA05007526A/es
Priority to CNB2005100859251A priority patent/CN100543009C/zh
Priority to JP2005205643A priority patent/JP2006028515A/ja
Publication of US20060011295A1 publication Critical patent/US20060011295A1/en
Priority to HK07100790.5A priority patent/HK1094188B/xx
Priority to US12/354,036 priority patent/US7759452B2/en
Abandoned legal-status Critical Current

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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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/24—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31547—Of polyisocyanurate

Definitions

  • the present invention relates to functional aspartic ester compounds and their use in adhesive, sealant, and coating compositions.
  • Aspartic esters represent a unique class of reactants in adhesive, coating, and sealant formulations. Their reactivity typically lies between slow classical polyols and faster reacting primary and secondary amines.
  • U.S. Pat. Nos. 5,412,056, 5,623,045, 5,126,170, and 5,821,326 disclose coating compositions in which the binding agent is a two-component system containing a polyisocyanate component and an isocyanate-reactive component.
  • the latter component includes at least one aspartic acid diester group formed by reacting an amine with a maleic or fumaric diester.
  • EP 0 667 362 A1 discloses coating compositions including a polyisocyanate component, a component that includes at least one aspartic acid diester group formed by reacting an amine with a maleic or fumaric diester, and a water-adsorbing zeolite.
  • Adhesives are commonly used to join or fasten two or more adherends. Adherends are considered as being any two or more materials, or pieces of material that are being joined together, including wood, metals, plastics, paper, ceramics, stone, glass, concrete, etc. Adhesives used for these purposes are based on a wide range of technologies, including elastomer/solvent/resin mixtures, epoxies, latexes, polyurethanes, silicones, cyanoacrylates, acrylics, hot melts, and others.
  • Such adhesives can have one or more drawback, such as they may contain solvents which are toxic and often flammable, they can be incompatible with one or more classes of adherends, they can have undesirably long cure times and in many cases the bonds they form of are of insufficient strength.
  • a sealant is typically a thin film, often containing a plastic, that is applied onto one or more surfaces on one or more substrates to prevent passage of a liquid or gas through the film.
  • the sealant can be used to prevent exposure of the substrate or is often additionally used to prevent exposure via defects in a substrate or between gaps that can exist between substrates.
  • desired functionality and/or molecular architectures in the aspartic ester materials may not be achievable using the established amine—maleic/fumaric ester synthetic pathway. This limits the possible aspartic ester containing materials available for formulation.
  • U.S. Pat. No. 2,569,200 discloses polyvalent alkylene imine esters and methods for preparing them.
  • the present invention is directed to functional dialkyl aspartic esters (aspartates) according to the formula: where
  • the present invention is also directed to a method of preparing a functional aspartate and the functional aspartate resulting from the method.
  • the method includes
  • the present invention is further directed to adhesive, sealant or coating compositions that include
  • alkyl refers to a monovalent radical of an aliphatic hydrocarbon chain of general formula C s H 2s+1 , where s is the number of carbon atoms, or ranges therefore, as specified.
  • substituted alkyl refers to an alkyl group, where one or more hydrogens are replaced with a non-carbon atom or group, non-limiting examples of such atoms or groups include halides, amines, alcohols, oxygen (such as ketone or aldehyde groups), and thiols.
  • cyclic alkyl or “cycloalkyl” refer to a monovalent radical of an aliphatic hydrocarbon chain that forms a ring of general formula C s H 2s ⁇ 1 , where s is the number of carbon atoms, or ranges therefore, as specified.
  • substituted cycloalkyl refers to a cycloalkyl group, containing one or more hetero atoms, non-limiting examples being —O—, —NR—, and —S— in the ring structure, and/or where one or more hydrogens are replaced with a non-carbon atom or group, non-limiting examples of such atoms or groups include halides, amines, alcohols, oxygen (such as ketone or aldehyde groups), and thiols.
  • R represents an alkyl group of from 1 to 24 carbon atoms.
  • aryl refers to a monovalent radical of an aromatic hydrocarbon.
  • Aromatic hydrocarbons include those carbon based cyclic compounds containing conjugated double bonds where 4t+2 electrons are included in the resulting cyclic conjugated pi-orbital system, where t is an integer of at least 1.
  • aryl groups can include single aromatic ring structures, one or more fused aromatic ring structures, covalently connected aromatic ring structures, any or all of which can include heteroatoms.
  • Non-limiting examples of such heteroatoms that can be included in aromatic ring structures include O, N, and S.
  • alkylene refers to acyclic or cyclic divalent hydrocarbons having a carbon chain length of from C 1 (in the case of acyclic) or C 4 (in the case of cyclic) to C 25 , typically C 2 to C 12 , which may be substituted or unsubstituted, and which may include substituents.
  • the alkylene groups can be lower alkyl radicals having from 1 to 12 carbon atoms.
  • propylene is are intended to include both n-propylene and isopropylene groups; and, likewise, “butylene” is intended to include both n-butylene, isobutylene, and t-butylene groups.
  • (meth)acrylic and “(meth)acrylate” are meant to include the corresponding derivatives of acrylic acid and methacrylic acid, without limitation.
  • cure is intended to include both crosslinking of the adhesive, sealant, or coating composition components and film formation as a result of evaporation of water and, if present, other solvents and diluents along with the development of physical and chemical properties in the resultant film such as bond strength and peel strength.
  • crosslink refers to the formation of short chains of molecules linking two longer molecular chains together through the reaction of two or more functional groups on the short chains.
  • the present invention is directed to a method of making functional dialkyl aspartic acid esters (“aspartate” or “aspartates”) and aspartates that can be made using the method.
  • embodiments of the invention include a method that includes:
  • aziridine refers to compounds according to Formula I, where each occurrence of R 31 and R 32 are independently selected from H, C 1 -C 20 linear, branched, or cyclic alkyl, aryl, alkaryl or aralkyl, in some cases H and C 1 -C 3 linear or branched alkyl, and in other cases H or C 1 -C 2 linear or branched alkyl groups.
  • R 32 is H and at least one occurrence of R 31 is H.
  • the aziridine is selected from unsubstituted aziridine (ethylene imine), 2-methyl aziridine, 2-ethyl aziridine, 2-n-propyl aziridine, and 2-isopropyl aziridine.
  • Michael-acceptor molecule refers to a molecule that contains one or more electron withdrawing groups (EWG) that cause a carbon in a carbon-carbon double bond to be electro positive and a good place for nucleophilic attack.
  • EWG electron withdrawing groups
  • Any suitable Michael-acceptor molecule, molecules or polymers containing a Michael-acceptor in the backbone can be used in the present invention.
  • a non-limiting example of a polymer backbone Michael-acceptor group is the maleic ester group in the formula below: where R p and R p′ are independently C 1 -C 20 linear, branched or cyclic alkyl, aryl, alkaryl or aralkyl, and s and t are independently 1 to 1,000, in some cases 1 to 500, and in other cases 1 to 100.
  • the suitable Michael-acceptor molecules include, but are not limited to those containing a carbon-carbon double bond and one or more EWGs selected from ketones, nitrites, nitro groups, carboxylic acids and their corresponding salts, C 1 -C 24 linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl, or aralkyl esters of carboxylic acids, and C 1 -C 24 linear, branched or cyclic alkyl sulfonyl groups.
  • EWGs selected from ketones, nitrites, nitro groups, carboxylic acids and their corresponding salts, C 1 -C 24 linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl, or aralkyl esters of carboxylic acids, and C 1 -C 24 linear, branched or cyclic alkyl sulfonyl groups.
  • the suitable Michael-acceptor molecules include, but are not limited to C 1 -C 8 linear, branched or cyclic dialkyl esters of maleic acid, C 1 -C 8 linear, branched or cyclic dialkyl esters of fumaric acid, maleimide, C 1 -C 8 linear, branched or cyclic N-alkyl maleimide, mono-amides of maleic acid, mono-amides of fumaric acid, di-amides of maleic acid, di-amides of fumaric acid, C 1 -C 8 linear, branched or cyclic N-alkyl amides of maleic acid, and C 1 -C 8 linear, branched or cyclic N-alkyl amides of fumaric acid.
  • active hydrogen containing compound refers to compounds that that contain a hydrogen atom that is sufficiently acidic to allow the compound to effectuate a ring opening reaction of the aziridine moiety.
  • the active hydrogen containing compounds include, but are not limited to C 1 -C 24 linear, branched or cyclic alkylenes, alkenylenes, arylenes, alkarylenes, or aralkylenes, polyethers, polyesters, or poly(meth)acrylic molecules containing two or more functional groups selected from the group consisting of hydroxyl, carboxylic acid, thiol, amine, acidic CH groups, and combinations thereof.
  • (meth)acrylic and “(meth)acrylate” encompass compounds that include moieties of or derived from both methacrylic acid and its corresponding esters, amides, and salts as well as acrylic acid and its corresponding esters, amides, and salts.
  • the active hydrogen containing compounds include at least one and in some cases a number average of at least 1.5, in other cases at least 2 active hydrogen containing groups.
  • the active hydrogen containing compound can have the following Formula II: Z-R 4 —Y′ (II) where Y′ can be a group selected from —OH, —SH, —NR 5 H, —COOH, —O—P(O) 2 —OH, —P(O) 2 —OH, —S(O) 2 —OH, and a group containing an acidic hydrogen on a carbon positioned adjacent to one or more electron withdrawing groups according to one of Formulas III and/or Formula IV: where
  • R 4 can be a linking group selected from
  • Particular embodiments of the invention are directed to functional aspartates where the group Z-R 4 —Y— is a polyester radical. Some aspects ot this embodiment are directed to situations where the polyester is a carboxylic acid functional polyester.
  • the group Z-R 4 —Y′ in the active hydrogen containing compound of Formula II is a polyether radical in the functional aspartate.
  • the polyether is a hydroxyl functional polyether.
  • Additional particular embodiments of the invention are directed to Z-R 4 —Y′ active hydrogen containing compounds of Formula II where the group Z-R 4 —Y′ is a poly(meth)acrylate containing one or more active hydrogen group.
  • the poly(meth)acrylate is a carboxylic acid functional polyacrylate.
  • the active hydrogen containing compounds of Formula II contains a group Z-R 4 —Y′, which is a C 1 -C 24 linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl, or aralkyl dicarboxylic acid.
  • the dicarboxylic acid is selected from adipic acid, malonic acid, succinic acid, maleic acid, fumaric acid, pentanedioc acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonadioic acid, and mixtures thereof.
  • the Michael-acceptor molecule is a diester or diamide of maleic acid where each ester or amide group is independently a C 1 -C 8 , in some cases C 2 -C 6 linear, branched or cyclic alkyl group, the aziridine conforms to Formula I, and the active hydrogen containing compound conforms to Formula II, where Y′ is a carboxylic acid.
  • a catalyst can be used in the method of making functional dialkyl aspartates.
  • Appropriate catalysts can be used in either A) or B).
  • a catalyst is used in A) can be selected from metal salts of saturated or unsaturated carboxylic acids, alcoholates, including, but not limited to sodium methylate and aluminum ethylate, and alkaline amides, including, but not limited to sodium amide.
  • a catalyst is used in B), which can be selected from Bronstead acids or Lewis acids.
  • Lewis acids that can be used as a catalyst include tris-(pentafluorophenyl)borane; metal halides such as CuCl 2 .2H 2 O or BiCl 3 ; and triflates (trifluoromethanesulfonate, abbreviated TF) of suitable metals such as Yb(OTF) 3 , LiNTF 2 , Sn(OTF) 2 or Cu(OTF) 2 .
  • Bronstead acids that can be used as a catalyst include hydrochloric acid, sulfuric acid, and perchloric acid.
  • heterogeneous catalysts can be used and the catalyst can include silica gel and/or montmorillonite clay.
  • the Michael-acceptor molecule and aziridine according to Formula I are mixed at a temperature of less than 30 C and stirred for from 30 minutes to 24 hours.
  • a vacuum is applied to remove unreacted aziridine and/or an electrophilic agent is used to react with and scavange the aziridine.
  • the reaction provides an aziridinyl aspartate which is combined with an acid functional polyether (active hydrogen containing compound) and stirred for four to 24 hours. Completion of the reaction can be confirmed by chromatography, gel permeation chromatography (GPC) being a non-limiting example of such.
  • Embodiments of the invention are directed to functional dialkyl aspartates that can be made according to the present method.
  • Particular embodiments of the invention are directed to functional dialkyl aspartates described according to Formula V: where
  • Y is a linking group that can be selected from —O—, —S—, —NR 5 —, —O—P(O) 2 —O—, —P(O) 2 —O—, —S(O) 2 —O—, a group resulting from the removal of the acidic hydrogen (H) from a carbon that is positioned adjacent to one or more electron withdrawing groups according to Formula III or Formula IV as shown in Formulas IIIa and IVa below, where W 1 and W 2 are as defined above.
  • R 4 is a linking group as defined above and Z is a group as defined above.
  • Particular embodiments of the invention are directed to functional aspartates where the group Z-R 4 —Y— is a polyester radical. Some aspects to this embodiment are directed to situations where the polyester is a carboxylic acid functional polyester.
  • the group Z-R 4 —Y— is a polyether radical in the functional aspartate.
  • the polyether is a hydroxyl functional polyether.
  • Additional particular embodiments of the invention are directed to functional aspartates where the group Z-R 4 —Y— is a poly(meth)acrylate radical.
  • the poly(meth)acrylate is a carboxylic acid functional polyacrylate.
  • the functional aspartate contains a group Z-R 4 —Y—, which is a monoester radical of a C 1 -C 24 linear, branched or cyclic alkyl, alkenyl, aryl, alkaryl, or aralkyl dicarboxylic acid.
  • the dicarboxylic acid is selected from adipic acid, malonic acid, succinic acid, maleic acid, fumaric acid, pentanedioc acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonadioic acid, and mixtures thereof.
  • functional aspartate according to Formula V conforms to Formula Va: where Z, R 4 , R 32 , R 31 , R 1 , and R 2 are as defined above and X can be O or NR 5 as defined above.
  • Embodiments of the present invention are directed to adhesive, sealant or coating compositions that include:
  • the isocyanate functional material can be a polyisocyanate containing from 2 to 6 isocyanate groups.
  • the polyisocyanate has a structure according to Formula VI: OCN—R 17 —NCO (VI) where R 17 is selected from C 2 to C 24 linear, branched, and cyclic alkylene, arylene, and aralkylene, which may optionally contain one or more isocyanate groups.
  • the polyisocyanate can be selected from 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, bis-(4-isocyanatocyclohexyl)-methane, 2,4′-dicyclohexyl-methane diisocyanate, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, ⁇ , ⁇ , ⁇ ′,
  • the polyisocyanates can include one or more polyisocyanate adducts containing biuret, urethane, uretdione, allophanate, isocyanurate, and/or iminooxadiazinedione groups.
  • biuret group-containing polyisocyanates include those prepared according to the processes disclosed in U.S. Pat. No. 3,124,605; 3,358,010; 3,644,490; 3,862,973; 3,903,126; 3,903,127; 4,051,165; 4,147,714; or 4,220,749 the pertinent portions of which are herein incorporated by reference, by using co-reactants such as water, tertiary alcohols, primary and secondary monoamines, and primary and/or secondary diamines.
  • These polyisocyanates can have an NCO content of 18 to 22% by weight and an average NCO functionality of from 3 to 3.5.
  • Non-limiting examples of urethane group-containing polyisocyanates include those prepared in accordance with the process disclosed in U.S. Pat. No. 3,183,112; the pertinent portions of which are herein incorporated by reference, by reacting excess quantities of polyisocyanates, in some cases diisocyanates, with low molecular weight glycols and polyols having molecular weights of less than 400, such as trimethylol propane, glycerine, 1,2-dihydroxy propane and mixtures thereof.
  • the urethane group-containing polyisocyanates can have an NCO content of 12 to 20% by weight and an (average) NCO functionality of 2.5 to 3.
  • Non-limiting examples of uretdione diisocyanates include those prepared by oligomerizing a portion of the isocyanate groups of a diisocyanate in the presence of a suitable catalyst, e.g., a trialkyl phosphine catalyst, and which can be used in admixture with other aliphatic and/or cycloaliphatic polyisocyanates, particularly the isocyanurate group-containing polyisocyanates set forth above.
  • a suitable catalyst e.g., a trialkyl phosphine catalyst
  • Non-limiting examples of allophanate group-containing polyisocyanates include those prepared according to the processes disclosed in U.S. Pat. Nos. 3,769,318; 4,160,080 and 4,177,342; the pertinent portions of which are herein incorporated by reference.
  • the allophanate group-containing polyisocyanates can have an NCO content of from 12 to 21% by weight and an (average) NCO functionality of 2 to 4.5.
  • Non-limiting examples of isocyanurate and allophanate group-containing polyisocyanates include those prepared in accordance with the processes set forth in U.S. Pat. Nos. 5,124,427; 5,208,334 and 5,235,018; the pertinent portions of which are herein incorporated by reference.
  • Such polyisocyanates can contain these groups in a ratio of monoisocyanurate groups to mono-allophanate groups of about 10:1 to 1:10, in some cases about 5:1 to 1:7.
  • Non-limiting examples of iminooxadiazine dione and optionally isocyanurate group-containing polyisocyanates include those that can be prepared in the presence of special fluorine-containing catalysts as described in U.S. Pat. No. 5,914,383, the pertinent portions of which are herein incorporated by reference. These polyisocyanates generally have an average NCO functionality of 3 to 3.5 and an NCO content of 5 to 30%, in some cases 10 to 25% and in other cases 15 to 25% by weight.
  • the adhesive, sealant or coating compositions can include iii) an amine chain extender.
  • the amine chain extender can include a C 1 -C 24 linear, branched or cyclic alkyl, aryl, alkaryl, or aralkyl difunctional amine, optionally containing one or more —O—, —NH—, or —S-hetero atoms.
  • the adhesive, sealant or coating compositions can be a two-component composition, where a first component comprises i) and a second component comprises ii).
  • the first component further comprises iii) an amine chain extender.
  • the adhesive, sealant or coating compositions can include one or more materials selected from leveling agents, wetting agents, flow control agents, antiskinning agents, antifoaming agents, fillers, adhesion promoters, viscosity regulators, plasticizers, pigments, dyes, UV absorbers, thermal stabilizers, antioxidants, and mixtures thereof.
  • Non-limiting examples of plasticizers that can be used in the present invention include dioctyl phthalate (DOP) dibutyl phthalate (DBP); diisodecyl phthalate (DIDP); dioctyl adipate isodecyl malonate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; tricresyl phosphate and trioctyl phosphate; polypropylene glycol adipate and polybutylene glycol adipate; and the like.
  • Such plasticizers can be used alone or in combination of two or more.
  • adhesion promoters that can be used in the present invention include epoxy resins, phenolic resins, silane and amino silane coupling agents known in the art, alkyl titanates and/or aromatic polyisocyanates.
  • Non-limiting examples of cure catalysts which may be used for curing, that can be used in the present invention include titanate esters, e.g., those of tetrabutyl titanate and tetrapropyl titanate; organotin compounds, e.g., dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin diacetate, tin octylate and tin naphthenate; lead octylate; amine-based compounds and salts of these compounds and carboxylates, e.g., butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, gu
  • Non-limiting examples of leveling agents that can be used in the present invention include cellulose, e.g., nitrocellulose and cellulose acetate butyrate.
  • wetting agents that can be used in the present invention include glycols, silanes, anionic surfactants, and any other wetting agents known in the art.
  • Non-limiting examples of flow control agents that can be used in the present invention include polyacrylic esters, non-ionic fluorinated alkyl ester surfactants, non-ionic alkylarylpolyether alcohols, silicones, and the like, as well as those available under the trade name RESIFLOW® by Estron Chemical, Inc., Parsippany, N.J., those sold under the trade name Benzoin® by DSM, Inc., those available under the trade name MODAFLOW® from Monsanto and those available under the trade name SURFYNOL® available from Air Products, Bethlehem, Pa.
  • Non-limiting examples of antiskinning agents that can be used in the present invention include lecithin, oximes, non-limiting examples being butyraldehayde oxime and methyl ethyl ketoxime, hydroqionones, non-limiting examples being 2,5-di-t-butyl-hydroquinone and the methyl esters of hydroquinone and anthraquinones.
  • Non-limiting examples of antifoaming agents that can be used in the present invention include those available as FOAMEX® from Rohm and Haas Company, Philadelphia, Pa., those available under the trade name BYK®, available from BYK-Chemie USA, Wallingford, Conn., and those available under the trade name FoamBrake® from BASF Corp., Mount Olive, N.J.
  • Non-limiting examples of fillers that can be used in the present invention include fumed silica, settling silica, silicic anhydride, silicic hydrate, talc, carbon black, limestone powder, coated and uncoated colloidal calcium carbonate, coated and uncoated ground calcium carbonate, coated and uncoated precipitated calcium carbonate, kaolin, diatomaceous earth, fired clay, clay, titanium dioxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, and fibrous fillers such as glass fibers or filaments.
  • the filler can have any suitable particle size, in an embodiment of the invention, the filler particle size can be from 5 nm to 10 ⁇ m, in some cases 10 nm to 5 ⁇ m, and in other cases from 25 nm to 1 ⁇ m.
  • Non-limiting examples of viscosity regulators that can be used in the present invention include alkali-soluble, acid-soluble, and hydrophobically-modified alkali-soluble or acid-soluble emulsion polymers, those available as ACRYSOL® from Rohm and Haas Company, cellulosics, modified cellulosics, natural gums, such as xanthan gum, and the like.
  • Non-limiting examples of pigments that can be used in the present invention include silica, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide and carbon black.
  • Non-limiting examples of dyes that can be used in the present invention include mordant dyes, i.e., dyes prepared from plants, insects, and algae, and direct dyes, non-limiting examples being those based on benzidine or benzidine derivatives.
  • ultra violet light absorbers that can be used in the present invention include benzotriazole-based ultra violet ray absorbers, salicylate-based ultraviolet ray absorbers, benzophenone-based ultraviolet ray absorbers, hindered amine-based light stabilizers and nickel-based light stabilizers.
  • HCl scavengers a non-limiting example being epoxidized soybean oil
  • esters of beta-thiodipropionic acid non-limiting examples being lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole the
  • Non-limiting examples of antioxidants that can be used in the present invention include 2,6-di-t-butyl phenol, 2,4-di-t-butyl phenol, 2,6-di-t-butyl-4-methyl phenol, 2,5-di-t-butylhydroquinone, n-octadecyl-3-(3,5-di-t-butyl-4-hydro-xyphenyl)propionate, pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyp-henyl) propionate], 2,2′-methylenebis(4-methyl-6-t-butyl phenol), 4,4′-butylidenebis(3-methyl-6-t-butyl phenol), 4,4′-thiobis(3-methyl-6--t-butyl phenol), N,N′-diphenyl-p-phenylenediamine, 6-ethoxy-2,2,4
  • the present invention also provides a method of joining a first adherend or substrate and a second adherend or substrate.
  • the method includes
  • the method of joining provides an assembly.
  • the assembly includes the first adherend and the second adherend, which independently include one or more materials selected from wood, metals, plastics, paper, ceramics, minerals, stone, glass, and concrete.
  • the metal can include iron or aluminum.
  • the plastic can include poly(ethylene), poly(propylene), poly(ethylene terephthalate), and mixtures thereof.
  • the first substrate and the second substrate are contacted at a temperature of from 0° C. to 150° C. Also the first substrate and the second substrate can be contacted at a pressure of from atmospheric pressure to 500 psi.
  • Embodiments of the present invention are also directed to assemblies made according to the above described method where at least the first adherend or substrate and the second adherend or substrate bonded together.
  • inventions of the invention are directed to an adhesive, sealant or coating composition that includes:
  • Another embodiment of the present invention is directed to a method of coating a substrate that includes applying the above-described coating composition including components i), ii), and optionally iii), to at least a portion of a surface of the substrate.
  • the invention also provides the coated substrate prepared according to the above-described method.
  • the substrate can be, but is not limited to one or more materials selected from wood, metals, plastic, paper, ceramics, minerals, stone, glass, and concrete.
  • the substrates can include wood, metals such as ferrous substrates and aluminum substrates, and plastics.
  • the coating composition can be applied by conventional means including brushing, dipping, flow coating, spraying, and the like. Upon application to a substrate, the composition is allowed to coalesce to form a substantially continuous film on the substrate. The film is formed on the surface of the substrate by driving off liquids out of the film by heating or by an air drying period.
  • compositions that are two-component compositions, where a first component includes i) and optionally iii), and a second component includes ii).
  • An embodiment of the present invention is directed to a method of applying a composition to a substrate that includes mixing component i) and component ii), as described above, together.
  • This example demonstrates the synthesis of diethyl 2-(2-methyl-1-aziridinyl) succinate, an intermediate according to the present invention.
  • a round-bottom flask equipped with a thermocouple, stirrer, nitrogen inlet, addition funnel and cold finger, 8.08 g (0.1415 mol) of 2-methyl aziridine was combined with diethyl maleate (24.36 g, 0.1415 mol) keeping the temperature below 30° C. and stirring overnight. A vacuum was applied to remove unreacted 2-methyl aziridine. Gas Chromatography (GC) was used to verify completion of the reaction.
  • GC Gas Chromatography
  • Aspartate-Functional compounds were prepared by combining the product from Example 1 with an active hydrogen containing compound at room temperature in a round bottom flask equipped with a stirrer at a 1:1 equivalent ratio of the product from Example 1: active hydrogen compound. GPC and GC were used to confirm completion of the reaction. Specific examples are listed in the following table.
  • the Aspartate-Functional compounds were hand mixed with a polyisocyanate (DESMODUR® N-3300) at a NCO:NH ratio of 1:1.
  • the Shore A hardness and Shore D hardness were determined in accordance with DIN 53505 and ASTM D2240.
  • Tensile strength and elongation at break were determined on an INSTRON® 4444, Instron Corp., Canton, Mass., in accordance with DIN/ISO 527.
  • Acid functional polyether prepared by reacting a polyether with a hydroxyl functionality of 3 and Mn of 439, MULTRANOL ® 4035 available from Bayer, with hexahydrophthalic anhydride as described in U.S. Pat. No. 6,384,175.
  • Aspartate-Functional compounds were prepared by combining the product from Example 1 with a combination of two active hydrogen containing compounds as described above. The Aspartate-Functional compounds were then hand mixed with DESMODUR® N-3300 at a NCO:NH ratio of 1:1 as described above. Evaluations were made as described above, the results of which are shown in the table below. Active Example Hydrogen Compound Tensile Elongation No. No. 1 No.

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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Sealing Material Composition (AREA)
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US10/890,873 2004-07-14 2004-07-14 Aspartic ester functional compounds Abandoned US20060011295A1 (en)

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DE200560003882 DE602005003882T2 (de) 2004-07-14 2005-07-01 Asparaginsäureesterfunktionelle Verbindungen
EP20050014361 EP1627868B1 (en) 2004-07-14 2005-07-01 Aspartic ester functional compounds
CA 2511793 CA2511793C (en) 2004-07-14 2005-07-11 Aspartic ester functional compounds
MXPA05007526A MXPA05007526A (es) 2004-07-14 2005-07-13 Compuestos con funcionalidad ester aspartico.
CNB2005100859251A CN100543009C (zh) 2004-07-14 2005-07-14 含有天冬氨酸酯官能化合物的黏合剂、密封剂或涂料组合物
JP2005205643A JP2006028515A (ja) 2004-07-14 2005-07-14 官能性アスパラギン酸エステル
HK07100790.5A HK1094188B (en) 2004-07-14 2007-01-23 Adhesive, sealant or coating composition containing aspartic ester functional compounds
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CN107522845B (zh) * 2017-08-31 2020-07-14 深圳飞扬骏研新材料股份有限公司 一种聚天门冬氨酸酯脲胶黏剂及其施工工艺
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DE602005003882T2 (de) 2008-12-04
US7759452B2 (en) 2010-07-20
MXPA05007526A (es) 2006-04-28
CA2511793A1 (en) 2006-01-14
HK1094188A1 (zh) 2007-03-23
CN1865229A (zh) 2006-11-22
JP2006028515A (ja) 2006-02-02
CA2511793C (en) 2013-05-28
EP1627868B1 (en) 2007-12-19
CN100543009C (zh) 2009-09-23
US20090142601A1 (en) 2009-06-04
EP1627868A2 (en) 2006-02-22
DE602005003882D1 (de) 2008-01-31

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